WO2020162195A1 - Film antireflet pourvu d'une couche adhésive sensible à la pression, dispositif d'affichage de type à émission de lumière spontanée et procédé de fabrication associé - Google Patents

Film antireflet pourvu d'une couche adhésive sensible à la pression, dispositif d'affichage de type à émission de lumière spontanée et procédé de fabrication associé Download PDF

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Publication number
WO2020162195A1
WO2020162195A1 PCT/JP2020/002222 JP2020002222W WO2020162195A1 WO 2020162195 A1 WO2020162195 A1 WO 2020162195A1 JP 2020002222 W JP2020002222 W JP 2020002222W WO 2020162195 A1 WO2020162195 A1 WO 2020162195A1
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Prior art keywords
adhesive layer
pressure
sensitive adhesive
weight
meth
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PCT/JP2020/002222
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English (en)
Japanese (ja)
Inventor
潤枝 長田
雄祐 外山
武史 仲野
有 森本
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日東電工株式会社
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Priority to KR1020217019309A priority Critical patent/KR20210116446A/ko
Priority to CN202080012326.XA priority patent/CN113383048A/zh
Publication of WO2020162195A1 publication Critical patent/WO2020162195A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details

Definitions

  • the present invention relates to an antireflection film with an adhesive layer, a self-luminous display device including the same, and a method for manufacturing a self-luminous display device.
  • a self-luminous display device such as an organic electroluminescence (organic EL) display device has advantages of display performance such as higher visibility, less viewing angle dependency, and faster response speed than a liquid crystal display device.
  • An organic EL display device usually has an organic EL element in which an anode, an organic EL layer including a light emitting layer, and a cathode are sequentially stacked. Since the electrode (anode or cathode) of the organic EL element is made of a transparent conductive material having a high refractive index such as ITO or a metal material having a high reflectance, external light is reflected by the electrode, resulting in a decrease in contrast and internal reflection. This may cause a problem of glare, which may deteriorate the display performance of the organic EL display device.
  • Patent Document 2 a method of incorporating an antireflection layer into a color filter
  • Patent Document 3 a method of using a transparent resin film including a light scattering layer on a panel
  • Optical films such as circular polarizing plates, color filters with antireflection layers, and light scattering films are usually attached to panels using adhesives.
  • sticking failure such as mixing of air bubbles or deviation of sticking position may occur.
  • the pressure-sensitive adhesive is required to have removability (reworkability) that allows it to be easily peeled off from the panel after a lapse of a certain time from pasting, and is usually required on the panel of the organic EL display device. Since there is a fragile layer such as a barrier layer, there is a problem that rework is difficult. Due to the trend of thinner and larger panels in recent years, there is an increasing demand for revitalization of the panels.
  • JP-A-2003-332068 Japanese Unexamined Patent Publication No. 2018-1212715 JP-A-2009-70815
  • the present invention includes the following embodiments.
  • An antireflection film with an adhesive layer Having an adhesive layer on at least one surface of the antireflection film,
  • the pressure-sensitive adhesive layer is a film having an initial adhesive force of 5 N/25 mm or less based on 90° peeling at a speed of 300 mm/min with respect to non-alkali glass.
  • the film according to [1] which is used for a self-luminous display device.
  • At least one of the antireflection film and the pressure-sensitive adhesive layer contains an ultraviolet absorber, and the light transmittance of the pressure-sensitive adhesive layer at 380 nm is 70% or less, [1] to [4] the film.
  • the pressure-sensitive adhesive layer contains a base polymer, a photocuring agent, a photopolymerization initiator having a molar extinction coefficient of 15 [L mol ⁇ 1 cm ⁇ 1 ] or more at a wavelength of 380 nm, and a sensitizer, if necessary.
  • the film according to any one of [1] to [5], which is a layer formed from the agent composition.
  • the base polymer contains an acrylic polymer
  • the photocuring agent contains a polyfunctional (meth)acrylate
  • the pressure-sensitive adhesive composition contains 1 to 50 parts by weight of the photo-curing agent, 0.01 to 3 parts by weight of the photopolymerization initiator, and 0 to 0 parts of the sensitizer with respect to 100 parts by weight of the base polymer.
  • the adhesive layer contains 1 to 20 parts by weight of the silicone oligomer with respect to 100 parts by weight of the base polymer,
  • the silicone oligomer has a Tg of ⁇ 70° C. or higher and 30° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight Mw of 10,000 or more and 300,000 or less, [12] or [12].
  • the silicone oligomer as a monomer component, A monomer having a polyorganosiloxane skeleton and a homopolymer having a glass transition temperature of ⁇ 70° C. or higher and 180° C. or lower,
  • the base polymer as a monomer component, [12] to [14] containing 80% by weight or more of alkyl (meth)acrylic acid and 0 to 20% by weight of at least one polar monomer selected from the group consisting of a carboxyl group-containing monomer and a nitrogen-containing monomer.
  • the monomer component of the base polymer 80% by weight or more of (meth)acrylic acid alkyl ester having a homopolymer glass transition temperature of -60° C. or higher and 0° C. or lower, and at least one polarity selected from the group consisting of a carboxyl group-containing monomer and a nitrogen-containing monomer. 0 to 20% by weight of monomer,
  • a self-luminous display device having the film according to any one of [1] to [17] on a viewing side panel.
  • the self-luminous display device in which the layer present on the viewing side panel is only the antireflection film and a transparent substrate arranged as necessary.
  • the antireflection film with an adhesive layer is the film described in any of [6] to [11], The method according to [21], wherein the adhesive strength increasing treatment of the pressure-sensitive adhesive layer includes irradiating the pressure-sensitive adhesive layer with energy actinic rays in a wavelength range of 380 nm to 450 nm to photo-cur the pressure-sensitive adhesive layer. .. [23]
  • the antireflection film with an adhesive layer is the film described in any of [12] to [16], The method according to [21], wherein the treatment for increasing the adhesive strength of the pressure-sensitive adhesive layer includes heat-treating the pressure-sensitive adhesive layer at 20 to 80° C. for 1 to 48 hours.
  • the present invention has one or more of the following effects.
  • An antireflection film with a pressure-sensitive adhesive layer that can be applied to a self-luminous display device is provided.
  • the antireflection film with the pressure-sensitive adhesive layer of the present invention is preferably used as an antireflection film for suppressing external light reflection, which is disposed on a panel in a self-luminous display device such as an organic EL display device and a ⁇ OLED.
  • the adhesive layer-provided antireflection film of the present invention can be increased in adhesive force by performing an adhesive force increasing treatment of the adhesive layer after adhering to an adherend such as a panel.
  • the adhesive force is increased after the adhesive force increasing process, and excellent long-term adhesiveness (durability) is imparted.
  • the antireflection film with a pressure-sensitive adhesive layer has an antireflection function and is excellent in light transmittance of 380 nm to 780 nm. Therefore, when applied to a self-luminous display device, it is possible to suppress reflection of external light and to efficiently transmit light from the light emitting layer, thereby achieving high brightness and/or long life of the self-luminous display device.
  • the antireflection film with a pressure-sensitive adhesive layer can be replaced with an expensive circularly polarizing plate when applied to a self-luminous display device, which reduces the manufacturing cost. Planned.
  • One aspect of the present invention relates to an antireflection film with an adhesive layer.
  • the film has a pressure-sensitive adhesive layer on at least one surface of the antireflection film, and the pressure-sensitive adhesive layer has an initial adhesive force of 5 N/25 mm or less based on 90° peeling at a speed of 300 mm/min to non-alkali glass. ..
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of an antireflection film with an adhesive layer.
  • the antireflection film 10 with an adhesive layer includes the adhesive layer 1 on one main surface of the antireflection film 2.
  • the pressure-sensitive adhesive layer 1 is fixedly laminated on one main surface of the antireflection film 2.
  • the antireflection film 2 has a structure in which a hard coat layer 6, an adhesion layer 4, an antireflection layer 4, and an antifouling layer 7 are sequentially laminated on one surface of a transparent resin film 3.
  • the adhesion layer 5, the hard coat layer 6, and the antifouling layer 7 are arbitrarily arranged layers and can be omitted.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of an antireflection film with an adhesive layer.
  • the adhesive layer 1 is provided on the surface of the transparent resin film 3 opposite to the antireflection layer 4, but the adhesive layer 1 has the antireflection layer 4 (or the antifouling layer 7). In some cases, it may be provided on the outermost layer).
  • the antireflection layer 4 may be provided on both sides of the transparent resin film 3.
  • the antireflection film 10 may have a layer such as an antiglare layer.
  • the antireflection film 10 with an adhesive layer is used by attaching the adhesive layer 1 to an adherend.
  • the separator 8 is temporarily attached to the surface of the pressure-sensitive adhesive layer 1 of the pressure-sensitive adhesive layer-attached antireflection film 10 shown in FIG.
  • a sheet-shaped base material liner base material
  • An antireflection film with a pressure-sensitive adhesive layer by peeling off the separator 8 from the surface of the pressure-sensitive adhesive layer 1 before bonding to an adherend and bonding the exposed surface of the pressure-sensitive adhesive layer 1 to the surface of the adherend. 10 is temporarily attached to the adherend.
  • the thickness of the separator 8 is usually 3 to 200 ⁇ m, preferably about 10 to 100 ⁇ m.
  • the separator 8 may be omitted, and the antireflection film 10 with an adhesive layer may be used in which the surface of the antireflection film 2 that does not face the adhesive layer 1 is a release surface.
  • the adhesive surface of the adhesive layer 1 that does not face the antireflection film 2 is protected by contacting the surface of the antireflection film 2 that does not face the adhesive layer 1. It may have a form (roll form).
  • the surface of the pressure-sensitive adhesive layer 1 Before bonding to an adherend, the surface of the pressure-sensitive adhesive layer 1 is exposed, and the exposed surface of the pressure-sensitive adhesive layer 1 is bonded to the surface of the adherend, whereby the antireflection film 10 with a pressure-sensitive adhesive layer is coated. It is temporarily attached to the body.
  • the adhesive force of the pressure-sensitive adhesive layer 1 is increased to increase the adhesive force of the pressure-sensitive adhesive layer 1 and prevent adhesion to the adherend.
  • the film 2 is fixed to the film 2 via the adhesive layer 1.
  • fixing means that the two laminated layers are firmly adhered to each other, and peeling at the interface between them is impossible or difficult.
  • Tempoary adhesion is a state in which the adhesive force between the two laminated layers is small and the layers can be easily separated at the interface between the two layers.
  • FIGS. 2 and 3 are schematic cross-sectional views of an organic EL display device including an antireflection film with an adhesive layer according to an embodiment of the present invention.
  • the organic EL display device 100 has a structure in which the pressure-sensitive adhesive layer-attached antireflection film 10 is laminated on the surface of the organic EL panel 20 on the viewing side.
  • the pressure-sensitive adhesive layer-attached antireflection film 10 is temporarily attached to the surface of the organic EL panel 20 on the visible side via the pressure-sensitive adhesive layer 1. After the temporary attachment, the adhesive layer 1 is subjected to the adhesive force increasing treatment, so that the adhesive force of the adhesive layer 1 is increased and the organic EL panel and the antireflection film 2 are fixed to each other via the adhesive layer 1.
  • the layers present on the viewing side panel of the organic EL panel 20 are only the adhesive layer 1 and the antireflection film 2.
  • the organic EL display device 100 shown in FIG. 2 may have other layers in addition to the pressure-sensitive adhesive layer 1 and the antireflection film 2.
  • the layer present on the viewing side panel of the organic EL panel 20 includes the pressure-sensitive adhesive layer 1, the antireflection film 2, and a transparent substrate 30 arranged as necessary. May be only.
  • the layers existing on the viewing side panel of the organic EL panel 20 are only the adhesive layer 1, the antireflection film 2, and the transparent substrate 30.
  • the transparent substrate 30 include a glass substrate and a plastic substrate such as polycarbonate.
  • the antireflection film is not particularly limited, and various types can be used.
  • a film having an antireflection layer on at least one surface of a transparent resin film can be used.
  • the transparent resin film is not particularly limited, and various kinds can be used.
  • a material forming the transparent resin film a material having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc. is preferable.
  • polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate
  • cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose
  • acrylic-based polymers such as polymethyl methacrylate
  • styrenes such as polystyrene and acrylonitrile-styrene copolymer (AS resin).
  • Polymers Polycarbonate polymers; Polyolefin polymers such as polyethylene, polypropylene, cycloolefin polymers, polyolefins having a norbornene structure, ethylene/propylene copolymers; Vinyl chloride polymers; Amide polymers such as nylon and aromatic polyamides; Imide polymer; Sulfone polymer; Polyether sulfone polymer; Polyether ether ketone polymer; Polyphenylene sulfide polymer; Vinyl alcohol polymer; Vinylidene chloride polymer; Vinyl butyral polymer; Arylate polymer; Polyoxymethylene polymer An epoxy polymer or a blend of the above polymers.
  • the thickness of the transparent resin film can be appropriately determined, but in general, it is preferably 3 to 200 ⁇ m in view of workability such as strength and handleability, and thin layer property. From the viewpoint of transparency and cost, 5 to 150 ⁇ m is more preferable, and 10 to 100 ⁇ m is further preferable.
  • the transparent resin film may be used in a plurality of layers or a plurality of layers.
  • Antireflection layer Any appropriate configuration can be adopted as the configuration of the antireflection layer.
  • a typical structure of the antireflection layer (i) a single layer of a low refractive index layer having an optical film thickness of 120 nm to 140 nm and a refractive index of 1.35 to 1.55, (ii) a transparent resin film side From the above, a laminated body having a medium refractive index layer, a high refractive index layer and a low refractive index layer in this order, and (iii) an alternate multilayer laminated body of a high refractive index layer and a low refractive index layer are listed.
  • Examples of the material capable of forming the low refractive index layer include silicon oxide (SiO 2 ) and magnesium fluoride (MgF 2 ).
  • the refractive index of the low refractive index layer is typically about 1.35 to 1.55.
  • Examples of the material capable of forming the high refractive index layer include titanium oxide (TiO 2 ), niobium oxide (Nb 2 O 3 or Nb 2 O 5 ), tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), ZrO 2 —TiO 2 may be mentioned.
  • the refractive index of the high refractive index layer is typically about 1.60 to 2.20.
  • Examples of the material capable of forming the medium refractive index layer include titanium oxide (TiO 2 ), a mixture of a material capable of forming the low refractive index layer and a material capable of forming the high refractive index layer (for example, titanium oxide and oxide). A mixture with silicon).
  • the refractive index of the medium refractive index layer is typically about 1.50 to 1.85.
  • the thicknesses of the low-refractive index layer, the medium-refractive index layer and the high-refractive index layer can be set so that an appropriate optical film thickness can be realized according to the layer structure of the antireflection layer, desired antireflection performance and the like.
  • the antireflection layer is typically formed by a dry process.
  • the dry process include a PVD (Physical Vapor Deposition) method and a CVD (Chemical Vapor Deposition) method.
  • the PVD method include a vacuum vapor deposition method, a reactive vapor deposition method, an ion beam assist method, a sputtering method, and an ion plating method.
  • the CVD method include a plasma CVD method.
  • the thickness of the antireflection layer is, for example, about 20 nm to 300 nm.
  • the difference between the maximum reflectance and the minimum reflectance in the wavelength range of 380 nm to 780 nm of the antireflection layer is preferably 10% or less, more preferably 7% or less, and further preferably 5% or less.
  • coloring of reflected light can be favorably prevented.
  • a hard coat layer may be formed on the surface of the transparent resin film on the antireflection layer side. That is, the antireflection film of one embodiment has an antireflection layer on the hard coat layer provided on the surface of the transparent resin film.
  • the reflectance can be further reduced by appropriately adjusting the refractive index difference between the hard coat layer and the antireflection layer.
  • the hard coat layer preferably has sufficient surface hardness, excellent mechanical strength, and excellent light transmittance.
  • the hard coat layer may be formed of any appropriate resin as long as it has such desired properties.
  • Specific examples of the resin include a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, an electron beam curable resin, and a two-liquid mixed resin. UV curable resins are preferred. This is because the hard coat layer can be formed with a simple operation and high efficiency.
  • UV curable resins include polyester, acrylic, urethane, amide, silicone and epoxy UV curable resins.
  • the UV curable resin includes UV curable monomers, oligomers and polymers.
  • a resin composition containing an acrylic monomer component or oligomer component having preferably 2 or more, more preferably 3 to 6 UV-polymerizable functional groups can be mentioned.
  • a photopolymerization initiator is blended with the ultraviolet curable resin.
  • the hard coat layer can be formed by any appropriate method.
  • the hard coat layer can be formed by applying a resin composition for forming a hard coat layer on a transparent resin film, drying the composition, and irradiating the dried coating film with ultraviolet rays to cure the film.
  • the thickness of the hard coat layer is, for example, 0.5 ⁇ m to 20 ⁇ m, preferably 1 ⁇ m to 15 ⁇ m.
  • an adhesion layer may be formed between the hard coat layer and the antireflection layer.
  • the antireflection film is a hard coat layer in which metal oxide particles are exposed on the surface, and a film is formed on the metal oxide particle exposed surface of the hard coat layer, and a metal of the same kind as the metal oxide particles is formed. It has an adhesion layer made of the metal oxide in the oxygen-deficient state or the same metal as the metal oxide particles, and an antireflection layer laminated on the adhesion layer.
  • the metal oxide particles include particles of a metal oxide selected from Si, Al, Ti, Zr, Ce, Mg, Zn, Ta, Sb, Sn, and Mn.
  • the oxygen-deficient metal oxide refers to a metal oxide in which the number of oxygen is less than the stoichiometric composition, and specifically, SiOx, AlOx, TiOx, ZrOx, CeOx, MgOx, ZnOx, TaOx, SbOx. , SnOx, MnOx (x is 0 or more and less than the stoichiometric amount), and the like.
  • x in SiOx of the adhesion layer is 0 or more and less than 2.0.
  • the film thickness of the adhesion layer is preferably 10 nm or less, for example, 1 to 10 nm.
  • an antifouling layer can be provided on the surface of the antireflection layer.
  • the antifouling layer contains, for example, a fluorine group-containing silane compound (for example, an alkoxysilane compound having a perfluoropolyether group) or a fluorine group-containing organic compound.
  • the antifouling layer preferably exhibits water repellency with a water contact angle of 110 degrees or more.
  • the antireflection film may have a layer such as an antiglare layer, if necessary.
  • the antireflection film is produced by forming an antireflection layer on a transparent resin film.
  • the transparent resin film may be surface-treated in advance, if necessary.
  • the surface treatment include low pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, and acid or alkali treatment.
  • an adhesion layer made of, for example, SiOx may be formed on the surface of the transparent resin film.
  • the antireflection layer is typically formed by a dry process (for example, sputtering).
  • the antireflection layer when the antireflection layer is a laminate having a medium refractive index layer, a high refractive index layer, and a low refractive index layer in this order from the transparent resin film side, the transparent resin film surface is sputtered, for example, by sputtering, for example
  • An antireflection layer may be formed by sequentially forming a refractive index layer (eg, antimony-doped tin oxide film), a high refractive index layer (eg, Nb 2 O 5 film), and a low refractive index layer (eg, SiO 2 film). ..
  • the laminate having the medium refractive index layer, the high refractive index layer, and the low refractive index layer are described in, for example, JP-A-2018-173447. The description of the publication is incorporated herein by reference.
  • the antireflection layer is an alternate multilayer laminate of a high refractive index layer and a low refractive index layer, for example, a high refractive index layer (for example, Nb 2 O 5 film), a low refractive index layer, or a low refractive index layer may be formed on the surface of the transparent resin film by sputtering.
  • the antireflection layer may be formed by sequentially forming a refractive index layer (eg, SiO 2 film), a high refractive index layer (eg, Nb 2 O 5 film), and a low refractive index layer (eg, SiO 2 film).
  • a refractive index layer eg, SiO 2 film
  • a high refractive index layer eg, Nb 2 O 5 film
  • a low refractive index layer eg, SiO 2 film.
  • the number of layers of the alternate multilayer laminate is not particularly limited, but the total number of laminated layers of the high refractive index layer and the low refractive index layer is usually 2 to 10. .
  • Details of the alternating multilayer laminate of the high refractive index layer and the low refractive index layer are described in, for example, JP-A-2017-227898. The description of the publication is incorporated herein by reference.
  • the pressure-sensitive adhesive layer has an initial adhesive force of 5 N/25 mm or less based on 90° peeling at a speed of 300 mm/min with respect to non-alkali glass.
  • an initial adhesive force By having such an initial adhesive force, it is excellent in removability (reworkability) that allows the antireflection film to be easily peeled off from the adherend without any adhesive residue after being temporarily adhered to the adherend such as a panel.
  • 3 N/25 mm or less is preferable, 2.5 N/25 mm or less is more preferable, and 2.0 N/25 mm or less is further preferable.
  • a fragile layer such as a barrier layer is usually present on a panel of a self-luminous display device such as an organic EL display device (for example, an organic EL panel). Even when the antireflection film is stuck on such a barrier layer via the pressure-sensitive adhesive layer, rework is possible.
  • the lower limit of the initial adhesive strength is not particularly limited, but is, for example, preferably 0.01 N/25 mm or more.
  • the adhesive strength of the pressure-sensitive adhesive layer changes before and after the adhesive strength increasing treatment. That is, the pressure-sensitive adhesive layer has a small adhesive force with the adherend before the adhesive force increasing process, and thus can be easily reworked.
  • the pressure-sensitive adhesive layer has an increased adhesive force with the adherend due to the adhesive force increasing treatment, and is excellent in long-term adhesiveness (peeling durability).
  • the treatment for increasing the adhesive strength is not particularly limited, and examples thereof include photocuring treatment by irradiation with energy actinic rays or heat treatment.
  • the pressure-sensitive adhesive layer may be a photo-curable pressure-sensitive adhesive layer whose adhesive strength is increased by a photo-curing treatment by irradiation with energy actinic rays.
  • the pressure-sensitive adhesive layer may be a heat-type pressure-sensitive adhesive layer whose adhesive strength is increased by heat treatment.
  • Adhesive force based on 90 degree peeling of the pressure-sensitive adhesive layer to the alkali-free glass at a speed of 300 mm/min after the adhesive strength increasing treatment (adhesive force after the adhesive strength increasing treatment; for example, for a photocurable pressure-sensitive adhesive layer).
  • adhesive force after photocuring for example, in the case of a heating type pressure-sensitive adhesive layer
  • the adhesive force after 24 hours at 60° C. is excellent in long-term adhesion (peeling strength, peeling durability) and adheres to an adherend.
  • peeling strength, peeling durability adheres to an adherend.
  • 5 N/25 mm or more is preferable
  • 6 N/25 mm or more is more preferable
  • 8 N/25 mm or more is further preferable.
  • the higher the adhesive strength after the adhesive strength increasing treatment is, the more preferable, and the upper limit is not limited, but it is usually 20 N/25 mm or less.
  • the adhesive strength of the adhesive layer after the adhesive strength increasing treatment is preferably larger than the initial adhesive strength.
  • the ratio to the initial adhesive strength ((adhesive strength after adhesive strength increasing treatment/initial adhesive strength) is preferably 1 or more, more preferably 1.5 or more, and further preferably 3 or more from the viewpoint of reworkability and adhesion.
  • the upper limit of the ratio is not particularly limited and is preferably as high as possible, but is usually 100 or less.
  • the method for measuring the initial adhesive force and the adhesive force after the adhesive strength increasing treatment based on 90° peeling of the pressure-sensitive adhesive layer to the alkali-free glass at a speed of 300 mm/min is not particularly limited.
  • the initial adhesive strength and the adhesive strength after the adhesive strength increasing treatment are the adhesive strength before the adhesive strength increasing treatment by the 90 degree peeling of the pressure-sensitive adhesive layer to the alkali-free glass at a speed of 300 mm/min and after the adhesive strength increasing treatment (compared to It is measured as the initial adhesive strength T1 of the alkali-free glass and the adhesive strength T2 of the alkali-free glass after the adhesion strength increasing treatment.
  • T1 and T2 are the peeling angles of the pressure-sensitive adhesive layers formed on the alkali-free glass before and after the adhesive strength increasing treatment in accordance with JIS Z0237:2009 90° peeling test. It is measured as the adhesive force when peeled from the alkali-free glass at 90° (that is, in the vertical direction) and at a pulling rate of 300 mm/min.
  • the ratio of the adhesive strength of the pressure-sensitive adhesive layer after the adhesive strength increasing treatment to the adhesive strength before the adhesive strength increasing treatment eg, the adhesive strength of the alkali-free glass after the adhesive strength increasing treatment/the adhesive strength of the alkali-free glass).
  • the adhesive strength (T2/T1) of the glass before the adhesive strength increasing treatment is preferably 1 or more, more preferably 1.5 or more, and further preferably 2 or more, from the viewpoint of reworkability and adhesion.
  • the thickness of the adhesive layer is, for example, about 1 to 300 ⁇ m.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and it is a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, a polyvinyl alcohol-based pressure-sensitive adhesive, a polyvinylpyrrolidone.
  • a system adhesive, a polyacrylamide system adhesive, a cellulosic system adhesive, etc. can be used.
  • Various base polymers can be used depending on the pressure-sensitive adhesive used. Among them, those having excellent optical transparency, exhibiting appropriate wettability, cohesiveness, and adhesive tackiness, and having excellent weather resistance and heat resistance are preferably used.
  • An acrylic pressure-sensitive adhesive is preferably used to exhibit such characteristics.
  • An acrylic polymer is used as the base polymer of the acrylic pressure-sensitive adhesive.
  • the (meth)acrylate contains acrylate and/or methacrylate.
  • the photocurable pressure-sensitive adhesive layer may undergo a photocuring reaction upon irradiation with energy actinic rays, and may improve its adhesive force to an adherend.
  • the photo-curable pressure-sensitive adhesive hardly cures in a general storage environment, but cures by irradiation with energy actinic rays.
  • the laminated body of the present invention has an advantage that the curing timing of the pressure-sensitive adhesive layer can be set arbitrarily and can flexibly correspond to the lead time of the process.
  • the composition of the pressure-sensitive adhesive layer is not particularly limited as long as the adhesive force to the adherend is improved by photocuring.
  • the photocurable pressure-sensitive adhesive layer of one embodiment is a layer formed from a pressure-sensitive adhesive composition containing a base polymer, a photocuring agent, a photopolymerization initiator, and optionally a sensitizer.
  • the pressure-sensitive adhesive layer can be a cured layer of a pressure-sensitive adhesive composition containing a base polymer, a photocuring agent, a photopolymerization initiator, and optionally a sensitizer.
  • the adhesive layer contains a curing reaction product of a base polymer and a photo-curing agent.
  • the pressure-sensitive adhesive layer is preferably one that can be cured by irradiation with energy actinic rays in the wavelength range of 380 nm to 450 nm.
  • the base polymer is a main constituent component of the pressure-sensitive adhesive layer (pressure-sensitive adhesive composition), and is a main element that determines the adhesive strength of the pressure-sensitive adhesive. From the viewpoint of making the pressure-sensitive adhesive layer before photocuring hard and facilitating the peeling from the adherend at the time of reworking, it is preferable that a crosslinked structure is introduced into the base polymer.
  • the type of base polymer is not particularly limited, and an acrylic polymer, a silicone polymer, a urethane polymer, a rubber polymer, or the like may be appropriately selected. As the base polymer, one type may be used alone, or two or more types may be selected and used.
  • the pressure-sensitive adhesive layer contains an acrylic polymer as a base polymer because it has excellent optical transparency and adhesiveness, and can easily control various properties such as frictional force. It is preferable that 50% by weight or more (more preferably 60% by weight or more, further preferably 70% by weight) of the pressure-sensitive adhesive layer (pressure-sensitive adhesive composition) is an acrylic polymer.
  • (meth)acrylic acid alkyl ester As the acrylic polymer, those containing (meth)acrylic acid alkyl ester as a main monomer component are preferably used.
  • (meth)acryl means acryl and/or methacryl.
  • the content of the (meth)acrylic acid alkyl ester is preferably 40% by weight or more, more preferably 50% by weight or more, and further preferably 55% by weight or more with respect to the total amount (100% by weight) of the monomer components constituting the acrylic polymer. preferable.
  • (Meth)acrylic acid alkyl ester As the (meth)acrylic acid alkyl ester, a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is preferably used.
  • the alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched.
  • alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, ( (Meth) t-butyl acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-(meth) acrylate Ethylhexyl, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate Dodecyl (
  • the acrylic polymer preferably contains a monomer component having a crosslinkable functional group as a copolymerization component.
  • the monomer having a crosslinkable functional group include a hydroxy group-containing monomer and a carboxy group-containing monomer. Above all, it is preferable to contain a hydroxy group-containing monomer as a copolymerization component of the base polymer.
  • the hydroxy group and carboxy group of the base polymer serve as reaction points with the crosslinking agent described below.
  • hydroxy group-containing monomer examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (meth) Examples thereof include 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and 4-(hydroxymethyl)cyclohexyl) (meth)acrylate.
  • carboxy group-containing monomer examples include (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, carboxypentyl carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid.
  • the total amount of the hydroxy group-containing monomer and the carboxy group-containing monomer is preferably 1 to 30% by weight, and more preferably 3 to 25% by weight, based on the total amount (100% by weight) of the constituent monomer components. More preferably, it is more preferably 5 to 20% by weight.
  • the content of the (meth)acrylic acid ester containing a hydroxy group is preferably in the above range.
  • the acrylic polymer has N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-acryloylmorpholine, as constituent monomer components. It is preferable to contain a nitrogen-containing monomer such as N-vinylcarboxylic acid amides and N-vinylcaprolactam. Acrylic polymers containing nitrogen-containing monomer components exhibit moderate water absorption under a humid heat environment and local water absorption of the adhesive is suppressed, so local whitening, local swelling and peeling of the adhesive layer Contribute to the prevention of such.
  • the content of the nitrogen-containing monomer is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, and more preferably 5 to 20% by weight based on the total amount (100% by weight) of the constituent monomer components. % Is more preferable.
  • the acrylic polymer particularly preferably contains N-vinylpyrrolidone in the above range as the nitrogen-containing monomer.
  • the acrylic polymer preferably contains a hydroxy group-containing monomer and a nitrogen-containing monomer as monomer components.
  • the acrylic polymer contains both a hydroxy group-containing monomer and a nitrogen-containing monomer as a monomer component, the cohesive force and transparency of the pressure-sensitive adhesive tend to be enhanced.
  • the total amount of the hydroxy group-containing monomer and the nitrogen-containing monomer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on the total amount (100% by weight) of the constituent monomer components. And more preferably 15 to 35% by weight.
  • the acrylic polymer may contain monomer components other than the above (other monomer components).
  • the acrylic polymer is a monomer component, for example, a cyano group-containing monomer, vinyl ester monomer, aromatic vinyl monomer, epoxy group-containing monomer, vinyl ether monomer, sulfo group-containing monomer, phosphoric acid group-containing monomer, acid anhydride group-containing monomer. Etc. may be included.
  • the content of these other monomer components is preferably 0 to 40% by weight, more preferably 0 to 30% by weight, and 0 to 20% based on the total amount (100% by weight) of the constituent monomer components. More preferably, it is wt %.
  • the acrylic polymer is used as a monomer component in an amount of 40 to 99% by weight (preferably 50 to 50% by weight) of the above (meth)acrylic acid alkyl ester monomer with respect to the total amount (100% by weight) of the constituent monomer components. 97% by weight, more preferably 55 to 95% by weight), and a monomer having the above-mentioned crosslinkable functional group (preferably the above-mentioned hydroxy group-containing monomer and/or the above-mentioned carboxy group-containing monomer, more preferably the above-mentioned hydroxy group-containing monomer). 1 to 30% by weight (preferably 3 to 25% by weight, more preferably 5 to 20% by weight), 1 to 30% by weight (preferably 3 to 25% by weight, more preferably 5 to 20% by weight) of the above nitrogen-containing monomer. %) included.
  • the weight average molecular weight of the acrylic polymer is preferably 100,000 to 5,000,000, more preferably 300,000 to 3,000,000, and further preferably 500,000 to 2,000,000.
  • the molecular weight of the base polymer means the molecular weight before the introduction of the crosslinked structure.
  • the weight average molecular weight of the acrylic polymer can be measured using gel permeation chromatography (GPC).
  • the high Tg monomer means a monomer having a high glass transition temperature (Tg) of the homopolymer.
  • the homopolymer monomers having a Tg of 40° C. or higher include dicyclopentanyl methacrylate (Tg: 175° C.), dicyclopentanyl acrylate (Tg: 120° C.), isobornyl methacrylate (Tg: 173° C.), isobornyl methacrylate.
  • (Meth)acrylic monomers such as nyl acrylate (Tg:97°C), methyl methacrylate (Tg:105°C), 1-adamantyl methacrylate (Tg:250°C), 1-adamantyl acrylate (Tg:153°C); acryloylmorpholine (Tg: 145° C.), dimethyl acrylamide (Tg: 119° C.), diethyl acrylamide (Tg: 81° C.), dimethylaminopropyl acrylamide (Tg: 134° C.), isopropyl acrylamide (Tg: 134° C.), hydroxyethyl acrylamide (Tg : 98° C.) and other amide group-containing vinyl monomers; N-vinylpyrrolidone (Tg: 54° C.) and the like.
  • the content of the monomer having a homopolymer Tg of 40° C. or higher is preferably 5 to 50% by weight, and more preferably 10 to 40% by weight based on the total amount of the constituent monomer components.
  • the homopolymer Tg contains a monomer component having a Tg of 80° C. or higher as the monomer component of the base polymer. It is more preferable to include a monomer component at 100° C. or higher.
  • the content of methyl methacrylate is preferably in the above range.
  • the method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as a synthetic method of the acrylic polymer such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method. Can be appropriately adopted.
  • the solution polymerization method may be preferably adopted.
  • the polymerization temperature at the time of solution polymerization can be appropriately selected according to the type of monomer and solvent used, the type of polymerization initiator, etc., and is, for example, about 20°C to 170°C (typically 40°C to 140°C). C.).
  • the initiator used for the polymerization can be appropriately selected from conventionally known thermal polymerization initiators, photopolymerization initiators, etc. according to the polymerization method.
  • the polymerization initiators may be used alone or in combination of two or more.
  • thermal polymerization initiator examples include azo-based polymerization initiators (for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis( 2-methylpropionic acid)dimethyl, 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis[2 -(5-Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis(N,N'-dimethylene Isobutylamidine) dihydrochloride, etc.); Persulfate such as potassium persulfate; Peroxide type polymerization initiator (eg, dibenzoyl peroxide, t-butyl permaleate,
  • the amount of the thermal polymerization initiator used is not particularly limited, but for example, 0.01 part by weight to 5 parts by weight, preferably 0.05 part by weight to 100 parts by weight of the monomer component used for the preparation of the acrylic polymer.
  • the amount can be within the range of 3 parts by weight.
  • the photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactivators.
  • Oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, acylphosphine oxide photopolymerization initiator Etc. can be used.
  • the amount of the photopolymerization initiator used is not particularly limited, but is, for example, 0.01 parts by weight to 5 parts by weight, preferably 0.05 parts by weight to 100 parts by weight of the monomer component used for preparing the acrylic polymer.
  • the amount can be within the range of 3 parts by weight.
  • the acrylic polymer is a mixture of a monomer component as described above and a polymerization initiator, for example, ethyl acetate, toluene or the like is used as a polymerization solvent, and the acrylic polymer is solution-polymerized. Can be obtained.
  • a polymerization initiator for example, ethyl acetate, toluene or the like is used as a polymerization solvent, and the acrylic polymer is solution-polymerized. Can be obtained.
  • solution polymerization the reaction is usually carried out under a stream of an inert gas such as nitrogen and a polymerization initiator at about 50 to 70° C. for about 5 to 30 hours.
  • a cross-linking structure is introduced into the base polymer by adding a cross-linking agent to the solution after the polymerization of the base polymer and heating it as necessary.
  • a cross-linking agent it is possible to use a commonly used cross-linking agent, for example, isocyanate-based cross-linking agent, epoxy-based cross-linking agent, oxazoline-based cross-linking agent, aziridine-based cross-linking agent, carbodiimide-based cross-linking agent, metal chelate-based cross-linking agent, silicone.
  • Examples thereof include a system-based crosslinking agent, a silane-based crosslinking agent, and an alkyl etherified melamine-based crosslinking agent. These cross-linking agents react with functional groups such as hydroxy groups introduced into the base polymer to form a cross-linked structure.
  • an isocyanate crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent can be preferably used.
  • the cross-linking agents may be used alone or in combination of two or more.
  • polyisocyanate crosslinking agent polyisocyanate having two or more isocyanate groups in one molecule is preferable.
  • the polyisocyanate-based cross-linking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; Aromatic isocyanates such as diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, tetramethylxylylene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylyl Hydrogenated products of aromatic isocyanates
  • a compound having at least one or more isocyanate group and one or more unsaturated bond in one molecule should also be used as an isocyanate cross-linking agent. You can These may be used alone or in combination of two or more.
  • epoxy crosslinking agent examples include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylol.
  • Propane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane Can be mentioned. These may be used alone or in combination of two or more.
  • metal chelate compounds include aluminum, iron, tin, titanium, nickel, etc. as metal components, and acetylene, methyl acetoacetate, ethyl lactate, etc. as chelate components. These may be used alone or in combination of two or more.
  • the amount of the cross-linking agent used may be appropriately adjusted according to the composition and molecular weight of the base polymer.
  • the amount of the crosslinking agent used can be, for example, 0.01 parts by weight or more, and preferably 0.05 parts by weight or more, based on 100 parts by weight of the base polymer. A higher cohesive force tends to be obtained by increasing the amount of the crosslinking agent used.
  • the amount of the cross-linking agent used may be 0.1 part by weight or more, 100 parts by weight or more, 0.5 parts by weight or more, and 1 part by weight or more. Good.
  • the amount of the cross-linking agent to be used is usually 15 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the base polymer. It may be 5 parts by weight or less.
  • the amount of the crosslinking agent used in the photocurable pressure-sensitive adhesive layer is about 0.1 to 10 parts by weight, preferably 100 parts by weight of the base polymer before crosslinking. Is 0.3 to 7 parts by weight, more preferably 0.5 to 5 parts by weight, still more preferably 1 to 4 parts by weight. Reworkability tends to be improved by increasing the amount of the cross-linking agent used as compared with a general acrylic transparent adhesive for optics.
  • a crosslinking catalyst may be used to promote the formation of a crosslinked structure.
  • the cross-linking catalyst include metal-based cross-linking catalysts (especially tin-based cross-linking catalysts) such as tetra-n-butyl titanate, tetraisopropyl titanate, ferric nacem, butyltin oxide and dioctyltin dilaurate.
  • the amount of the crosslinking catalyst used is not particularly limited, but can be, for example, 0.0001 parts by weight to 1 part by weight relative to 100 parts by weight of the base polymer.
  • the gel fraction is increased by introducing a crosslinked structure into the base polymer.
  • the gel fraction of the pressure-sensitive adhesive layer before photocuring is preferably 30% or more, more preferably 50% or more, further preferably 60% or more, particularly preferably 65% or more.
  • the gel fraction of the pressure-sensitive adhesive layer before photocuring may be 70% or more or 75% or more. Since the pressure-sensitive adhesive layer contains an unreacted photo-curing agent, the gel fraction of the pressure-sensitive adhesive layer before photo-curing is generally 90% or less.
  • the gel fraction of the pressure-sensitive adhesive layer before photocuring is preferably 85% or less, more preferably 80% or less.
  • the gel fraction can be obtained as an insoluble matter in a solvent such as ethyl acetate, and specifically, the insoluble component after immersing the pressure-sensitive adhesive layer in ethyl acetate at 23° C. for 7 days with respect to the sample before immersion. It is obtained as a weight fraction (unit:% by weight).
  • the gel fraction of a polymer is equal to the degree of crosslinking, the more crosslinked portions in the polymer the greater the gel fraction.
  • the larger the amount of the photo-curing agent the smaller the gel fraction.
  • the pressure-sensitive adhesive layer containing the photo-curing agent is subjected to photo-curing after being adhered to the adherend, whereby the frictional force is increased and the adhesive force to the adherend is improved.
  • a photo-curable monomer or photo-curable oligomer is used as the photo-curing agent.
  • the photocuring agent is preferably a compound having two or more ethylenically unsaturated bonds in one molecule. Further, the photo-curing agent is preferably a compound showing compatibility with the base polymer.
  • the photo-curing agent is preferably a liquid at room temperature because it exhibits an appropriate compatibility with the base polymer.
  • an adhesion inhibiting layer (Weak Boundary Layer; WBL; A fragile layer) may be formed.
  • WBL Wired Boundary Layer
  • the characteristics of the surface (adhesion interface) change while maintaining the characteristics of the bulk of the pressure-sensitive adhesive layer. That is, when the WBL is formed, the pressure-sensitive adhesive layer retains its hardness and the frictional force and the frequency dependence of the frictional force are reduced, so that the peeling at the time of reworking is facilitated and the adhesive residue on the adherend is left. It can be reduced.
  • the photo-curing agent reacts and the WBL disappears or the thickness of the WBL becomes thin, so that the adhesive strength is improved. Thereby, excellent reworkability before photocuring and excellent peel strength after photocuring can be achieved.
  • Compatibility of the base polymer and photo-curing agent is mainly influenced by the structure of the compound.
  • the structure and compatibility of the compound can be evaluated by, for example, the Hansen solubility parameter, and the smaller the difference in solubility parameter between the base polymer and the photocuring agent, the higher the compatibility tends to be.
  • polyfunctional (meth)acrylate polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, bisphenol A propylene oxide Modified di(meth)acrylate, alkanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di( (Meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaery
  • Compatibility of the base polymer and the photo-curing agent depends on the molecular weight of the compound.
  • the molecular weight of the photo-curing agent is preferably 1500 or less, more preferably 1000 or less.
  • the type and content of photo-curing agent mainly affect the adhesive strength after photo-curing.
  • the functional group equivalent (g/eq) of the photocuring agent is preferably 500 or less, more preferably 450 or less.
  • the functional group equivalent of the photocuring agent is preferably 100 or more, more preferably 130 or more, further preferably 150 or more, particularly preferably 180 or more.
  • the functional group equivalent of the photo-curing agent is preferably within the above range.
  • the content of the photo-curing agent in the pressure-sensitive adhesive layer is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and 10 to 35 parts by weight with respect to 100 parts by weight of the base polymer. More preferable.
  • the photo-curing agent is likely to bleed out on the surface. The photocuring agent bleeding out on the surface forms WBL and contributes to the reduction of the frictional force of the pressure-sensitive adhesive layer.
  • the adhesive force with the adherend can be appropriately reduced, and the reworkability tends to be improved.
  • the transparency and the adhesive strength may decrease. From this viewpoint, it is preferable to control the amount of the photo-curing agent within the above range.
  • the photopolymerization initiator generates active species by irradiation with energy actinic rays and accelerates the curing reaction of the photocuring agent.
  • the photopolymerization initiator preferably has a molar extinction coefficient at a wavelength of 380 nm of 15 [L mol ⁇ 1 cm ⁇ 1 ] or more.
  • the molar extinction coefficient of the photopolymerization initiator at a wavelength of 380 nm can be measured using an absorptiometer.
  • the molar absorption coefficient of the photopolymerization initiator at a wavelength of 380 nm is preferably 20 [L mol ⁇ 1 cm ⁇ 1 ] or more, more preferably 25 [L mol ⁇ 1 cm ⁇ 1 ] or more.
  • the upper limit of the molar extinction coefficient of the photopolymerization initiator at a wavelength of 380 nm is not particularly limited, but is, for example, 1000 [L mol ⁇ 1 cm ⁇ 1 ] or less.
  • an initiator having absorption in a long wavelength region is preferable, and examples thereof include oxime compounds, metallocene compounds, acylphosphine compounds, and aminoacetophenone compounds.
  • acylphosphine compounds and oxime compounds are preferable in terms of wide-range absorption characteristics (especially, large absorption coefficient of 380 nm or more).
  • Examples of the oxime-based compound include compounds described in JP 2001-233842 A, compounds described in JP 2000-80068 A, compounds described in JP 2006-342166 A, JCSPerkin II (1979). pp.1653-1660, JC Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp. Compounds described in each document of 202-232, JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534797, JP-A-2006-342166, WO2015/36910, WO2017. The compounds and the like described in paragraphs 0154 to 0156 of /146152 can be used. In addition, compounds described in Japanese Patent Publication No.
  • the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be preferably used.
  • the cyclic oxime-based compounds the cyclic oxime-based compounds condensed with a carbazole dye described in JP 2010-32985 A and JP 2010-185072 A have high light absorption and high sensitivity. It is preferable from the viewpoint.
  • compounds having an unsaturated bond at a specific site of the oxime compound for example, compounds described in JP 2009-242469 A
  • oxime compounds having a fluorine atom for example, described in JP 2010-262028 A
  • oxime compounds include oxime ester compounds.
  • a commercially available product may be used as the oxime compound. Examples of commercially available products include IRGACURE OXE-01 (manufactured by BASF), IRGACURE OXE-02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Power Electronics Co., Ltd.), DFI. -091 (manufactured by Daito Chemix Co., Ltd.) and the like can be used.
  • Examples of the metallocene compound include, for example, JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, and JP-A-2-291.
  • the titanocene compounds described in paragraphs 0159 to 0153 of JP-A-2-4705 and WO2017/146152 and the iron-arene complexes described in JP-A-1-304453 and 1-152109 are mentioned. be able to.
  • a commercial item can be used as a metallocene compound.
  • Examples of bis(methylcyclopentadienyl)-Ti-bis(2,6-difluorophenyl) include IRGACURE-727 (manufactured by BASF), and bis(cyclopentadienyl)-bis(2,6).
  • Examples of -difluoro-3-(pyrid-1-yl)phenyl)titanium include IRGACURE-784 (manufactured by BASF).
  • acylphosphine compound examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. A commercially available product can be used as the acylphosphine compound. For example, commercially available Omnirad-819 and Omnirad-TPO (trade names: all manufactured by IGM Japan) can be used.
  • aminoacetophenone compound for example, the compounds described in JP-A-10-291969 can be used. Further, as the aminoacetophenone-based compound, the compound described in JP-A-2009-191179 in which the maximum absorption wavelength is matched with a long wave region such as 365 nm or 405 nm can also be used. Among them, a preferable aminoacetophenone compound is 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.
  • a commercially available product can be used as the aminoacetophenone compound. For example, commercially available products Omnirad-907, Omnirad-369, and Omnirad-379 (trade names: all manufactured by IGM Japan) can be used.
  • the photopolymerization initiator may be used alone or in combination of two or more kinds.
  • the content of the photopolymerization initiator in the pressure-sensitive adhesive layer (pressure-sensitive adhesive composition) is preferably 0.01 to 3 parts by weight, more preferably 0.02 to 1 part by weight, and more preferably 0 to 100 parts by weight of the base polymer. 0.04 to 0.5 part by weight is more preferable.
  • the pressure-sensitive adhesive layer (adhesive
  • the content of the photopolymerization initiator in the composition) is preferably 3 parts by weight or less, more preferably 1 part by weight or less, still more preferably 0.5 part by weight or less.
  • the content of the photopolymerization initiator in the pressure-sensitive adhesive layer (pressure-sensitive adhesive composition) is preferably 0.01 parts by weight or more, from the viewpoint of sufficiently advancing photocuring by UV irradiation or the like to enhance adhesion reliability. It is more preferably 0.02 parts by weight or more.
  • the pressure-sensitive adhesive layer may include a sensitizer.
  • a sensitizer By using the photopolymerization initiator and the sensitizer together, the reaction rate of the photocuring reaction can be delayed. Therefore, even if the laminated body is stored under visible light irradiation such as a fluorescent lamp after bonding, the initial adhesive force is kept low, and a laminate having excellent reworkability can be obtained.
  • the sensitizer is not particularly limited, and examples thereof include compounds represented by general formula (e1) shown below.
  • R 1 and R 2 each independently represent —H, —CH 3 , —CH 2 CH 3 , —CH(CH 3 ) 2 or Cl, and R 1 and R 2 may be the same or different. good
  • diethylthioxanthone in which R 1 and R 2 are —CH 2 CH 3 is particularly preferable.
  • the sensitizers may be used alone or in combination of two or more.
  • the content of the sensitizer in the pressure-sensitive adhesive layer is preferably 0 to 10 parts by weight, more preferably 0.001 to 10 parts by weight, and 0.01 to 10 parts by weight with respect to 100 parts by weight of the base polymer. More preferably 5 parts by weight.
  • the pressure-sensitive adhesive layer may be formed by laminating the pressure-sensitive adhesive layer on the surface of the antireflection film.
  • a direct method of forming on the surface of the antireflection film may be used, and a pressure-sensitive adhesive layer formed in a sheet shape on the surface having peelability (peeling surface) is formed on the surface of the antireflection film.
  • a transfer method for transferring may be used, or these methods may be combined.
  • An anchor layer can be formed on the surface of the antireflection film, or a pressure-sensitive adhesive layer can be formed after various easy-adhesion treatments such as corona treatment and plasma treatment.
  • the surface of the pressure-sensitive adhesive layer may be subjected to easy adhesion treatment.
  • the release surface the surface of the release liner, the back surface of the release-treated substrate, or the like can be used.
  • the base material having the release surface used for forming the pressure-sensitive adhesive layer may be used as it is as the separator.
  • a silicone release liner is preferably used as the release-treated separator.
  • a pressure-sensitive adhesive composition containing a component and a solvent of the pressure-sensitive adhesive layer, on an antireflection film or a substrate roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat
  • a pressure-sensitive adhesive layer is formed by applying by bar coating, knife coating, air knife coating, curtain coating, lip coating, die coating or the like, and drying and removing the solvent if necessary.
  • a drying method an appropriate method can be adopted as appropriate.
  • the heat drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and further preferably 70°C to 170°C.
  • the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, still more preferably 10 seconds to 10 minutes.
  • the pressure-sensitive adhesive composition contains a cross-linking agent
  • the heating temperature and the heating time are appropriately set depending on the type of the crosslinking agent used, and usually crosslinking is carried out by heating in the range of 20° C. to 160° C. for about 1 minute to 7 days.
  • the heating for drying and removing the solvent may also serve as the heating for crosslinking.
  • the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release-treated sheet (separator) until practical use.
  • a release-treated sheet As the constituent material of the separator, for example, polyethylene, polypropylene, polyethylene terephthalate, a plastic film such as a polyester film, a porous material such as paper, cloth, non-woven fabric, a net, a foamed sheet, a metal foil, and a laminated body thereof are appropriately used.
  • a thin film can be used, but a plastic film is preferably used because of its excellent surface smoothness.
  • the plastic film is not particularly limited as long as it is a film capable of protecting the pressure-sensitive adhesive layer, and examples thereof include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer. Examples thereof include a united film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film and the like.
  • the thickness of the separator is usually 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • antistatic treatment such as.
  • the peelability from the pressure-sensitive adhesive layer can be further enhanced by appropriately performing a peeling treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the separator.
  • the release-treated separator used for forming the pressure-sensitive adhesive layer can be used as it is as a separator of the pressure-sensitive adhesive layer-attached antireflection film, and the process can be simplified.
  • the pressure-sensitive adhesive layer is photocured by irradiating the pressure-sensitive adhesive layer with energy actinic rays.
  • the timing of curing of the antireflection film using the photocurable pressure-sensitive adhesive layer can be set arbitrarily. Rework or processing can be performed at any time after the adhesive layer-attached antireflection film is attached to the adherend and before the adhesive is photocured. It is possible to respond flexibly to the time.
  • the energy actinic rays include ultraviolet rays, visible light, infrared rays, X rays, ⁇ rays, ⁇ rays, and ⁇ rays. Since the curing of the pressure-sensitive adhesive layer in the storage state can be suppressed and the pressure-sensitive adhesive layer can be easily cured, the energy active ray is preferably the energy active ray in the wavelength range of 380 nm to 450 nm.
  • the photocuring reaction by the polymerization initiator is promoted even when the antireflection film containing the ultraviolet absorber is used, and after the photocuring,
  • the function of the pressure-sensitive adhesive can be sufficiently exhibited by increasing the pressure-sensitive adhesive strength.
  • a light source of energy active rays in the wavelength range of 380 nm to 450 nm a gallium-encapsulated metal halide lamp or an LED light source emitting light in the wavelength range of 380 to 440 nm is preferable.
  • low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight as the light source It is also possible to use by blocking light having a wavelength shorter than 380 nm using a bandpass filter.
  • the irradiation intensity and irradiation time of the energy actinic radiation may be appropriately set according to the composition and thickness of the pressure-sensitive adhesive layer.
  • the irradiation amount of the energy actinic radiation in the wavelength range of 380 nm to 450 nm is preferably 1,000 mJ/cm 2 or more, more preferably 2,000 mJ/cm 2 or more. Yes, and more preferably 3,000 mJ/cm 2 or more.
  • the irradiation amount of the energy active rays is preferably not 50,000J / cm 2 or less, more preferably 30,000J / cm 2 or less, more preferably 10,000 J / cm 2 or less.
  • the dose of the energy active rays for example, a range of 1,000 ⁇ 50,000mJ / cm 2 or in the range of 1,000 ⁇ 30,000mJ / cm 2, or,, 2,000 ⁇ 30,000mJ / cm The range is 2 .
  • the heat-type pressure-sensitive adhesive layer may have improved adhesion to the adherend by heat treatment.
  • the composition of the pressure-sensitive adhesive layer is not particularly limited as long as the adhesive strength to the adherend is improved by heat treatment.
  • the heat-type adhesive layer of one embodiment comprises a base polymer and a rework enhancer.
  • the heat-type adhesive layer of one embodiment includes a base polymer and a silicone oligomer having a siloxane skeleton. Since such an adhesive layer can improve the adhesive strength by autoclave treatment or the like which is indispensable at the time of bonding and long-term storage at room temperature, it is possible to use the existing equipment without increasing the steps at the time of bonding. it can.
  • the base polymer is not particularly limited, and various base polymers can be used, but it is preferable to use an acrylic polymer as the base polymer.
  • an acrylic polymer those containing (meth)acrylic acid alkyl ester as a main monomer component are preferably used.
  • (meth)acrylic acid alkyl ester As the (meth)acrylic acid alkyl ester, (meth)acrylic acid alkyl ester used in (base polymer) of ⁇ photocurable pressure-sensitive adhesive layer> is also suitable. Can be used.
  • the acrylic polymer may preferably include one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) as monomer components.
  • Examples of other (meth)acrylic acid alkyl esters that can be preferably used as the monomer component of the acrylic polymer include methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate. (2EHMA) and the like.
  • the (meth)acrylic acid alkyl ester used as the monomer component of the base polymer has a homopolymer having a glass transition temperature of ⁇ 80° C. or higher and 0° C. or lower.
  • the glass transition temperature of the homopolymer of (meth)acrylic acid alkyl ester is preferably ⁇ 70° C. to ⁇ 5° C., more preferably ⁇ 60° C. to ⁇ 10° C.
  • the (meth)acrylic acid alkyl ester used as the monomer component of the base polymer may be contained in an amount of 80% by weight or more based on the weight of the base polymer.
  • the (meth)acrylic acid alkyl ester is preferably 85% by weight or more, more preferably 90% by weight or more, based on the weight of the base polymer.
  • 80% by weight or more of a (meth)acrylic acid alkyl ester having a homopolymer glass transition temperature of ⁇ 60° C. or higher and 0° C. or lower can be contained as a monomer component of the base polymer.
  • the acrylic polymer may be, in addition to the (meth)acrylic acid alkyl ester as the main component, optionally copolymerizable with the (meth)acrylic acid alkyl ester. It may further contain the monomer (copolymerizable monomer).
  • a monomer having a polar group for example, a carboxy group, a hydroxyl group, a nitrogen atom-containing ring, etc.
  • the monomer having a polar group can be useful for introducing a cross-linking point in the acrylic polymer and for enhancing the cohesive force of the acrylic polymer.
  • the copolymerizable monomer may be used alone or in combination of two or more.
  • Non-limiting specific examples of the copolymerizable monomer include a carboxy group-containing monomer, an acid anhydride group-containing monomer, a hydroxy group-containing monomer, a sulfonic acid group- or phosphoric acid group-containing monomer, an epoxy group-containing monomer, and a cyano group.
  • carboxy group-containing monomer examples include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.
  • acid anhydride group-containing monomer examples include maleic anhydride and itaconic anhydride.
  • hydroxy group-containing monomer examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, ( 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, ( Examples thereof include hydroxyalkyl (meth)acrylates such as 4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
  • Examples of the monomer having a sulfonic acid group or a phosphoric acid group include styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid. , Sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalene sulfonic acid, 2-hydroxyethyl acryloyl phosphate and the like.
  • Examples of the epoxy group-containing monomer include epoxy group-containing acrylates such as (meth)acrylic acid glycidyl and (meth)acrylic acid-2-ethylglycidyl ether, allyl glycidyl ether, and (meth)acrylic acid glycidyl ether.
  • Examples of the cyano group-containing monomer include cyano(meth)acrylate-based monomers such as acrylonitrile and methacrylonitrile.
  • Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth)acrylate.
  • Examples of the amide group-containing monomer include (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl( N,N-dialkyl(meth)acrylamides such as (meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide; N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, Nn-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, etc.
  • N-alkyl(meth)acrylamide N-vinyl carboxylic acid amides such as N-vinyl acetamide;
  • Examples thereof include acrylamide, N-methoxyethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-(meth)acryloylmorpholine.
  • Examples of the monomer having a nitrogen atom-containing ring include vinyl monomers having a lactam ring (vinylpyrrolidone monomers such as N-vinyl-2-pyrrolidone and N-methylvinylpyrrolidone; N-vinyl-2-caprolactam).
  • Vinyl monomers having lactam rings such as vinyl lactam monomers having lactam rings such as ⁇ -lactam ring, ⁇ -lactam ring, and ⁇ -lactam ring
  • N-vinylpyridine N-vinylpiperidone, N-vinylpyrimidine , N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth) Acryloylpyrrolidine, N-vinylmorpholine, N-vinyl-3-morpholinone, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinyliso Examples thereof include oxazole, N-vinyl
  • succinimide-based monomer examples include N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, and N-(meth)acryloyl-8-oxyhexamethylenesuccinimide.
  • maleimide-based monomer examples include maleimide, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like.
  • Examples of the itaconimide-based monomer include N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, Examples thereof include N-lauryl itaconimide.
  • aminoalkyl (meth)acrylate-based monomer examples include aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N (meth)acrylate, Examples thereof include N-diethylaminoethyl, t-butylaminoethyl (meth)acrylate, and 3-(3-pyridinyl)propyl(meth)acrylate.
  • alkoxyalkyl (meth)acrylate monomers examples include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and (meth)acrylic. Examples include ethoxypropyl acid and the like.
  • vinyl ester-based monomers examples include vinyl acetate and vinyl propionate.
  • vinyl ether-based monomers include vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether.
  • the aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, vinyltoluene and the like.
  • Examples of the olefin-based monomer include ethylene, butadiene, isoprene and isobutylene.
  • Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate and the like.
  • Examples of the (meth)acrylic acid ester having an aromatic hydrocarbon group include phenyl(meth)acrylate, phenoxyethyl(meth)acrylate, and benzyl(meth)acrylate.
  • the amount used is not particularly limited, but it is usually appropriate to set it to 0.01% by weight or more of the total amount of the monomer components.
  • the amount of the copolymerizable monomer used may be 0.1% by weight or more, or 1% by weight or more based on the total amount of the monomer components.
  • the amount of the copolymerizable monomer used can be 50% by weight or less, and preferably 40% by weight or less, based on the total amount of the monomer components. This can prevent the cohesive force of the pressure-sensitive adhesive from becoming too high, and improve the tackiness at room temperature (25° C.).
  • the acrylic polymer contains a hydroxy group-containing monomer (typically, as described above) as a monomer component, if necessary, in addition to the (meth)acrylic acid alkyl ester as a main component.
  • a (meth)acrylic monomer containing a hydroxy group include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA).
  • the hydroxy group-containing monomer can also serve to suppress the decrease in transparency due to moisture by increasing the hydrophilicity of the pressure-sensitive adhesive layer.
  • the amount of the hydroxy group-containing monomer used is not particularly limited, but is usually 0.01% by weight or more, 0.1% by weight or more, based on the total amount of the monomer components for preparing the acrylic polymer. The amount can be, for example, 0.5% by weight or more, 0.5% by weight or more.
  • the acrylic polymer is, in addition to the (meth)acrylic acid alkyl ester as the main component, a polyfunctional compound for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive layer, if necessary. It may contain a monomer.
  • polyfunctional monomer examples include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecane Diol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate,
  • trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be preferably used.
  • the polyfunctional monomers may be used alone or in combination of two or more.
  • the amount of the polyfunctional monomer used varies depending on the molecular weight and the number of functional groups, but is usually 0.01% by weight to 3.0% by weight based on the total amount of the monomer components for preparing the (meth)acrylic acid alkyl ester. It is suitable to be in the range of %, and may be 0.02% to 2.0% by weight, or 0.03% to 1.0% by weight.
  • the base polymer may include, as a copolymerizable monomer component, at least one polar monomer selected from the group consisting of a carboxyl group-containing monomer and a nitrogen-containing monomer.
  • the carboxyl group-containing monomer may be acrylic acid or methacrylic acid.
  • the carboxyl group-containing monomer may be acrylic acid (AA).
  • the nitrogen-containing monomer examples include the cyano group-containing monomer, the amide group-containing monomer, the nitrogen atom-containing ring-containing monomer, the succinimide-based monomer, the maleimide-based monomer, the amide group-containing monomer, and the aminoalkyl (meth)acrylate-based monomer, which are exemplified above. Examples thereof include monomers.
  • the nitrogen-containing monomer is at least one selected from N-vinylpyrrolidone, methylvinylpyrrolidone, N,N-dimethyl(meth)acrylamide.
  • the nitrogen containing monomer is N-vinylpyrrolidone.
  • the polar monomer may be included in an amount of 0 to 20% by weight based on the weight of the base polymer.
  • the polar monomer is preferably 0.1 to 17.5% by weight, more preferably 1 to 15% by weight, based on the weight of the base polymer.
  • the method for obtaining the acrylic polymer is not particularly limited, and the acrylic polymer can be produced in the same manner as the acrylic polymer as the base polymer of the ⁇ photocurable pressure-sensitive adhesive layer>.
  • the cross-linking agent used in the ⁇ photo-curable pressure-sensitive adhesive layer> can be similarly suitably used.
  • the heating type pressure-sensitive adhesive layer an embodiment in which at least an isocyanate crosslinking agent is used as the crosslinking agent is particularly preferable.
  • the amount of the isocyanate-based cross-linking agent based on 100 parts by weight of the base polymer is, for example, 5 parts by weight or less.
  • the amount may be 3 parts by weight or less, 1 part by weight or less, 0.7 parts by weight or less, and 0.5 parts by weight or less.
  • the use amount of the cross-linking agent is not too large. It may be advantageous from the viewpoint of expression.
  • the weight average molecular weight (Mw) of the base polymer may be 500,000 to 2,500,000. In one embodiment, the weight average molecular weight (Mw) of the base polymer may be preferably 700,000 to 2.7 million, more preferably 800,000 to 2.5 million.
  • the heating type pressure-sensitive adhesive layer preferably contains a rework improver together with the base polymer.
  • the rework improver is a chemical substance that has a polar group, easily interacts with the glass interface, and is easily segregated at the glass interface.
  • Examples of the rework improver include a diol having an alkyleneoxy group such as EO (ethyleneoxy) and PO (propyleneoxy), an oligomer having a perfluoroalkyl group, a polyether compound having a reactive silyl group, and an ether group. Examples thereof include polysiloxane.
  • the polyether compound for example, those disclosed in JP 2010-275522A can be used.
  • polyether compound having a reactive silyl group examples include MS polymers S203, S303, S810; SILYL EST250, EST280; SAT10, SAT200, SAT220, SAT350, SAT400, EXCESTAR S2410, S2420 manufactured by Asahi Glass Co., Ltd. Or S3430 etc. are mentioned.
  • the ether group-containing polysiloxane examples include polyether-modified silicone oils KF-353, KF-351A, and KF-352A manufactured by Shin-Etsu Chemical Co., Ltd.
  • the rework improver may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the acrylic polymer.
  • the rework improver is preferably contained in an amount of 0.25 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the above-mentioned acrylic polymer.
  • the content of the silicone oligomer contained in the pressure-sensitive adhesive layer is within the above range, the initial pressure-sensitive adhesive force can be suppressed, and a higher pressure-sensitive adhesive force after heating can be obtained.
  • the heating type pressure-sensitive adhesive layer preferably contains a base polymer and a silicone oligomer having a siloxane skeleton. Due to the low polarity and motility of the siloxane structure, the silicone oligomer can function as a tackiness increase retarder that contributes to the suppression of initial tackiness and the improvement of the tack ratio. As the silicone oligomer, a polymer having a siloxane structure in its side chain can be preferably used.
  • the silicone oligomer used in the present invention has a glass transition temperature (Tg) in the range of -50°C to 100°C.
  • Tg glass transition temperature
  • the Tg of the silicone oligomer may be preferably -30°C or higher and 70°C or lower, more preferably -20°C or higher and 60°C or lower.
  • the silicone oligomer used in the present invention has a weight average molecular weight Mw of 10,000 or more and 300,000 or less.
  • the weight average molecular weight Mw of the silicone oligomer may be preferably 12,500 or more and 2500000 or less, more preferably 15000 or more and 2000000 or less.
  • the weight average molecular weight Mw of the silicone oligomer is within the above range, it is easy to adjust the compatibility and mobility in the pressure-sensitive adhesive layer to an appropriate range, and the initial low tackiness and strong tackiness at the time of use are at a high level. It becomes easier to realize a pressure sensitive adhesive sheet that is compatible with
  • the silicone oligomer has a Tg of ⁇ 70° C. or higher and 30° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight Mw of 10,000 or more and 300,000 or less.
  • the silicone oligomer may include (i) a monomer having a polyorganosiloxane skeleton and (ii) a monomer having a glass transition temperature of the homopolymer of ⁇ 70° C. or higher and 180° C. or lower as monomer components. ..
  • the monomer having a polyorganosiloxane skeleton that can be used in the silicone oligomer is not particularly limited, and any monomer having a polyorganosiloxane skeleton can be used.
  • Examples of the polyorganosiloxane skeleton include, but are not limited to, trimethylsiloxane (TM), dimethylsiloxane (DM), polyoxyethylmethylsiloxane (EOM), and the like.
  • the monomer having a polyorganosiloxane skeleton for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, as one end reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174ASX, X-22-2426, X-22-2475, KF-2012, X-22-174BX, X -22-2404 and the like.
  • the monomer having a polyorganosiloxane skeleton may be used alone or in combination of two or more.
  • R 3 in the general formulas (1) and (2) is hydrogen or methyl
  • R 4 is a methyl group or a monovalent organic group
  • m and n are integers of 0 or more.
  • the silicone oligomer preferably has a side chain silicone functional group equivalent of 1000 to 20000 g/mol.
  • the silicone functional group equivalent weight of the side chain of the silicone oligomer may be preferably 1200 to 18000 g/mol, more preferably 1500 to 15000 g/mol.
  • the silicone functional group equivalent of the side chain of the silicone oligomer is within the above range, it is easy to adjust the compatibility (for example, the compatibility with the base polymer) and the mobility in the pressure-sensitive adhesive layer to an appropriate range, and the initial low It becomes easy to realize a pressure-sensitive adhesive sheet that achieves a high level of both tackiness and strong tackiness during use.
  • the “functional group equivalent” means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to each functional group.
  • the unit of g/mol is converted to 1 mol of the functional group.
  • the functional group equivalent of the monomer having a polyorganosiloxane skeleton can be calculated from the spectrum intensity of 1 H-NMR (proton NMR) based on nuclear magnetic resonance (NMR), for example. Calculation of the functional group equivalent (g/mol) of the monomer having a polyorganosiloxane skeleton based on the 1 H-NMR spectrum intensity is necessary based on a general structural analysis method related to 1 H-NMR spectrum analysis. If there is, it can be performed with reference to the description of Japanese Patent No. 5915153.
  • an arithmetic average value can be used as the functional group equivalent of the monomer. That is, the functional group equivalent of the monomer S1 composed of n kinds of monomers (monomer S11, monomer S12... Monomer S1n) having different functional group equivalents can be calculated by the following formula.
  • the content of the monomer having a polyorganosiloxane skeleton may be, for example, 5% by weight or more based on the total amount of the monomer components for preparing the silicone oligomer, and the effect as a tackiness increase retarder is better exhibited. Is preferably 10% by weight or more, and may be 15% by weight or more. In some embodiments, the content of the monomer may be, for example, 20% by weight or more. In addition, the content of the monomer having a polyorganosiloxane skeleton is appropriately 60% by weight or less based on the total monomer components for preparing the silicone oligomer, from the viewpoint of polymerization reactivity and compatibility.
  • the content of the monomer having a polyorganosiloxane skeleton is within the above range, it becomes easy to realize a pressure-sensitive adhesive sheet that achieves a high level of both low initial tackiness and increased tackiness during use (strong tackiness). ..
  • Examples of the (meth)acrylic acid alkyl ester include methyl methacrylate (MMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2-EHMA), butyl acrylate (BA), and 2-ethylhexyl acrylate (2-EHA).
  • MMA methyl methacrylate
  • BMA butyl methacrylate
  • EHMA 2-ethylhexyl methacrylate
  • BA butyl acrylate
  • 2-EHA 2-ethylhexyl acrylate
  • Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA), cyclopentyl (meth)acrylate, Examples thereof include, but are not limited to, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, and the like.
  • At least one selected from 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA) and isobornyl methacrylate (IBXMA) is used as a monomer component.
  • EHAMA 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate
  • IBXMA isobornyl methacrylate
  • at least one selected from dicyclopentanyl methacrylate, isobornyl methacrylate and cyclohexyl methacrylate may be contained as a monomer component. These monomers may be used alone or in combination of two or more.
  • the amount of the above-mentioned (meth)acrylic acid alkyl ester and the above-mentioned (meth)acrylic acid ester having an alicyclic hydrocarbon group used is, for example, 10% by weight or more and 95% by weight, based on all the monomer components for preparing the silicone oligomer. % Or less, 20% by weight or more and 95% by weight or less, 30% by weight or more and 90% by weight or less, 40% by weight or more and 90% by weight or less, 50 It may be not less than 85% by weight.
  • the monomer that can be contained together with the monomer having a polyorganosiloxane skeleton as a monomer component constituting the silicone oligomer a carboxyl group-containing monomer and an acid anhydride exemplified above as the monomer that can be used for the (meth)acrylic acid alkyl ester.
  • Oxyalkylene di(meth)acrylates such as acrylates, propylene glycol di(meth)acrylates, dipropylene glycol di(meth)acrylates, tripropylene glycol di(meth)acrylates; monomers having a polyoxyalkylene skeleton, such as polyethylene glycol and A polyoxyalkylene chain such as polypropylene glycol has a polymerizable functional group such as a (meth)acryloyl group, a vinyl group or an allyl group at one end and an ether structure (alkyl ether, aryl ether, arylalkyl ether) at the other end.
  • methoxyethyl (meth)acrylate methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxypropyl (meth)acrylate.
  • Alkoxyalkyl (meth)acrylates such as; Salts such as alkali metal salts of (meth)acrylic acid; Polyvalent (meth)acrylates such as trimethylolpropane tri(meth)acrylic acid ester: vinylidene chloride, (meth)acrylic acid- Halogenated vinyl compounds such as 2-chloroethyl; 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline and other oxazoline group-containing monomers; (meth)acryloylaziridine , Aziridine group-containing monomers such as 2-aziridinylethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lactones and (meth)acrylic acid Hydroxyl group-containing vinyl monomer such as an adduct with 2-hydroxyethyl; fluorine-containing vinyl monomer such
  • the monomer component used for preparing the silicone oligomer includes a monomer having a polyorganosiloxane skeleton and a (meth)acrylic monomer
  • a monomer having a polyorganosiloxane skeleton and a (meth)acrylic monomer occupying the entire monomer components May be, for example, 50% by weight or more, 70% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or substantially 100% by weight. Good.
  • the composition of the (meth)acrylic monomer contained in the monomer component can be set so that the glass transition temperature T m1 based on the composition of the (meth)acrylic monomer is higher than 0° C., for example.
  • the glass transition temperature T m1 based on the composition of the (meth)acrylic monomer is determined by the Fox equation based on the composition of only the (meth)acrylic monomer among the monomer components used for preparing the silicone oligomer.
  • the Tg that can be obtained.
  • the T m1 is the glass transition temperature of the homopolymer of each (meth)acrylic monomer, which is obtained by applying the above-described Fox equation for only the (meth)acrylic monomer among the monomer components used for the preparation of the silicone oligomer. Can be calculated from the weight fraction of each (meth)acrylic monomer in the total amount of the (meth)acrylic monomer.
  • T m1 may be ⁇ 20° C. or higher, ⁇ 10° C. or higher, 0° C. or higher, or 10° C. or higher. As T m1 increases, the adhesive force in the early stage of application generally tends to be better suppressed. Further, T m1 may be, for example, 90° C. or lower, 80° C. or lower, 70° C. or lower, or lower than 70° C. When T m1 is low, increase in adhesive strength due to heating tends to be facilitated.
  • the technique disclosed herein can be preferably carried out using a silicone oligomer Ps having a T m1 in the range of, for example, ⁇ 20° C. to 90° C., or ⁇ 10° C. to 80° C., and 0° C. to 70° C.
  • the silicone oligomer can be produced, for example, by polymerizing the above-mentioned monomer by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a photopolymerization method.
  • a chain transfer agent can be used to adjust the molecular weight of the silicone oligomer.
  • chain transfer agents used include octyl mercaptan, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, ⁇ -thioglycerol, and other compounds having a mercapto group; thioglycolic acid, methyl thioglycolate, Ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, ethylene Thioglycolic acid est
  • the amount of the chain transfer agent used is not particularly limited, but is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the monomer. And more preferably 0.2 to 10 parts by weight.
  • the chain transfer agents may be used alone or in combination of two or more.
  • the silicone oligomer may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the above-mentioned acrylic polymer. In an embodiment of the present invention, the silicone oligomer is included in an amount of preferably 0.25 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the acrylic polymer. obtain.
  • the content of the silicone oligomer contained in the pressure-sensitive adhesive layer is within the above range, the initial pressure-sensitive adhesive force can be suppressed, and a higher pressure-sensitive adhesive force after heating can be obtained.
  • the silicone oligomer as described above can function favorably as an adhesive force increase retarder when blended in the adhesive layer.
  • the silicone oligomer functions as an adhesive force increase retarder, the initial adhesive force is suppressed by the silicone oligomer present on the surface of the adhesive layer in the pressure-sensitive adhesive sheet from before being attached to the adherend and in the initial stage of attachment, It is considered that the adhesive flows due to the passage of time after application, heating, or the like, whereby the amount of silicone oligomer present on the surface of the adhesive layer decreases, the silicone oligomer is compatible with the adhesive, and the adhesive strength increases.
  • the present invention is not limited to this mechanism.
  • the adhesive force increase retarder in the technology disclosed herein other materials capable of exhibiting the same type of function may be used instead of the silicone oligomer or in combination with the silicone oligomer.
  • a non-limiting example of such a material is a polymer having a polyoxyalkylene structure in the molecule (hereinafter, also referred to as “polymer Po”).
  • the polymer Po can be, for example, a polymer including a monomer component derived from a monomer having a polyoxyalkylene skeleton.
  • polystyrene resin examples thereof include homopolymers or copolymers of any one of the above-mentioned monomers having a polyoxyalkylene skeleton, and one or more of monomers having a polyoxyalkylene skeleton and others.
  • a copolymer with the monomer (for example, a (meth)acrylic monomer) or the like can be used as the polymer Po.
  • the amount of the monomer having a polyoxyalkylene skeleton is not particularly limited, but for example, the amount of the monomer having a polyorganosiloxane skeleton in the above-mentioned silicone oligomer is set to the amount of the monomer having a polyoxyalkylene skeleton in polymer Po. Can also be applied.
  • the amount of the polymer Po used in the pressure-sensitive adhesive layer is not particularly limited.
  • the amount of the silicone oligomer Ps used for the base polymer described above can be applied to the amount of the polymer Po used for the base polymer.
  • a part of the amount of the silicone oligomer used with respect to the above-mentioned base polymer for example, about 5% to 95% by weight, or about 15% to 85% by weight, or 30% by weight of the total amount of the silicone oligomer used). (About 70% by weight) may be replaced with the polymer Po.
  • the melting temperature of the silicone oligomer may be -20 to 120°C. In another embodiment of the present invention, the melting temperature of the silicone oligomer may be ⁇ 10 to 90° C., 0 to 80° C.
  • the method of forming the above-mentioned heating type pressure-sensitive adhesive layer is not particularly limited, and the same method as (Forming method of pressure-sensitive adhesive layer) in ⁇ Photocurable pressure-sensitive adhesive layer> can be used. Even after heat-drying the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer has a small adhesive force with the adherend, and therefore reworking is easy.
  • the adhesive strength of the pressure-sensitive adhesive layer may be significantly increased depending on the heating and drying conditions for forming the pressure-sensitive adhesive layer. From this viewpoint, the heating and drying temperature is preferably 50 to 200° C. (more preferably 70 to 170° C.), and the drying time is preferably 20 seconds to 5 minutes (more preferably 40 seconds to 3 minutes). preferable.
  • the pressure-sensitive adhesive layer-attached antireflection film is attached to the adherend, the pressure-sensitive adhesive layer is heat-treated to increase the adhesive force of the pressure-sensitive adhesive layer.
  • the conditions of the heat treatment are, for example, 20 to 80° C. for 1 to 100 hours (preferably 20 to 80° C. for 1 to 48 hours, more preferably 25 to 80° C. for 1 to 48 hours).
  • the photocurable pressure-sensitive adhesive layer and the heat-type pressure-sensitive adhesive layer may further contain a silane coupling agent.
  • the durability can be improved by using the silane coupling agent.
  • the silane coupling agent one having any appropriate functional group can be used.
  • the functional group include a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, and a polysulfide group.
  • vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, and vinyltributoxysilane; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycine Epoxy group-containing silane coupling agents such as cidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, ⁇ -triethoxysilyl-N-(1,3-dimethylbutylidene) Amino group-
  • silane coupling agent for example, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane and ⁇ -mercaptopropylmethyldimethoxysilane are preferably used. You can
  • the silane coupling agent may be used alone or in combination of two or more kinds, but the total content is 100 parts by weight of the base polymer and the silane coupling agent.
  • the amount is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, further preferably 0.02 to 1 part by weight, further preferably 0.05 to 0.6 part by weight.
  • a tackifier In the photocurable pressure-sensitive adhesive layer and the heat-type pressure-sensitive adhesive layer, in addition to the components illustrated above, a tackifier, a leveling agent, a plasticizer, a softener, and deterioration.
  • Known additives that can be used for pressure-sensitive adhesives such as an inhibitor, a filler, a colorant, an ultraviolet absorber, an antioxidant, a surfactant, an antistatic agent, a light stabilizer, and an antiseptic agent have the characteristics of the present invention. You may contain in the range which does not spoil.
  • the ultraviolet absorber is contained in at least one of the antireflection film and the pressure-sensitive adhesive layer mainly for the purpose of preventing deterioration of the light emitting element in the panel.
  • the ultraviolet absorber In order to absorb a certain amount of ultraviolet rays, it is necessary to increase the addition amount for thinner layers. On the other hand, if the added amount increases, the ultraviolet absorber may bleed. Therefore, from the viewpoint of suppressing bleeding while exhibiting a sufficient ultraviolet absorbing effect, the ultraviolet absorber is preferably contained in the antireflection film, and more preferably contained in the transparent resin film constituting the antireflection film.
  • the ultraviolet absorber is not particularly limited, and various types can be used. Specific examples include benzophenone-based compounds, oxalic acid anilide-based compounds, cyanoacrylate-based compounds, benzotriazole-based compounds, and triazine-based compounds.
  • the ultraviolet absorbers may be used alone or in combination of two or more. Of these, benzotriazole compounds and triazine compounds are preferable, and triazine compounds are particularly preferable.
  • the triazine-based compound can obtain a sufficient ultraviolet absorbing effect with a small addition amount, and can prevent bleed-out and the like during film formation.
  • benzophenone compound examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-n- Examples thereof include octyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, and 1,4-bis(4-benzoyl-3-hydroxyphenone)-butane.
  • oxalic acid anilide compound examples include N-(2-ethylphenyl)-N'-(2-ethoxy-phenyl)oxalic acid amide and N-(2-dodecylphenyl)-N'-(2-ethoxy- Phenyl) oxalic acid amide and the like.
  • Examples of the cyanoacrylate compound include octyl-2-cyano-3,3-diphenylacrylate.
  • benzotriazole compound examples include 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(3-dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2 -(3,5-Di-(2-methyloctane-2-yl)-2-hydroxyphenyl)benzotriazole, 2-(3-tert-methyl-5-(octoxycarbonylethyl)-2-hydroxyphenyl) Benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(3,5-di- tert-Butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4,6- Bis(1-methyl-
  • the triazine compound is not particularly limited, and various compounds can be used.
  • the triazine compounds described in WO 2005/109052 and JP 2009-52021 A can be preferably used.
  • Examples of commercially available triazine-based compounds include Tinuvin 1577, Tinuvin 460, Tinuvin 477 (manufactured by BASF Japan). Examples of commercially available benzotriazole-based compounds include ADEKA STAB LA-31 (made by ADEKA).
  • the content of the ultraviolet absorber is not particularly limited.
  • the content of the ultraviolet absorber is preferably 0.01 to 5% by weight, and 0.01 to 5% by weight based on the weight (100% by weight) of the transparent resin film. 4% by weight is more preferable, and 0.05 to 3% by weight is further preferable.
  • the content of the ultraviolet absorber is preferably 1 to 10% by weight, more preferably 3 to 10% by weight, based on 100 parts by weight of the acrylic polymer. More preferably, it is up to 8% by weight.
  • the light transmittance of the adhesive layer from 380 nm to 780 nm is preferably 20 to 85%.
  • the pressure-sensitive adhesive layer having such transparency has an advantage of absorbing reflected light.
  • “the light transmittance of 380 nm to 780 nm is 20 to 85%” means that the light transmittance of each wavelength is 20 to 85% over the entire wavelength range of 380 nm to 780 nm.
  • the light transmittance of the pressure-sensitive adhesive layer is, for example, relative when the transmittance of the laminate in which the pressure-sensitive adhesive layer is formed on the substrate and the transmittance of the substrate are measured, and the value of the transmittance of the substrate is 100%. It can be calculated as a value.
  • Light transmittance can be measured using a spectrophotometer.
  • the light transmittance at 380 nm of the pressure-sensitive adhesive layer is preferably 70% or less.
  • the adherend to which the antireflection film with the adhesive layer is attached is, for example, a panel of a self-luminous display device.
  • the laminated body may be attached to the entire surface of the adherend, or may be selectively attached to only a part of the adherend. Further, after adhering the laminated body to the entire surface of the adherend, the laminated body at an unnecessary portion may be cut and removed. Before the adhesive strength increasing process, since the laminate is temporarily attached to the surface of the adherend, the laminate can be easily peeled and removed from the surface of the adherend.
  • the antireflection film with the pressure-sensitive adhesive layer of the above embodiment can be used as an optical film laminated with another optical layer in practical use.
  • the optical layer is not particularly limited, but examples thereof include window glass.
  • the pressure-sensitive adhesive layer-attached antireflection film or optical film of the above embodiment can be preferably used for a self-luminous display device such as an organic EL display device and a micro LED. That is, according to one embodiment of the present invention, there is provided a self-luminous display device including the antireflection film with the pressure-sensitive adhesive layer of the above embodiment.
  • the self-luminous display device of one embodiment has the antireflection film with the pressure-sensitive adhesive layer of the above embodiment on the viewing side panel.
  • the self-luminous display device of one embodiment has the pressure-sensitive adhesive layer-attached antireflection film of the above embodiment directly on the barrier layer on the panel surface on the viewing side.
  • the self-luminous display device of one embodiment has a structure in which an antireflection film is laminated on the panel surface on the viewing side via an adhesive layer.
  • the pressure-sensitive adhesive layer-attached antireflection film of the present embodiment can replace the circularly polarizing plate and the polarizing plate that are conventionally arranged on the panel for preventing reflection of external light. Therefore, the self-luminous display device of one embodiment does not include the circularly polarizing plate and the polarizing plate.
  • One embodiment of the present invention relates to a method of manufacturing a self-luminous display device.
  • the manufacturing method includes disposing an antireflection film with a pressure-sensitive adhesive layer on a panel via the pressure-sensitive adhesive layer, and subjecting the pressure-sensitive adhesive layer to increasing adhesive strength.
  • the irradiation direction of the energy actinic ray is not particularly limited, but it is preferable to irradiate from the antireflection layer side in that the panel does not transmit light due to wiring or the like.
  • HC-TAC film (thickness: 7 ⁇ m) made of acrylic resin on one side of a TAC film (product name: KC2UA, thickness: 25 ⁇ m, containing an ultraviolet absorber) manufactured by Konica Minolta Co., Ltd.
  • HC-TAC film (thickness: 32 ⁇ m) was obtained.
  • An adhesion layer (thickness: 10 nm) made of SiO x is formed on the surface of the HC layer of this HC-TAC film by sputtering, and a Nb 2 O 5 film (high refractive index layer) and a SiO 2 film are further formed on the adhesion layer. (Low refractive index layer), Nb 2 O 5 film (high refractive index layer), and SiO 2 film (low refractive index layer) are sequentially formed to form an antireflection layer (thickness or optical film thickness: 200 nm). Formed. Furthermore, an antifouling layer (thickness: 10 nm) made of an alkoxysilane compound having a perfluoropolyether group was formed on the antireflection layer, to prepare an antireflection film 1.
  • Photocurable Adhesive Compositions 1 to 3 A carbon black pigment dispersant, a cross-linking agent, a photo-curing agent, a photo-polymerization initiator and, if necessary, a sensitizer were added to a solution of an acrylic polymer, and the resulting mixture was uniformly mixed to obtain a composition of An adhesive composition was prepared.
  • the addition amount in Table 1 is the addition amount (parts by weight) with respect to the solid content (100 parts by weight) of the acrylic polymer solution. Details of the cross-linking agent, photo-curing agent, photo-polymerization initiator and carbon black pigment dispersant used are as follows.
  • (Crosslinking agent) B1 Takenate D110N (75% ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate; manufactured by Mitsui Chemicals) (Photopolymerization initiator)
  • C1 Omnirad819 (acylphosphine compound: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; manufactured by IGM Japan; molar extinction coefficient 828 [L/(mol ⁇ cm)] at a wavelength of 380 nm)
  • C2 Omnirad907 (aminoacetophenone compound; 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one; manufactured by IGM Japan; molar absorption coefficient at a wavelength of 380 nm: 28.8 [L/( mol ⁇ cm)])
  • the pressure-sensitive adhesive composition obtained above is uniformly applied to the surface of a 38 ⁇ m-thick substrate (polyethylene terephthalate film) treated with a silicone-based release agent with a fountain coater, It was dried in an air-circulating constant temperature oven at 130° C. for 1 minute to form an adhesive layer having a thickness of 20 ⁇ m on the surface of the base material.
  • a separator having an adhesive layer formed thereon is transferred to the surface (corona-treated) opposite to the antireflection layer of the antireflection film to form an antireflection layer base material (HC-TAC film) constituting the antireflection film.
  • a photocurable pressure-sensitive adhesive layer-attached antireflection film having a pressure-sensitive adhesive layer formed on the surface (the surface opposite to the HC layer) was produced. Then, aging treatment was carried out for 4 days in an atmosphere of 25° C. to promote crosslinking, and a crosslinked structure was introduced into the acrylic polymer as the base polymer. As a result, a pressure-sensitive adhesive layer was fixedly laminated on the antireflection film, and a photocurable pressure-sensitive adhesive layer-attached antireflection film having a separator temporarily adhered thereon was obtained.
  • a monomer mixture containing 99 parts by weight of butyl acrylate (BA) and 1 part by weight of 4-hydroxybutyl acrylate (HBA) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser. .. Further, with respect to 100 parts by weight of the monomer mixture (solid content), 0.1 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged together with ethyl acetate, and nitrogen gas was added with gentle stirring. After introducing and purging with nitrogen, the liquid temperature in the flask was kept at around 55° C.
  • methacrylic polymer (S1)> A 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel, 100 parts of ethyl acetate, 60 parts of MMA, 10 parts of n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate (2EHMA).
  • polyorganosiloxane skeleton-containing methacrylate monomer having a functional group equivalent of 900 g/mol (trade name: X-22-174ASX, manufactured by Shin-Etsu Chemical Co., Ltd.) 8.7 parts, polyorgano having a functional group equivalent of 4600 g/mol.
  • a siloxane skeleton-containing methacrylate monomer (trade name: KF-2012, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.2 part of methyl thioglycolate as a chain transfer agent were added. Then, after stirring at 70° C.
  • Cross-linking agent B1 Takenate D110N (75% ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate; manufactured by Mitsui Chemicals)
  • B2 Coronate L (isocyanate-based crosslinking agent: trimethylolpropane/tolylene diisocyanate; manufactured by Nippon Polyurethane Industry Co., Ltd.)
  • B3 Niper BMT (peroxide type crosslinking agent: benzoyl peroxide; manufactured by NOF Corporation) (Rework improver)
  • G1 Modified silicone oil KF-353 (polysiloxane containing ether group; manufactured by Shin-Etsu Chemical Co., Ltd.)
  • G2 Cyryl SAT10 (polyether-modified silicone compound; manufactured by Kaneka Corporation)
  • the pressure-sensitive adhesive composition obtained above is evenly applied by a fountain coater to the surface of a substrate (polyethylene terephthalate film) having a thickness of 38 ⁇ m which has been treated with a silicone-based release agent, and then applied at 155° C. Was dried for 2 minutes in a constant temperature air-circulation oven to form a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m on the surface of the substrate.
  • a separator having an adhesive layer is transferred to the surface (corona treated) opposite to the antireflection layer of the obtained antireflection film to form an antireflection film substrate (HC-TAC).
  • An antireflection film with a heating type pressure-sensitive adhesive layer in which a pressure-sensitive adhesive layer was formed on the surface of the film) (the surface opposite to the HC layer) was produced.
  • a pressure-sensitive adhesive layer was fixedly laminated on the antireflection film, and a separator was temporarily attached thereon to obtain a heat-resistant pressure-sensitive adhesive layer-attached antireflection film.
  • the pressure-sensitive adhesive layer was a photo-curable pressure-sensitive adhesive layer (Examples 1 and 2, Comparative Example 1)
  • the following photo-curing treatment was performed.
  • the pressure-sensitive adhesive layer was a heat-type pressure-sensitive adhesive layer (Examples 3 to 5, Comparative Example 2)
  • the following heat treatment was performed.
  • An ultraviolet ray (light source: LED wavelength: 405 nm) of the test sample before curing was irradiated with ultraviolet rays (light source: LED wavelength: 405 nm) at an integrated light amount of 4000 mJ/cm 2 to photo-cur the pressure-sensitive adhesive layer, which was used as a test sample after photo-curing.
  • the test sample before the heat treatment was stored at 60° C. for 24 hours and used as the test sample after the heat treatment. 3. Measurement of adhesive strength (90° peeling adhesive strength) Using the test sample before and after the adhesive strength increasing treatment obtained above, a tensile tester (device name: precision universal tester, Autograph AG-IS, Shimadzu) is used. According to JIS Z0237:2009, 90° peeling adhesive force (adhesive force) was measured under conditions of a peeling angle of 90° and a pulling speed of 300 mm/min. The measurement was performed 3 times, and the average value thereof was calculated.
  • the reworkability was judged according to the following criteria from the value of the adhesive strength (initial adhesive strength) of the test sample before the adhesive strength increasing treatment.
  • Durability Durability (adhesion) was judged according to the following criteria from the value of the adhesive strength of the test sample after the adhesive strength increasing treatment.
  • the results are shown in Table 3.
  • Each pressure-sensitive adhesive composition was evenly coated with a fountain coater on the surface of a substrate (polyethylene terephthalate film) having a thickness of 38 ⁇ m that had been treated with a silicone-based release agent, and was kept in an air circulating constant temperature oven at 130° C. for 1 minute. After drying, a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m was formed on the surface of the base material.
  • the antireflection film with a photocurable pressure-sensitive adhesive layer obtained in Example 1 was cut into a size of 30 mm ⁇ 30 mm.
  • An OLED panel member was taken out from an organic EL display (OLED) (manufactured by Samsung, product name "Galaxy S5"), and the window glass and the polarizing film attached to the OLED panel member were peeled off and used as an OLED panel.
  • the separator was peeled off from the cut out antireflection film with a photocurable pressure-sensitive adhesive layer obtained in Example 1 above, and the exposed pressure-sensitive adhesive surface was bonded onto an OLED panel using a hand roller to obtain an OLED sample.
  • the transmittance of white display and the reflectance of black display were measured by the following methods.
  • the luminance Y value was measured using a spectroradiometer (SR-UL1R, manufactured by Topcon Technohouse Co., Ltd.).
  • the ratio of the luminance Y value of the OLED sample (Example 1+AR film) when the measured luminance Y value of only the OLED panel was set to 100% was calculated as the transmittance.
  • the luminous reflectance Y value was measured using a spectrophotometer (CM-2600d manufactured by Konica Minolta Co., Ltd.).
  • the ratio of the luminous reflectance Y value of the OLED sample (Example 1+AR film) when the measured value of the luminous reflectance Y value of only the OLED panel was set to 100% was calculated as the reflectance.
  • the results are shown in Table 4. As shown in Table 4, it was possible to reduce the reflectance by 70% while securing the transmittance of about 80%.
  • an antireflection film with an adhesive layer that has both reworkability and high durability.
  • the antireflection film with an adhesive layer of the present invention is suitable for use in a self-luminous display device.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)
  • Optical Filters (AREA)
  • Polarising Elements (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

L'invention concerne un film antireflet pourvu d'une couche adhésive sensible à la pression. Ce film antireflet pourvu d'une couche adhésive sensible à la pression possède une couche adhésive sensible à la pression sur au moins l'une des surfaces du film antireflet. La couche adhésive sensible à la pression possède une force adhésive initiale qui n'est pas supérieure à 5 N/25 mm sur la base d'un décollement à 90 degrés effectué à une vitesse de 300 mm/min par rapport au verre non alcalin.
PCT/JP2020/002222 2019-02-06 2020-01-23 Film antireflet pourvu d'une couche adhésive sensible à la pression, dispositif d'affichage de type à émission de lumière spontanée et procédé de fabrication associé WO2020162195A1 (fr)

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KR1020217019309A KR20210116446A (ko) 2019-02-06 2020-01-23 점착제층 구비 반사 방지 필름, 자발광형 표시 장치 및 그 제조 방법
CN202080012326.XA CN113383048A (zh) 2019-02-06 2020-01-23 带粘合剂层的防反射膜、自发光型显示装置及其制造方法

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JP2019-019411 2019-02-06
JP2019019411A JP7366552B2 (ja) 2019-02-06 2019-02-06 粘着剤層付き反射防止フィルム、自発光型表示装置およびその製造方法

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WO2022144752A1 (fr) * 2020-12-28 2022-07-07 Jade Bird Display (shanghai) Limited Structure de micro-del et puce à micro-del comprenant celle-ci
WO2023163149A1 (fr) * 2022-02-28 2023-08-31 日東電工株式会社 Stratifié optique pour dispositif d'affichage oled
US20240023418A1 (en) * 2021-05-27 2024-01-18 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Display module

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