WO2021200678A1 - 反射防止フィルム積層体及びそれを備える物品 - Google Patents

反射防止フィルム積層体及びそれを備える物品 Download PDF

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Publication number
WO2021200678A1
WO2021200678A1 PCT/JP2021/012932 JP2021012932W WO2021200678A1 WO 2021200678 A1 WO2021200678 A1 WO 2021200678A1 JP 2021012932 W JP2021012932 W JP 2021012932W WO 2021200678 A1 WO2021200678 A1 WO 2021200678A1
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Prior art keywords
layer
base material
transparent base
antireflection film
refractive index
Prior art date
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PCT/JP2021/012932
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English (en)
French (fr)
Japanese (ja)
Inventor
田村　崇
匡明 豊嶋
加藤　裕司
弘樹 井上
貴行 久
悠之介 藤田
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Dexerials Corp
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Dexerials Corp
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Publication date
Application filed by Dexerials Corp filed Critical Dexerials Corp
Priority to CN202180023422.9A priority Critical patent/CN115315637A/zh
Priority to KR1020227031058A priority patent/KR102850156B1/ko
Priority to US17/911,718 priority patent/US12461281B2/en
Priority to EP21780574.6A priority patent/EP4130807A4/en
Priority to KR1020257011137A priority patent/KR20250052480A/ko
Publication of WO2021200678A1 publication Critical patent/WO2021200678A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • 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
    • 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
    • G02B1/115—Multilayers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/08—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/354—Applications of adhesives in processes or use of adhesives in the form of films or foils for automotive applications
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Definitions

  • the present invention relates to an antireflection film laminate, and more particularly to an antireflection film laminate that is preferably used in combination with a display or the like provided in an interior of a transportation machine such as an automobile.
  • the present application claims priority based on Japanese Patent Application No. 2020-063354 filed in Japan on March 31, 2020, the contents of which are incorporated herein by reference.
  • an adhesive layer is provided on an optical film such as an antireflection film and attached to the display to improve visibility, prevent the display surface from scattering in the event of an accident, and break the broken glass. It is also conceivable to protect the occupants by suppressing the occurrence of so-called sharp edges protruding from the surface.
  • An object of the present invention is to provide an antireflection film laminate excellent in preventing scattering of the display surface and suppressing the generation of sharp edges while improving visibility, and an article provided with the same.
  • the present invention provides the following means for solving the above problems.
  • the antireflection film laminate according to one aspect of the present invention is a first transparent base material having a first surface and a second surface which is a surface on the back side of the first surface, and on the first surface in order.
  • the antireflection layer including at least the provided hard coat layer, the inorganic multilayer film layer, and the antifouling layer, and the adhesive layer provided on the second surface are provided, and the adhesive layer is a two-layer adhesive layer.
  • a second transparent base material that is sandwiched between the two layers of the pressure-sensitive adhesive layer and directly adheres to each of the two layers of the pressure-sensitive adhesive layer, and emits light having a wavelength of 380 nm to 780 nm from the standard light source D65 at an incident angle of 5 °.
  • the reflectance Y when incident is 0.8% or less, and the breaking force when a conical probe having a diameter of 8 mm is pressed at a piercing test speed of 500 mm / min is 5.7 N or more.
  • the first transparent base material is a plastic film.
  • the antireflection film laminate according to the above aspect may be a PET film in which the second transparent base material has a thickness of less than 12 ⁇ m.
  • the second transparent base material may be a TAC film.
  • the inorganic multilayer film layer is a laminate of a low refractive index material layer and a high refractive index material layer, and the low refractive index material layer and the high refractive index material layer are sputtering films. May be good.
  • the antireflection film laminate according to the above aspect has a storage elastic modulus of 0.20 to 0.10 MPa and a loss tangent of 0.40 to 0.20 at 25 ° C. of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer. There may be.
  • the antireflection film laminate according to the above aspect may have a thickness of 170 ⁇ m or less.
  • the antireflection film laminate according to the above aspect further includes a protective film on the surface of the antifouling layer opposite to the first transparent base material, and is the first transparent base material of the two layers of the pressure-sensitive adhesive layer.
  • a release film may be further provided on the surface of the pressure-sensitive adhesive layer on the side away from the surface opposite to the second transparent base material.
  • the article according to another aspect of the present invention includes the antireflection film laminate of the above aspect.
  • an antireflection film laminate that is excellent in preventing scattering of the display surface and suppressing the generation of sharp edges while improving visibility.
  • FIG. 3A is an enlarged cross-sectional schematic view of a part of the state in which the antireflection film laminate sample shown in FIG. 3A is sandwiched between the sample setting table and the holding plate.
  • FIG. 1 shows a schematic cross-sectional view of the antireflection film laminate according to the embodiment of the present invention.
  • the antireflection film laminate 100 shown in FIG. 1 is formed on a first transparent base material 10 having a first surface 10a and a second surface 10b which is a back surface with respect to the first surface 10a, and on the first surface 10a.
  • the adhesive layer 30 includes an antireflection layer 20 including at least a hard coat layer 21, an inorganic multilayer film layer 22, and an antifouling layer 23 provided in this order, and an adhesive layer 30 provided on the second surface 10b. It consists of two layers of pressure-sensitive adhesive layers 31 and 33 and a second transparent base material 32 sandwiched between the two layers of pressure-sensitive adhesive layers 31 and 33 and directly adhered to each of the two-layer pressure-sensitive adhesive layers 31 and 33.
  • the antireflection film laminate 100 is thin. Specifically, it is preferably 170 ⁇ m or less, and more preferably 140 ⁇ m or less.
  • the antifouling layer 23 has a surface 23a opposite to the surface 23b on the side of the first transparent base material 10.
  • a known protective film 40 may be provided.
  • the protective film 40 include those using polypropylene, polyethylene, polyethylene terephthalate or the like as a base material and having an adhesive layer containing natural rubber, synthetic rubber, acrylic resin or the like as a main component.
  • the surface 33b of the pressure-sensitive adhesive layer 33 on the side away from the first transparent base material 10 on the side opposite to the side surface 33a of the second transparent base material is further known.
  • the release film 50 of the above may be provided. Examples of the release film 50 include a polyethylene terephthalate film having a surface coated with a silicone material or a fluorine-based material.
  • the first transparent base material 10 has a first surface 10a and a second surface 10b which is a surface on the back side of the first surface 10a.
  • the first transparent base material 10 may be formed of a transparent material capable of transmitting light in the visible light region, and for example, a plastic film is preferably used.
  • a plastic film is preferably used.
  • the constituent materials of the plastic film include polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, and polychloride.
  • a reinforcing material may be contained as long as the optical characteristics are not impaired, and examples thereof include cellulose nanofibers and nanosilica.
  • polyester-based resins, acetate-based resins, polycarbonate-based resins, and polyolefin-based resins are preferably used, and specifically, triacetyl cellulose (TAC) base materials and polymethyl methacrylate base materials are preferably used.
  • TAC triacetyl cellulose
  • a glass film can also be used as an inorganic base material.
  • the plastic film is a TAC base material
  • the hard coat layer 21 is formed on one surface side thereof, a permeation layer in which a part of the components constituting the hard coat layer 21 permeates can be formed, and the transparent base material and the hard It is possible to suppress the occurrence of interference fringes due to the adhesion to the coat layer 21 and the difference in refractive index between the layers.
  • the first transparent base material 10 may be a film to which an optical function or a physical function is imparted.
  • films having optical or physical functions include polarizing plates, retardation compensation films, thermal warfare blocking films, transparent conductive films, and luminance improving films.
  • the thickness of the first transparent base material 10 is not particularly limited, but is preferably 25 ⁇ m or more, for example. More preferably, it is 40 ⁇ m or more. If the thickness of the first transparent base material 10 is less than 25 ⁇ m, wrinkles are likely to occur when stress is applied, and when the antireflection film laminate 100 is manufactured, a hard coat is applied on the first transparent base material 10. The operation of continuously forming the layer 21 may be difficult. In addition, there is a concern that the curl will become large and the scratch hardness will deteriorate.
  • the first transparent base material 10 When the first transparent base material 10 is manufactured in roll form, if the thickness of the first transparent base material 10 exceeds 300 ⁇ m, the first transparent base material 10 may not be rolled when the antireflection film laminate 100 is manufactured. , It may be disadvantageous for thinning, weight reduction and cost reduction of the antireflection film laminate 100. Further, when the hard coat layer 21 is laminated, gas (moisture, organic matter, etc.) is likely to be generated from the first transparent base material 10, which may be an obstacle to the formation of the hard coat layer 21.
  • the surface of the first transparent base material 10 may be subjected to etching treatment such as sputtering, corona discharge, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc., or undercoating treatment in advance.
  • etching treatment such as sputtering, corona discharge, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc., or undercoating treatment in advance.
  • etching treatment such as sputtering, corona discharge, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc.
  • undercoating treatment in advance.
  • the antireflection layer 20 is provided on the first surface 10a of the first transparent base material 10, and includes a hard coat layer 21, an inorganic multilayer film layer 22, and an antifouling layer 23 in this order from the first surface 10a side. ..
  • the hard coat layer 21 is a cured layer of an organic substance formed between the first transparent base material 10 and the inorganic multilayer film layer 22, or a cured layer of an organic substance containing an inorganic substance.
  • the hard coat layer 21 may contain silica (Si oxide) particles or alumina (aluminum oxide) particles as a filler in the binder resin. These silica particles and alumina particles may be exposed from the surface of the hard coat layer 21 on the inorganic multilayer film layer 22 side. According to such a configuration, the inorganic multilayer film layer 22 can be strongly bonded to the binder resin of the hard coat layer 21, and more firmly adheres to the exposed silica particles and alumina particles. The adhesion to the inorganic multilayer film layer 22 is improved, and the scratch resistance of the antireflection film laminate 100 can be improved.
  • the silica particles and alumina particles that are the fillers of the hard coat layer 21 have an average particle diameter of 800 nm or less, preferably 780 nm or less, and more preferably 100 nm or less in a single particle state, and the binder resin of the hard coat layer 21. It is preferable that the particles are dispersed in. By dispersing silica particles and alumina particles as such a filler, fine irregularities can be formed on the surface of the hard coat layer 21, and the hardness of the hard coat layer 21 is increased and the antireflection film laminate 100 is formed. It is possible to improve the adhesion with.
  • a transparent resin is preferable, and for example, an ionizing radiation curable resin, a thermoplastic resin, a thermosetting resin, etc., which are resins that are cured by ultraviolet rays or electron beams, can be used.
  • Examples of the ionizing radiation curable resin used for the binder resin of the hard coat layer 21 include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like.
  • Examples of the compound which is an ionizing radiation curable resin having two or more unsaturated bonds include trimethylpropantri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and dipropylene.
  • Glycoldi (meth) acrylate pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, Trimethylol Propanetri (meth) Acrylate, Ditrimethylol Propanetetra (Meta) Acrylate, Dipentaerythritol Penta (Meta) Acrylate, Tripentaerythritol Octa (Meta) Acrylate, Tetrapentaerythritol Deca (Meta) Acrylate, Isocyanuric Acid Tri (meth) acrylate, di (meth) isocyanurate acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate
  • pentaerythritol triacrylate PETA
  • dipentaerythritol hexaacrylate DPHA
  • pentaerythritol tetraacrylate PETA
  • (meth) acrylate refers to methacrylate and acrylate.
  • a resin obtained by modifying the above-mentioned compound with PO (propylene oxide), EO (ethylene oxide, CL (caprolactone), or the like can also be used as the ionizing radiation curable resin.
  • thermoplastic resin used for the binder resin of the hard coat layer 21 examples include a styrene resin, a (meth) acrylic resin, a vinyl acetate resin, a vinyl ether resin, a halogen-containing resin, an alicyclic olefin resin, and a polycarbonate resin.
  • examples thereof include resins, polyester resins, polyamide resins, cellulose derivatives, silicone resins and rubbers or elastomers.
  • the thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds).
  • styrene resin, (meth) acrylic resin, alicyclic olefin resin, polyester resin, cellulose derivative (cellulose ester, etc.) and the like are preferable.
  • thermosetting resin used for the binder resin of the hard coat layer 21 examples include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine.
  • phenol resin urea resin
  • diallyl phthalate resin diallyl phthalate resin
  • melamine resin guanamine resin
  • unsaturated polyester resin polyurethane resin
  • epoxy resin epoxy resin
  • aminoalkyd resin aminoalkyd resin
  • melamine examples of the thermosetting resin used for the binder resin of the hard coat layer 21
  • -Urea cocondensate resin silicon resin
  • polysiloxane resin including so-called silsesquioxane such as cage and ladder
  • the hard coat layer 21 may contain an organic resin and an inorganic material, or may be an organic-inorganic hybrid material.
  • an organic resin and an inorganic material may be an organic-inorganic hybrid material.
  • examples of the inorganic material include silica, alumina, zirconia and titania
  • examples of the organic material include acrylic resin.
  • the thickness of the hard coat layer 21 is not particularly limited, but is preferably 0.5 ⁇ m or more, for example. More preferably, it is 1 ⁇ m or more. The upper limit is 100 ⁇ m or less. If the thickness of the hard coat layer 21 is less than 0.5 ⁇ m, there is a concern that the strength will be insufficient and the scratch hardness will deteriorate. On the other hand, if the thickness of the hard coat layer 21 is too thick, it may be disadvantageous in reducing the thickness, weight and cost of the antireflection layer 10.
  • the hard coat layer 21 may be a single layer or a plurality of layers. Further, the hard coat layer 21 may be further provided with known functions such as an ultraviolet absorbing performance, an antistatic performance, a refractive index adjusting function, and a hardness adjusting function. Further, the function imparted to the hard coat layer 21 may be imparted to a single hard coat layer 21 or may be imparted to a plurality of layers separately.
  • the inorganic multilayer film layer 22 is a laminate that exhibits an optical function, and in the present embodiment, an antireflection function.
  • the inorganic multilayer film layer 22 of the present embodiment is formed by alternately laminating low refractive index layers a and high refractive index layers b in order from the hard coat layer 21 side.
  • the layer 23 side can be a laminated body of a total of 5 layers each having a low refractive index layer a. Of these, the low refractive index layer a in contact with the hard coat layer 21 has a function as an adhesive layer to the hard coat layer 21.
  • the number of layers of the low refractive index layer a and the high refractive index layer b is not limited to five, and the low refractive index layer a and the high refractive index layer b having an arbitrary number of layers are formed. Can be done.
  • the low refractive index layer a is a layer containing SiO 2 (an oxide of Si) or the like as a main component.
  • the SiO 2 monolayer film is colorless and transparent, and the refractive index of the low refractive index layer is preferably 1.20 to 1.60, and more preferably 0 to 1.50.
  • the inorganic thin film layer containing an oxide of Si may contain another element within 50%. Na may be contained for the purpose of improving durability, and Zr, Al, or N may be contained for the purpose of improving hardness. The content is preferably 10% or less.
  • the refractive index of the high refractive index layer is preferably 2.00 to 2.60, and more preferably 2.10 to 2.45.
  • Examples of such a high refractive index dielectric include niobium pentoxide (Nb 2 O 5 , refractive index 2.33), titanium oxide (TiO 2 , refractive index 2.33 to 2.55), and tungsten oxide (WO 3). , Refractive index 2.2), Celium oxide (CeO 2 , Refractive index 2.2), Tantalum pentoxide (Ta 2 O 5 , Refractive index 2.16), Zinc oxide (ZnO, Refractive index 2.1), Oxidation Examples thereof include indium tin (ITO, refractive index 2.06).
  • the light incident from the antifouling layer 23 side is prevented from being reflected in one direction, and the antireflection function is exhibited. be able to.
  • the low refractive index layer a and the high refractive index layer b can be formed by sputtering.
  • the sputtering target may be changed between the time of forming the low refractive index layer a and the time of forming the high refractive index layer b.
  • a layer made of the target material and a layer made of an oxide of the target material are alternately formed, and a low refractive index layer and a high refractive index layer are formed. May be.
  • the film thickness of the low refractive index layer a constituting the inorganic multilayer film layer 22 is appropriately selected according to the wavelength range in which the antireflection function is required, but may be, for example, 1 nm or more and 200 nm or less.
  • the film thickness of the high refractive index layer b may be in the range of 15 nm or more and 200 nm or less.
  • the film thicknesses of the low refractive index layer a and the high refractive index layer b do not necessarily have to be the same, and can be appropriately selected according to the design of the inorganic multilayer film layer 22.
  • the antifouling layer 23 is formed on the outermost surface of the inorganic multilayer film layer 22 to prevent the inorganic multilayer film layer 22 from being soiled, and also to prevent the inorganic multilayer film layer 22 from being worn due to wear resistance when applied to a touch panel or the like. Suppress.
  • a compound composed of a fluorine-modified organic group and a reactive silyl group is preferably used.
  • a fluorine-modified organic group and a reactive silyl group for example, alkoxysilane
  • FDTS perfluorodecyltriethoxysilane
  • Examples of commercially available products include Optool DSX (manufactured by Daikin Corporation) and KY-1901 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the antifouling layer 23 is a light stabilizer, an ultraviolet absorber, a colorant, an antistatic agent, a lubricant, a leveling agent, an antifoaming agent, an antioxidant, a flame retardant, an infrared absorber, and a surfactant, if necessary. Additives such as may be further included.
  • the antifouling layer 23 may be formed by diluting the above-mentioned fluorine compound with a soluble solvent, applying it on the inorganic multilayer film layer 22 using a known coating device such as a bar coater, and then drying it. It may be formed by a vapor deposition method or the like.
  • the adhesive layer 30 is provided on the second surface 10b of the first transparent base material 10, and is provided on both sides of the second transparent base material 32 and the second transparent base material 32. It consists of. The entire surface of the second transparent base material 32 is directly adhered to each of the two adhesive layers 31 and 33.
  • the second transparent base material 32 may be formed of a transparent material capable of transmitting light in the visible light region, and for example, a plastic film is preferably used.
  • a plastic film is preferably used.
  • the constituent materials of the plastic film include polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, and polychloride.
  • polyester-based resins preferably, acetate-based resins, polycarbonate-based resins, and polyolefin-based resins are preferably used, and specifically, triacetyl cellulose (TAC) base materials, polyethylene terephthalate base materials, and polymethyl methacrylate resins are preferably used. Used.
  • TAC triacetyl cellulose
  • the tensile elastic modulus of the material of the second transparent base material 32 is preferably 490 to 4500 MPa.
  • the refractive index of the second transparent base material 32 preferably has a small difference from the refractive index of the first transparent base material 10 so as not to impair the optical characteristics of the antireflection film laminate, but is, for example, less than 0.1. can do.
  • the pressure-sensitive adhesive layers 31 and 33 of the present embodiment can use various pressure-sensitive pressure-sensitive adhesives such as rubber-based pressure-sensitive adhesives, acrylic-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives, but can be colorless and transparent. Therefore, an acrylic pressure-sensitive adhesive is preferable from the viewpoints of reducing the loss of optical properties of the antireflection film laminate, easily adjusting the adhesiveness, and selecting the material.
  • the difference in refractive index between the pressure-sensitive adhesive layers 31 and 33 and the second transparent base material 32 is preferably as small as possible from the viewpoint of not impairing the optical characteristics of the antireflection film laminate, but is preferably 0.12 or less, for example. It can be, and even 0.05 or less.
  • the pressure-sensitive adhesive layers 31 and 33 formed on both surfaces of the second transparent base material 32 are made of the same composition but different compositions from the viewpoint of desired optical properties and impact resistance. Although it may be one, it is preferable that the difference in refractive index on both sides is small in terms of optical characteristics.
  • the storage elastic moduli of the pressure-sensitive adhesive layers 31 and 33 have a storage elastic modulus of 0.20 to 0.10 MPa at 25 ° C. and a loss tangent of 0.40 to 0.20. It is desirable to have.
  • the method for producing the pressure-sensitive adhesive layer 30 is not particularly limited, and a method of applying a pressure-sensitive adhesive composition diluted with a solvent to the second transparent base material 32 and drying the pressure-sensitive adhesive layer 30 and an ultraviolet curable composition in which the pressure-sensitive adhesive composition is solvent-free.
  • the thickness of the adhesive layer is not particularly limited, but is preferably about 5 to 30 ⁇ m.
  • the adhesive layer produced by the above method is used with one of the adhesive layers. There is a method of pasting them together.
  • the adhesive layer may be first attached to the second surface of the first transparent base material, and then the antireflection layer may be formed on the first surface.
  • one of the pressure-sensitive adhesive layers is formed on the second surface of the first transparent base material, and then a release film is attached for protection, and an antireflection layer is formed on the first surface of the first transparent base material. After that, the release film is peeled off, and a separately manufactured material having an adhesive layer provided on only one side of the second transparent base material is attached.
  • the article in the present embodiment is provided with the above-mentioned antireflection film laminate on the display surface of the image display unit, such as a liquid crystal display panel or an organic EL display panel.
  • the image display unit such as a liquid crystal display panel or an organic EL display panel.
  • the article is not limited to an image display device, for example, a window glass or goggles on which the antireflection film laminate of the present embodiment is provided on the surface, a light receiving surface of a solar cell, a smartphone screen, or a personal computer display.
  • the first transparent base material is a TAC film having a thickness of 80 ⁇ m, and the photocurable resin composition shown in Table 1 below is applied to the first surface of the TAC film with a bar coater, and then the resin composition is photopolymerized and dried. , A hard coat layer having a thickness of 5 ⁇ m was formed.
  • the surface treatment of the hard coat layer was performed at a processing speed of 8300 W ⁇ min / m 2 for the glow discharge treatment.
  • an adhesion layer made of SiOx having a thickness of 10 nm is formed by sputtering, and an Nb 2 O 5 film (high refractive index layer) and a SiO 2 layer (low refractive index layer) are formed on the adhesion layer.
  • Nb 2 O 5 film high refractive index layer
  • SiO 2 layer low refractive index layer
  • an AR layer inorganic multilayer film layer
  • an antifouling layer having a thickness of 10 nm made of an alkoxysilane compound having a perfluoropolyether group was formed on the AR layer to obtain an antireflection layer.
  • a TAC film (refractive index 1.49) having a thickness of 25 ⁇ m is used as the second transparent base material, and an acrylic adhesive having a refractive index of 1.47 is applied to both sides thereof with a bar coater so as to have a thickness of 10 ⁇ m.
  • a pressure-sensitive adhesive layer was formed to obtain a pressure-sensitive adhesive layer.
  • the first surface of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive layer was bonded to the second surface of the first transparent base material to obtain an antireflection film laminate having the pressure-sensitive adhesive layer.
  • Example 2 An antireflection film laminate was obtained in the same manner as in Example 1 except that the second transparent base material was a transparent PET film having a thickness of 6 ⁇ m (refractive index 1.58).
  • Example 3 An antireflection film laminate was obtained in the same manner as in Example 1 except that the second transparent base material was a transparent PET film having a thickness of 9 ⁇ m (refractive index 1.58).
  • Example 2 An antireflection film laminate was obtained in the same manner as in Example 1 except that the second transparent base material was a transparent PET film (refractive index 1.58) having a thickness of 16 ⁇ m.
  • Example 3 An antireflection film laminate was obtained in the same manner as in Example 1 except that the second transparent base material was a transparent PET film (refractive index 1.58) having a thickness of 25 ⁇ m.
  • the puncture test is a sticking of an antireflection film laminated sample using an adhesive layer on an opening of a sample setting table (thickness 9 mm) provided with a circular opening having a height of 9 mm and a diameter of 9 mm.
  • a sample setting table thickness 9 mm
  • FIG. 3B after preparing a holding plate (thickness 3 mm) having a circular opening with a height of 3 mm and a diameter of 11 mm, holding and fixing the openings so that the openings overlap each other (see FIG. 4), antireflection is prevented.
  • a predetermined piercing jig probe
  • the antireflection film laminate sample breaks (breaks). It measures the force (breaking force) at the time.
  • the sample for the piercing test was prepared by cutting out the antireflection film laminates of the above-mentioned Examples and Comparative Examples into 30 mm squares.
  • a stainless steel piercing jig (conical probe) having a diameter of 8 mm and a conical tip side was used. The length of the conical portion is 6 mm, and the tip of the conical portion is sharp.
  • the antireflection film laminate of the present invention requires a breaking force of 5.7 N or more.
  • the ball drop test is a test sample prepared by laminating the antireflection film laminates of the above-mentioned Examples and Comparative Examples to the cover glass of an 8-inch LCD module with a cover glass, and the bonded surface.
  • a 6.8 kg iron ball is dropped from a height of 2.4 m on the test sample with the upper surface as the upper surface to prevent the broken cover glass from scattering and to prevent the broken cover glass from generating sharp edges. It is to evaluate.
  • the LCD module with a cover glass is an LCD module provided with chemically strengthened soda lime glass having a thickness of 1.1 mm as a cover glass.
  • the reflectance Y means the luminosity factor correction reflectance (the luminosity factor corresponds to the color sensation of the human eye, that is, the sensitivity of the color sensory cells of the retina). Is the luminosity factor corrected by using the color matching function Y ( ⁇ ) defined by CIE for the spectral reflectance of 380 nm to 780 nm with respect to the C light source defined in JIS Z8701.
  • the reflected light Y can be measured using a spectrophotometer or the like. The measurement was performed using a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Science Corporation) under the conditions of an incident angle of 5 ° and a standard light source D65.
  • the reflectance Y needs to be 0.8% or less.
  • Total light transmittance means all the light transmitted when the light equivalent to the standard light source D65 is incident on the measurement target, and is measured using a haze meter manufactured in accordance with the method specified in JIS K7361. The value.
  • the total light transmittance was measured using a haze meter NDH-5000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
  • the total light transmittance is preferably 94% or more.
  • Rainbow unevenness refers to rainbow-colored interference unevenness in which when light is reflected at each interface, the reflected light interferes with each other.
  • rainbow unevenness a laminated product of antireflection film and soda lime glass were laminated and rotated while being superimposed on a liquid crystal display displaying white, and it was confirmed whether or not there was a change in color tone.
  • the difference in refractive index between the second transparent base material and the pressure-sensitive adhesive layer is preferably 0.12 or less.
  • the antireflection film laminate according to the embodiment has a reflectance lower than a predetermined value, sharp edges are generated while having antireflection performance particularly suitable when combined with a display provided in a transportation machine such as an automobile. Therefore, when an occupant hits the head of the display due to an impact such as an accident, even if the glass constituting the display breaks, it can be expected to reduce the injury to the occupant. ..
  • the antireflection laminate according to Comparative Example 1 has a reflectance satisfying a predetermined performance, the breaking force in the piercing test is low, the occurrence of sharp edges cannot be suppressed, and the occupant protection performance in the event of an accident is inferior. Is inferred.
  • the antireflection film laminates according to Comparative Examples 2 to 3 have high breaking force in the piercing test, but have high reflectance and inferior antireflection function, and are particularly suitable when combined with a display provided in a transportation machine such as an automobile. It doesn't become a thing.

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  • Organic Chemistry (AREA)
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US17/911,718 US12461281B2 (en) 2020-03-31 2021-03-26 Anti-reflective film laminate and product provided with same
EP21780574.6A EP4130807A4 (en) 2020-03-31 2021-03-26 Anti-reflective film laminate and product provided with same
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