WO2017068788A1 - Film antireflet et son procédé de production - Google Patents

Film antireflet et son procédé de production Download PDF

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Publication number
WO2017068788A1
WO2017068788A1 PCT/JP2016/004647 JP2016004647W WO2017068788A1 WO 2017068788 A1 WO2017068788 A1 WO 2017068788A1 JP 2016004647 W JP2016004647 W JP 2016004647W WO 2017068788 A1 WO2017068788 A1 WO 2017068788A1
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Prior art keywords
layer
antireflection
silver fine
refractive index
antireflection film
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PCT/JP2016/004647
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English (en)
Japanese (ja)
Inventor
直希 小糸
英正 細田
亮 松野
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富士フイルム株式会社
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Priority to JP2017546409A priority Critical patent/JPWO2017068788A1/ja
Publication of WO2017068788A1 publication Critical patent/WO2017068788A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters

Definitions

  • the present invention relates to a transparent antireflection film having an antireflection function for incident light, and a method for producing the same.
  • an antireflection film provided with an antireflection film on a transparent substrate has been provided on the glass surface of the display in order to prevent a decrease in visibility due to reflection of an external light source or landscape.
  • an antireflection film for visible light a structure including a dielectric multilayer film or a visible light wavelength absorption layer formed of a metal fine particle layer in the multilayer film is known.
  • Patent Document 1 proposes an antireflection film that includes a laminate composed of a flat particle, particularly a metal fine particle-containing layer containing silver nanodisks, and a dielectric on a transparent substrate. According to such an antireflection film, a low antireflection effect in a wide band can be obtained.
  • Examples of the optical surface to which the antireflection film is applied include a glass surface of a display, a window glass surface of a building material or an in-vehicle use. Unlike display, window glass for building materials and in-vehicle use is installed outdoors, so it is exposed to sunlight for a long time (several years). Therefore, material deterioration is remarkable, and it is necessary to provide an ultraviolet absorbing layer in the antireflection film to protect the substrate.
  • Patent Document 2 a hard coat containing a specific ultraviolet absorber and an active energy ray curable resin (ultraviolet curable resin) is paid attention to the problem that reflection characteristics are deteriorated or haze is deteriorated by ultraviolet light such as sunlight.
  • An antireflection film having improved light resistance by providing a layer (ultraviolet absorbing layer) has been proposed.
  • JP 2015-129909 A Japanese Patent Laying-Open No. 2015-102621
  • Patent Document 2 increasing the light resistance is considered to mean suppressing the deterioration of reflection characteristics and the deterioration of haze.
  • the present inventors have found that when the antireflection film having the configuration of Patent Document 2 is exposed to sunlight outdoors for a long period of time, the antireflection film turns yellow. In the conventional antireflection film, yellowing of the base material that occurs when exposed to sunlight for a long time cannot be prevented, and there is actually no antireflection film that can be practically used outdoors.
  • the antireflection film of the present invention comprises a transparent base material, an antireflection layer provided on one side of the transparent base material, and a binder resin and an ultraviolet absorber provided between the transparent base material and the antireflection layer.
  • An antireflection laminate having an ultraviolet absorbing layer containing, The binder resin consists of a cured product of an aqueous resin composition, The content of the ultraviolet absorber is 290 mg / m 2 or more, The average absorbance of light having a wavelength of 320 nm to 330 nm in the antireflection laminate is 1.5 or more.
  • the thickness of the ultraviolet absorbing layer is preferably 1.0 ⁇ m or more and 10 ⁇ m or less.
  • the ultraviolet absorber preferably contains a compound containing a triazine ring.
  • the content of the ultraviolet absorber is preferably 3000 mg / m 2 or less.
  • the resin in the aqueous resin composition is preferably polyurethane or acrylic resin.
  • the glass transition temperature of the resin in the aqueous resin composition is preferably 125 ° C. or higher.
  • the antireflection layer comprises a high refractive index layer having a higher refractive index than the transparent substrate and a low refractive index layer having a lower refractive index than the transparent substrate from the transparent substrate side. It can be set as the structure prepared in order.
  • the antireflection layer includes a silver fine particle-containing layer containing a plurality of silver fine particles, and 60% or more of the total number of the plurality of silver fine particles has a ratio of the diameter to the thickness of 3 or more. It is a tabular grain, and the main plane of the tabular grain is oriented in the range of 0 ° to 30 ° with respect to the surface of the silver fine particle-containing layer, and a plurality of silver fine particles form a conductive path in the silver fine particle-containing layer. It is preferable that it is arranged without doing.
  • the method for producing an antireflection film of the present invention includes a transparent substrate, an antireflection layer provided on one side of the transparent substrate, and a binder resin and an ultraviolet absorber provided between the transparent substrate and the antireflection layer.
  • a method for producing an antireflection film comprising an antireflection laminate having an ultraviolet absorbing layer comprising: The content of the ultraviolet absorber is 290 mg / m 2 or more by applying a coating solution containing the ultraviolet absorber and the aqueous resin composition that becomes a binder resin by curing on a transparent substrate and drying it. Forming an ultraviolet absorbing layer; A process for forming an antireflection layer on the ultraviolet absorbing layer.
  • the antireflection film of the present invention comprises an ultraviolet absorbing layer containing a binder resin composed of a cured product of an aqueous resin composition and an ultraviolet absorber between a transparent substrate and an antireflection layer, and contains an ultraviolet absorber.
  • the figure explaining the angle (theta) made is shown. It is a figure which shows the distribution state (100% isolation) of the silver fine particle in a silver fine particle content layer. It is a figure which shows the distribution state (50% isolation) of the silver fine particle in a silver fine particle content layer. It is a figure which shows the distribution state (10% isolation) of the silver fine particle in a silver fine particle content layer.
  • FIG. 1 is a schematic cross-sectional view showing a configuration of an antireflection film 1 according to an embodiment of the present invention.
  • the antireflection film 1 of this embodiment includes a transparent substrate 10, an antireflection layer 30 provided on one surface side of the transparent substrate 10, and the transparent substrate 10 and the antireflection layer 30.
  • an antireflection laminate 40 having an ultraviolet absorbing layer 20 including a binder resin 22 and an ultraviolet absorber 21, which are provided between the two.
  • the binder resin 22 is made of a cured product of an aqueous resin composition.
  • the aqueous resin composition refers to a composition having a property of solidifying when the aqueous solvent contained therein is removed.
  • the types of general water-based resin compositions include forced emulsification resin obtained by forcibly emulsifying a non-emulsifiable / water-soluble polymer using a surfactant or the like, and self-emulsified / dispersed self-emulsifiable polymer. Examples thereof include emulsifying resins and water-soluble resins in which a water-soluble polymer is dissolved.
  • the forced emulsifying resin and the self-emulsifying resin are in a dispersed state in which the resin has a particle size at the stage of the composition.
  • the water-soluble resin means that the resin does not have a particle size and is in a dissolved state at the composition stage.
  • the aqueous solvent is a dispersion medium whose main component is water, and the content of water contained in the solvent is preferably 70% to 100%, more preferably 80% to 100%.
  • Solvents other than water are soluble in water, such as alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, glycol ethers such as N-methylpyrrolidone (NMP), tetrahydrofuran and butyl cellosolve, etc.
  • a solvent is preferably used.
  • amines such as surfactants, ammonia, triethylamine, N, -N dimethylethanolamine are added to the dispersion to improve the dispersion stability of the polymer in the water-based resin composition, coating properties, and film properties after drying. It may contain several percent.
  • Specific examples of the water-based resin composition include polyester, polyolefin, polyester, acrylic resin, polyurethane and the like.
  • the binder resin 22 preferably contains at least one resin selected from the group consisting of polyurethane and acrylic resin from the viewpoint that the strength and transparency of the formed coating film are good.
  • the acrylic resin in the present invention is a resin containing a monomer having at least one group selected from an acryloyl group and a methacryloyl group as a polymerization component, and is formed by polymerization when the total mass of the acrylic resin is 100% by mass. It is preferable that the total mass of the repeating units is more than 50% by mass.
  • a monomer having at least one group selected from an acryloyl group and a methacryloyl group is hereinafter referred to as “(meth) acryl monomer” as appropriate.
  • the acrylic resin is obtained by homopolymerizing (meth) acrylic monomers or copolymerizing with other monomers.
  • the acrylic resin is a copolymer of a (meth) acrylic monomer and another monomer
  • the other monomer to be copolymerized with the (meth) acrylic monomer may be a monomer having a carbon-carbon double bond, and an ester A monomer having a bond or urethane bond may be used.
  • the copolymer of the (meth) acrylic monomer and other monomer may be any of a random copolymer, a block copolymer, and a graft copolymer.
  • the acrylic resin in the present invention includes a polymer, a polyurethane solution or a polyurethane dispersion obtained by homopolymerizing or copolymerizing a (meth) acrylic monomer with another monomer in a polyester solution or a polyester dispersion.
  • a polymer solution or dispersion other than an acrylic resin such as a polymer obtained by homopolymerizing an acrylic monomer or copolymerizing with another monomer
  • the (meth) acrylic monomer is homopolymerized or copolymerized with another monomer.
  • Polymers obtained by polymerization and mixtures containing other polymers such as polyester resins and urethane resins are included.
  • the acrylic resin may have at least one group selected from a hydroxy group and an amino group in order to further improve the adhesion between the ultraviolet absorbing layer and the adjacent layer.
  • (meth) acrylic monomer that can be used for the synthesis of the acrylic resin.
  • Representative (meth) acrylic monomers include, for example, (meth) acrylic acid; hydroxyalkyl (meta) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate; (meth) acrylamide; diacetone acrylamide, N -N-substituted acrylamides such as methylolacrylamide; (meth) acrylonitrile; silicon-containing (meth) acrylic monomers such as ⁇ -methacryloxypropyltrimethoxysilane.
  • a commercially available product may be used as the acrylic resin.
  • Commercially available acrylic resins that can be used in the UV absorbing layer include Julimer (registered trademark) ET-410 (manufactured by Toa Gosei Chemical Co., Ltd.), AS-563A (trade name: manufactured by Daicel Finechem Co., Ltd.), Bonron (registered) (Trademark) XPS-002 (made by Mitsui Chemicals, Inc.) etc. are mentioned.
  • Polyurethane resin is a general term for polymers having a urethane bond in the main chain, and is usually a reaction product of diisocyanate and polyol.
  • diisocyanate that can be used for the synthesis of the polyurethane resin include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). It is done.
  • the polyol that can be used for the synthesis of the polyurethane resin include ethylene glycol, propylene glycol, glycerin, hexanetriol, and the like.
  • a binder for the ultraviolet absorbing layer in addition to a general polyurethane resin, a polyurethane resin obtained by subjecting a polyurethane resin obtained by the reaction of diisocyanate and polyol to chain extension treatment to increase the molecular weight can be used.
  • the diisocyanate, polyol, and chain extension treatment described for the polyurethane resin are described in detail in, for example, “Polyurethane Handbook” (edited by Keiji Iwata, Nikkan Kogyo Shimbun, published in 1987), and described in the “Polyurethane Handbook”.
  • the description relating to the polyurethane resin and its raw materials can be applied to the present invention depending on the purpose.
  • polyurethane resin Commercial products may be used as the binder.
  • Commercially available products include Superflex (registered trademark) 470, 210, 150HS, 150HF, Elastron (registered trademark) H-3 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Hydran (registered trademark) AP-20, AP -40F, WLS-210 (above, manufactured by DIC Corporation), Takelac (registered trademark) W-6061, WS-5100, WS-4000, WSA-5920, Olester (registered trademark) UD-350 (above, Mitsui) Chemical Co., Ltd.).
  • the glass transition temperature Tg of resin of the water-system resin composition which comprises the binder resin 22 is 125 degreeC or more. If Tg is 125 degreeC or more, the fall of film
  • the ultraviolet absorber 21 is contained in the coated and formed ultraviolet absorbing layer 20 in an amount of 290 mg or more per unit area (1 m 2 ).
  • the content of the ultraviolet absorber 21 in the ultraviolet absorbing layer 20 is mass (mg / m 2 ) per unit area.
  • the ultraviolet absorber 21 preferably contains a compound containing a triazine ring.
  • the compound containing a triazine ring is represented by the following general formula (I).
  • Formula (I) Q 1 -Q 2 -OH In the formula, Q 1 represents a 1,3,5-triazine ring.
  • Q 2 represents an aromatic ring, preferably a benzene ring.
  • R 1 represents an alkyl group having 1 to 18 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; a phenyl group, a hydroxy group, or one carbon atom.
  • R 2 is independently of each other an alkyl group having 6 to 18 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; COOR 4 ; CN; —CO—R 5 ; a halogen atom; a trifluoromethyl group; —O—R 3 is represented.
  • R 3 represents the definition given for R 1 .
  • R 4 represents an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; Or R 4 may be interrupted with one or more —O—, —NH—, —NR 7 —, —S— and substituted with OH, a phenoxy group or an alkylphenoxy group having 7 to 18 carbon atoms; And represents an alkyl group having 3 to 50 carbon atoms.
  • R 5 is H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 2 to 18 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; A bicycloalkyl group having 6 to 15 carbon atoms; a bicycloalkenyl group having 6 to 15 carbon atoms; and a tricycloalkyl group having 6 to 15 carbon atoms.
  • R 6 is H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; To express.
  • R 7 and R 8 each independently represent an alkyl group having 1 to 12 carbon atoms; an alkoxyalkyl group having 3 to 12 carbon atoms; a dialkylaminoalkyl group having 4 to 16 carbon atoms; or the number of carbon atoms Represents a cycloalkyl group having 5 to 12; or R 7 and R 8 together represent an alkylene group having 3 to 9 carbon atoms, an oxaalkylene group having 3 to 9 carbon atoms, or an aza having 3 to 9 carbon atoms. Represents an alkylene group.
  • R 9 is an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 2 to 18 carbon atoms; a phenyl group; a cycloalkyl group having 5 to 12 carbon atoms; a phenylalkyl group having 7 to 11 carbon atoms; A bicycloalkyl group having 6 to 15 carbon atoms; a bicycloalkylalkyl group having 6 to 15 carbon atoms, a bicycloalkenyl group having 6 to 15 carbon atoms; or a tricycloalkyl group having 6 to 15 carbon atoms.
  • R 10 represents an alkyl group having 1 to 12 carbon atoms; a phenyl group; a naphthyl group; or an alkylphenyl group having 7 to 14 carbon atoms.
  • R 11 is independently of each other H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 6 carbon atoms; a phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; a halogen atom; Represents an alkoxy group of ⁇ 18.
  • R 12 represents an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 3 carbon atoms.
  • R 13 and R ′ 13 each independently represent H; an alkyl group having 1 to 18 carbon atoms; a phenyl group.
  • R 14 represents an alkyl group having 1 to 18 carbon atoms; an alkoxyalkyl group having 3 to 12 carbon atoms; a phenyl group; a phenyl-alkyl group having 1 to 4 carbon atoms.
  • R 15 , R ′ 15 and R ′′ 15 each independently represent H or CH 3 .
  • R 16 represents H; —CH 2 —COO—R 4 ; an alkyl group having 1 to 4 carbon atoms; or CN.
  • R 17 represents H; —COOR 4 ; an alkyl group having 1 to 17 carbon atoms; or a phenyl group.
  • X represents —NH—; —NR 7 —; —O—; —NH— (CH 2 ) p —NH—; or —O— (CH 2 ) q —NH—.
  • R 1 , R 2 and R 11 contains two or more carbon atoms.
  • a commercially available product may be used as the compound containing a triazine ring.
  • TINUVIN registered trademark
  • 479DW, 477DW above, manufactured by BASF Corporation
  • the ultraviolet absorber 21 only one type of compound containing a triazine ring may be used, or a mixture of two or more types of compounds containing a triazine ring may be used.
  • UV absorbers such as benzotriazole, benzophenone, oxanilide, salicylate, cyanoacrylate, and formamidine are used alone or mixed with a compound containing a triazine ring. May be used.
  • the content of the ultraviolet absorber 21 is preferably 3000 mg / m 2 or less, and more preferably 400 mg / m 2 or more.
  • the average absorbance of light having a wavelength of 320 to 330 nm in the antireflection laminate 40 of the antireflection film 1 having the above structure is 1.5 or more.
  • the average absorbance is more preferably 1.7 or more.
  • the average absorbance of the antireflection laminate 40 is transparent in a state where the antireflection laminate 40 is not provided from the average absorbance obtained by irradiating the antireflection film 1 with ultraviolet light from the surface on the antireflection layer 30 side.
  • the average absorbance obtained by irradiating only the substrate 10 with ultraviolet light is subtracted.
  • the content of the ultraviolet absorber 21 in the ultraviolet absorbing layer 20 is 290 mg / m 2 or more, an average absorbance of 1.5 or more with respect to light having a wavelength of 320 to 330 nm in the laminate 40 is realized.
  • the thickness of the ultraviolet absorbing layer 20 is preferably 1 ⁇ m to 10 ⁇ m, more preferably 3 ⁇ m to 8 ⁇ m, and particularly preferably 4 ⁇ m to 6 ⁇ m. If the thickness of the ultraviolet absorption layer 20 is 1 ⁇ m or more, an increase in haze due to the ultraviolet absorbent 21 contained in the ultraviolet absorption layer 20 can be suppressed, and if the thickness is 10 ⁇ m or less, the ultraviolet absorption layer 20. An increase in haze due to the binder resin 22 inside can be suppressed.
  • the antireflection film of the present invention satisfies the absorbance of 1.5 or more in the antireflection laminate, and thus is caused by exposure to sunlight for a long time. Yellowing of the transparent substrate can be suppressed.
  • an ultraviolet (UV ray) curable resin as a binder resin of an ultraviolet absorbing layer. This is because thermosetting resins are generally considered inferior to UV ray curable resins in terms of film hardness and haze.
  • the inventors may be able to add a sufficient UV absorber because a curing failure may occur if the UV absorber is sufficiently added. It was found that it was difficult to suppress yellowing of the substrate. And, the present inventors are not so-called thermosetting type resin among so-called thermosetting resins, but as described above, so-called water-based resin composed of water-soluble resin and water-dispersible resin as binder resin. As a result, the inventors have found that a sufficient amount of an ultraviolet absorber can be added without causing a decrease in film hardness and an increase in haze, and the present invention has been achieved.
  • the combination of the binder resin and the ultraviolet absorber include Takelac WS-4000 as the binder resin and TINUVIN-479DW as the ultraviolet absorber.
  • the process for forming the ultraviolet absorbing layer in the method for producing an antireflection film of the present invention will be described.
  • the ultraviolet absorbing layer is formed by applying a coating liquid containing an ultraviolet absorbent and an aqueous resin composition that becomes a binder resin by curing on a transparent substrate and drying it.
  • the addition amount and coating thickness of the ultraviolet absorber are controlled so that the ultraviolet absorbing layer has an ultraviolet absorber content of 290 mg / m 2 or more.
  • the addition amount of the ultraviolet absorber in the coating solution is, for example, 2 to 15% by mass. It is also preferable to add a surfactant or a film-forming aid to the coating solution for forming the ultraviolet absorbing layer.
  • a coating method is preferable.
  • Prepare a coating solution for forming an ultraviolet absorbing layer and use a known method such as a dip coater, die coater, slit coater, bar coater, or gravure coater to apply the coating solution for forming an ultraviolet absorbing layer on a transparent substrate. Apply.
  • the coating liquid amount of the ultraviolet absorbing layer is preferably 1.0 to 100 g / m 2 , more preferably 3.0 to 50 g / m 2 .
  • the transparent substrate prefferably, it is also preferable to perform surface treatment such as corona treatment, glow treatment, atmospheric pressure plasma treatment, flame treatment, and UV treatment on the transparent substrate before applying the ultraviolet absorbing layer. It is preferable to provide a step of drying the ultraviolet absorbing layer after the coating liquid for forming the ultraviolet absorbing layer is applied.
  • surface treatment such as corona treatment, glow treatment, atmospheric pressure plasma treatment, flame treatment, and UV treatment
  • the drying step is a step of supplying drying air to the ultraviolet absorbing layer.
  • the average wind speed of the dry air is preferably 5 to 30 m / second, more preferably 7 to 25 m / second, and further preferably 9 to 20 m / second or less.
  • the drying air temperature is preferably 80 ° C. to 200 ° C., more preferably 100 ° C. to 180 ° C., and further preferably 120 ° C. to 160 ° C.
  • the drying time is preferably 30 seconds to 300 seconds, and more preferably 60 seconds to 180 seconds.
  • the easy adhesion layer preferably contains, for example, one or more polymers selected from a polyolefin resin, an acrylic resin, a polyester resin, and a polyurethane resin formed with a thickness of about 10 nm to 200 nm.
  • the transparent substrate 10 preferably has a visible light transmittance of 70% or more, more preferably 80% or more. There is no restriction
  • Examples of the shape of the transparent substrate 10 include a film shape and a flat plate shape, and the structure may be a single-layer structure or a laminated structure. You just have to decide.
  • Examples of the material of the transparent base material 10 include polyolefin resins such as glass, polyethylene, polypropylene, poly-4-methylpentene-1, and polybutene-1, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resins, Cellulose-based resins such as polyvinyl chloride resin, polyphenylene sulfide-based resin, polyether sulfone-based resin, polyethylene sulfide-based resin, polyphenylene ether-based resin, styrene-based resin, acrylic resin, polyamide-based resin, polyimide-based resin, and cellulose acetate Examples thereof include a film made of a resin or the like or a laminated film thereof. In particular, a triacetyl cellulose (TAC) film and a polyethylene terephthalate (PET) film are suitable.
  • TAC triacetyl cellulose
  • PET polyethylene terephthalate
  • the thickness is not particularly limited and can be appropriately selected according to the purpose of use for antireflection. In the case of a film, it is usually about 10 ⁇ m to 500 ⁇ m.
  • the thickness of the transparent substrate 10 is preferably 10 ⁇ m to 100 ⁇ m, more preferably 20 to 75 ⁇ m, and particularly preferably 35 to 75 ⁇ m. The thicker the transparent substrate, the less likely it is that adhesive failure will occur.
  • the thickness of the transparent base material when it is bonded to a building material or a window glass of an automobile as an antireflection film, the waist is not too strong and the construction tends to be easy.
  • the transparent substrate is sufficiently thin, the transmittance increases and the raw material cost tends to be suppressed.
  • the antireflection layer 30 is a layer having an antireflection function with respect to incident light having a predetermined wavelength, and is composed of a single layer or a plurality of layers of two or more layers.
  • the antireflection layer a known layer having an antireflection function can be applied without particular limitation.
  • the incident light having a predetermined wavelength is light having a wavelength for which reflection is desired to be prevented.
  • visible light 380 nm to 780 nm
  • the antireflection function for example, the reflectance is preferably 1.0% or less for light having a wavelength of 550 nm, and further, the reflectance is 1.0% or less for light having a wavelength of 550 nm. And it is preferable that the wavelength range of reflectance 1.0% or less covers the range of 100 nm or more.
  • the antireflection layer 30 may have a configuration in which at least a low refractive index layer is provided on the surface side most distant from the transparent substrate 10 in the stacking direction.
  • the low refractive index layer is a layer having a refractive index smaller than the refractive index of the transparent substrate 10.
  • the refractive index of the low refractive index layer is preferably 1.40 or less, for example, about 1.35.
  • the optical film thickness of the low refractive index layer is preferably 30 nm to 100 nm, for example, about 70 nm.
  • the low refractive index layer has a refractive index lower than the refractive index of the transparent substrate 10, and its constituent material is not particularly limited as long as it has an antireflection function by itself or a laminated structure with other layers.
  • its constituent material is not particularly limited as long as it has an antireflection function by itself or a laminated structure with other layers.
  • it contains a binder resin, refractive index control particles and a surfactant, and further contains other components as necessary.
  • the binder resin for the low refractive index layer is not particularly limited and can be appropriately selected according to the purpose.
  • acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin, fluorine resin examples thereof include thermosetting resins such as resins or photocurable resins.
  • the refractive index control particles are added for adjusting the refractive index and can be appropriately selected according to the purpose. Examples thereof include hollow silica.
  • the antireflection layer 30 may be composed of the above-described low refractive index layer and a high refractive index layer disposed closer to the ultraviolet absorbing layer than the low refractive index layer.
  • a high refractive index layer is a layer which has a refractive index higher than the refractive index of the transparent base material 10, and can raise the antireflection effect by combining with a low refractive index layer.
  • the optical film thickness of the high refractive index layer may be about 20 nm to 30 nm, for example.
  • the refractive index of the high refractive index layer is preferably 1.55 or more, particularly 1.6 or more, for example, about 1.7.
  • the constituent material of the high refractive index layer is not particularly limited. For example, it contains a binder resin, metal oxide fine particles, a matting agent, and a surfactant, and further contains other components as necessary.
  • the binder resin for the high refractive index layer is not particularly limited and can be appropriately selected depending on the purpose.
  • acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin, fluorine resin examples thereof include thermosetting resins such as resins or photocurable resins.
  • the metal oxide fine particles are added for adjusting the refractive index, and fine particles having a refractive index larger than that of the binder resin can be appropriately selected according to the purpose, for example, tin-doped oxidation.
  • Indium hereinafter abbreviated as “ITO”), zinc oxide, titanium oxide, zirconium oxide, and the like can be given.
  • the antireflection layer 30 further includes a silver fine particle-containing layer containing a plurality of silver fine particles.
  • FIG. 2 shows a schematic cross-sectional view of an antireflection film provided with an antireflection layer 30 in a particularly preferred form.
  • the antireflection layer 30 is formed by laminating a high refractive index layer 32, a silver fine particle containing layer 36 containing a plurality of silver fine particles 35, and a low refractive index layer 38 from the ultraviolet absorbing layer 20 side.
  • the silver fine particle-containing layer 36 is a layer in which a plurality of silver fine particles 35 are contained in the binder resin 33.
  • the silver fine particles 35 are randomly (non-periodically) arranged in the layer in plan view.
  • 60% or more of the total number of silver fine particles 35 contained in the silver fine particle-containing layer 36 is a tabular grain having a ratio of diameter to thickness (aspect ratio) of 3 or more.
  • the tabular grains are tabular grains having two opposing main planes. Tabular grains have their main planes oriented in the plane of 0 ° to 30 ° with respect to the surface of the silver fine particle-containing layer.
  • a plurality of silver fine particles 35 are arranged without forming a conductive path.
  • -Silver fine particles- As described above, it is preferable that 60% or more of the total number of the plurality of silver fine particles 35 contained in the silver fine particle-containing layer 36 is tabular grains, and 65% or more, more preferably 70% or more are tabular grains. The tabular grains are preferably segregated on one surface of the silver fine particle-containing layer 36.
  • the tabular grain is not particularly limited as long as it is a grain having two opposing main planes.
  • Examples of the shape of the main plane include hexagonal, triangular, and circular shapes. Among these, it is preferable that the shape of the main plane is a hexagonal shape as shown in FIG. 3, a polygonal shape equal to or more than a hexagon, or a circular shape as shown in FIG.
  • the circular shape means a shape in which the number of sides having a length of 50% or more of the average equivalent circle diameter of tabular silver fine particles described later is 0 per tabular grain.
  • the circular tabular grain is not particularly limited as long as it has no corners and has a round shape when the tabular grain is observed from above the main plane with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the hexagonal shape means a shape in which the number of sides having a length of 20% or more of the average equivalent circular diameter of tabular grains described later is 6 per tabular grain.
  • the hexagonal tabular grains are not particularly limited as long as they are hexagonal when the tabular grains are observed from above the main plane with a transmission electron microscope (TEM), and can be appropriately selected according to the purpose.
  • the hexagonal corners may be sharp or dull, but the corners are preferably dull in that the absorption in the visible light region can be reduced.
  • corner According to the objective, it can select suitably.
  • the equivalent circle diameter is represented by the diameter of a circle having an area equal to the projected area of each particle.
  • the projected area of each particle can be obtained by a known method in which the area on an electron micrograph is measured and corrected with the photographing magnification.
  • the average particle diameter (average equivalent circle diameter) is an arithmetic average value obtained by calculating a particle size distribution (particle size distribution) from the statistics of the equivalent circle diameter D of 200 tabular grains and calculating from the particle size distribution.
  • the coefficient of variation in the particle size distribution of the tabular grains is a value (%) obtained by dividing the standard deviation of the particle size distribution by the average particle diameter.
  • the coefficient of variation in the particle size distribution of the tabular grains is preferably 35% or less, more preferably 30% or less, and particularly preferably 20% or less.
  • the coefficient of variation is preferably 35% or less from the viewpoint of reducing absorption of visible light in the antireflection structure.
  • the size of the tabular grain is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the average grain diameter is preferably 10 to 500 nm, more preferably 20 to 300 nm, and even more preferably 50 to 200 nm.
  • the thickness T of the tabular grains is preferably 20 nm or less, more preferably 2 to 15 nm, and particularly preferably 4 to 12 nm.
  • the grain thickness T corresponds to the distance between the main planes of the tabular grains, and is as shown in FIGS. 3 and 4, for example.
  • the particle thickness T can be measured by an atomic force microscope (AFM) or a transmission electron microscope (TEM).
  • Examples of the method for measuring the average particle thickness by AFM include a method in which a particle dispersion containing tabular grains is dropped on a glass substrate and dried to measure the thickness of one particle.
  • a method for measuring the average particle thickness by TEM for example, a particle dispersion containing tabular grains is dropped on a silicon substrate, dried, and then subjected to coating treatment by carbon vapor deposition or metal vapor deposition, and a focused ion beam (FIB).
  • FIB focused ion beam
  • the ratio D / T (aspect ratio) of the diameter (average equivalent circle diameter) D of the tabular grains to the average thickness T is not particularly limited as long as it is 3 or more, and can be appropriately selected according to the purpose. From the viewpoint of reducing absorption and haze, 3 to 40 is preferable, and 5 to 40 is more preferable. If the aspect ratio is 3 or more, visible light absorption can be suppressed, and if it is less than 40, haze in the visible region can also be suppressed.
  • Fig. 5 shows a simulation result of the wavelength dependence of the transmittance when the aspect ratio of the circular particles is changed.
  • the aspect ratio is preferably 5 or more.
  • the main surfaces of the tabular grains (tabular silver fine particles) 35 are plane-oriented in the range of 0 ° to 30 ° with respect to the surface of the silver fine particle-containing layer 36. That is, in FIG. 6, the angle ( ⁇ ⁇ ) between the surface of the silver fine particle-containing layer 36 and the main plane of the tabular grains 35 (the plane that determines the equivalent circle diameter D) or the extension of the main plane is 0 ° to 30 °. It is. More preferably, the angle ( ⁇ ⁇ ) is in a plane orientation in the range of 0 ° to 20 °, and particularly preferably in the range of 0 ° to 10 °.
  • the tabular grains 35 are more preferably oriented in a state where the tilt angle ( ⁇ ⁇ ) shown in FIG. 6 is small. If ⁇ exceeds ⁇ 30 °, the absorption of visible light in the antireflection film may increase. Further, the tabular grains in which the angle ⁇ is in the range of 0 ° to ⁇ 30 ° are preferably 50% or more, more preferably 70% or more of the total number of tabular grains, and 90% % Or more is more preferable.
  • Whether or not the main plane of the tabular grain is plane-oriented with respect to one surface of the silver fine particle-containing layer is evaluated by, for example, preparing an appropriate cross-sectional slice and observing the silver fine particle-containing layer and the tabular grain in this slice. Can be taken. Specifically, a cross-section sample or a cross-section sample of an antireflection film is prepared using a microtome or a focused ion beam (FIB), and this is prepared using various microscopes (for example, a field emission scanning electron microscope (FE-SEM), And a method of evaluating from an image obtained by observation using a transmission electron microscope (TEM) or the like.
  • FIB focused ion beam
  • the cross-section sample or cross-section sample prepared as described above if it can be confirmed whether the main plane of the tabular grain is plane-oriented with respect to one surface of the silver fine particle-containing layer in the sample, although there is no particular limitation, for example, a method using FE-SEM, TEM or the like can be mentioned.
  • observation may be performed by FE-SEM
  • observation may be performed by TEM.
  • TEM When evaluating by FE-SEM, it is preferable to have a spatial resolution that can clearly determine the shape and inclination ( ⁇ ⁇ in FIG. 6) of the tabular grains.
  • the distribution state of the silver fine particles 35 is not particularly limited as long as the conductive path is not formed by the plurality of silver fine particles 35.
  • 7A to 7D are plan views schematically showing the distribution state of the silver fine particles 35 in the silver fine particle-containing layer 36.
  • FIG. The white portions in the figure are silver fine particles 35.
  • the plurality of silver fine particles 35 are all distributed (100%) in the plane direction.
  • FIG. 7B shows a state in which 50% of the plurality of silver fine particles 35 are isolated and the other 50% are in contact with adjacent particles and distributed in a partially connected state 24.
  • FIG. 7C shows a state in which only 10% of the plurality of silver fine particles 35 are present in isolation, and the others are in contact with adjacent particles and distributed in a partially connected state 24.
  • FIG. 7A it is most preferable that the silver fine particles 35 are isolated from each other. However, if 10% or more are arranged in isolation, a sufficient antireflection effect can be obtained.
  • FIG. 7D shows the distribution of silver fine particles when only 2% of the plurality of silver fine particles 35 are isolated. In FIG. 7D, the silver fine particles are connected from one end to the other end in the image to conduct electricity. A path 26 is formed. When the conductive path 26 is formed in this way, the absorption rate of visible light wavelength by the silver fine particles increases, and the reflectance also increases. Therefore, the present invention requires that the conductive path is not formed by at least the silver fine particles 35 as shown in FIGS. 7A to 7C.
  • a conductive path is formed when silver fine particles are continuously connected from one end of the region to the other opposite end in a 2.5 ⁇ m ⁇ 2.5 ⁇ m region observed by SEM. If the silver fine particles are separated on the way, it is determined that the conductive path is not formed.
  • FIGS. 8 and 9 are schematic cross-sectional views showing the existence state of the silver fine particles 35 in the silver fine particle-containing layer 36.
  • the coating film thickness d of the silver fine particle-containing layer 36 is 100 nm or less because the angle range of the plane orientation of the tabular grains tends to approach 0 ° and the absorption of visible light can be reduced as the coating thickness is lowered. It is preferably 3 to 50 nm, more preferably 5 to 40 nm.
  • the tabular particles 35 are used. Is preferably present in the range of d / 2 from the surface of the silver fine particle-containing layer, more preferably in the range of d / 3, and 60% by number or more of the tabular grains contain silver fine particles. More preferably, it is exposed on one surface of the layer.
  • the presence of tabular grains in the range of d / 2 from the surface of the silver fine particle-containing layer means that at least a part of the tabular grains are contained in the range of d / 2 from the surface of the silver fine particle-containing layer.
  • FIG. 8 is a schematic diagram showing the case where the thickness d of the silver fine particle-containing layer is d> D / 2.
  • 80% by number or more of the tabular grains are included in the range f, and f ⁇ d / FIG.
  • the tabular grains are exposed on one surface of the silver fine particle-containing layer means that a part of one surface of the tabular grains is an interface position with the low refractive index layer.
  • FIG. 9 is a view showing a case where one surface of the tabular grain 35 coincides with the interface with the low refractive index layer 38.
  • the distribution of tabular grains in the silver fine particle-containing layer can be measured, for example, from an image obtained by SEM observation of the cross section of the antireflection film.
  • the coating film thickness d of the silver fine particle-containing layer is preferably d ⁇ D / 2, more preferably d ⁇ D / 4, and even more preferably d ⁇ D / 8 with respect to the average equivalent circular diameter D of the tabular grains. . Lowering the coating thickness of the silver fine particle-containing layer is preferable because the angle range of the plane orientation of the tabular grains tends to approach 0 ° and the absorption of visible light can be reduced.
  • the plasmon resonance wavelength ⁇ (absorption peak wavelength in FIG. 5) of the tabular grain in the silver fine particle-containing layer is not limited as long as it is longer than the predetermined wavelength to be prevented from being reflected and can be appropriately selected according to the purpose.
  • the thickness is preferably 700 nm to 2,500 nm.
  • the area of the silver fine particles relative to the area A of the base material when viewed from the top (plan view) of the antireflection film (the total projected area A of the silver fine particle-containing layer when viewed from the direction perpendicular to the silver fine particle-containing layer)
  • the area ratio [(B / A) ⁇ 100] which is the ratio of the total value B, is preferably 5% or more, and more preferably 10% or more and less than 70%. If the area ratio is 5% or more, a sufficient antireflection effect can be obtained. If the area ratio is less than 70%, a conductive path is not formed, and absorption and reflection of visible light can be suppressed and a decrease in transmittance can be suppressed.
  • the area ratio is preferably set to an optimum value according to the thickness T of the tabular grains and the refractive index of the low refractive index layer.
  • the area ratio is preferably 40% or more and less than 70%, and more preferably 50% or more and less than 65%.
  • the area ratio is preferably 5% or more and less than 40%, more preferably 6% or more and less than 30%.
  • the area ratio is preferably 5% or more and less than 30%, more preferably 5% or more and less than 25%.
  • the area ratio can be measured, for example, by performing image processing on an image obtained by SEM observation of the antireflection film from above or an image obtained by AFM (atomic force microscope) observation.
  • the arrangement of tabular grains in the silver fine particle-containing layer is preferably uniform.
  • the variation coefficient of the closest interparticle distance is preferably as small as possible, preferably 30% or less, more preferably 20% or less, more preferably 10% or less, and ideally 0%.
  • the distance between the closest particles can be measured by observing the coated surface of the silver fine particle-containing layer with an SEM or the like.
  • the boundary between the silver fine particle-containing layer and the low refractive index layer can be similarly determined by observation with an SEM or the like, and the thickness d of the silver fine particle-containing layer can be determined. Even when a low refractive index layer is formed on the silver fine particle-containing layer using the same type of polymer as the polymer contained in the silver fine particle-containing layer, the silver fine particle-containing layer is usually obtained by an SEM observation image. And the thickness d of the silver fine particle-containing layer can be determined. When the boundary is not clear, the surface of the flat metal that is located farthest from the substrate is regarded as the boundary.
  • the method for synthesizing the silver tabular grains is not particularly limited and can be appropriately selected depending on the purpose.
  • liquid phase methods such as a chemical reduction method, a photochemical reduction method, and an electrochemical reduction method are hexagonal or thorough. It is mentioned as what can synthesize circular tabular grains.
  • a liquid phase method such as a chemical reduction method or a photochemical reduction method is particularly preferable in terms of shape and size controllability.
  • the corners of the hexagonal to triangular tabular grains can be obtained, for example, by performing etching treatment with a dissolved species that dissolves silver such as nitric acid and sodium sulfite, and aging treatment by heating. May be obtained to obtain hexagonal or circular tabular grains.
  • silver grains may be grown on a flat plate after fixing a seed crystal on the surface of a transparent substrate such as a film or glass in advance.
  • Further processing may be applied to the tabular grains in order to impart desired characteristics.
  • Examples of the further treatment include formation of a high refractive index shell layer, addition of various additives such as a dispersant and an antioxidant.
  • the binder resin 33 in the silver fine particle-containing layer 36 preferably contains a polymer, and more preferably contains a transparent polymer.
  • the polymer include natural materials such as polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polymethyl methacrylate resin, polycarbonate resin, polyvinyl chloride resin, (saturated) polyester resin, polyurethane resin, gelatin, and cellulose. Examples thereof include polymers such as polymers.
  • the main polymer is preferably a polyvinyl alcohol resin, a polyvinyl butyral resin, a polyvinyl chloride resin, a (saturated) polyester resin, or a polyurethane resin
  • the polyester resin and the polyurethane resin preferably represent 80% by number or more of the tabular grains. It is more preferable from the viewpoint of being easily present in the range of d / 2 from the surface of the silver fine particle-containing layer.
  • polyester resins a saturated polyester resin is particularly preferable from the viewpoint of imparting excellent weather resistance because it does not contain a double bond. Moreover, it is more preferable to have a hydroxyl group or a carboxyl group at the molecular terminal from the viewpoint of obtaining high hardness, durability, and heat resistance by curing with a water-soluble / water-dispersible curing agent or the like.
  • the polymer commercially available polymers can be preferably used, and examples thereof include PLUSCOAT Z-687, which is a water-soluble polyester resin manufactured by Kyoyo Chemical Industry Co., Ltd.
  • the main polymer contained in a silver fine particle content layer means the polymer component which occupies 50 mass% or more of the polymer contained in a silver fine particle content layer.
  • the content of the polyester resin and the polyurethane resin with respect to the silver fine particles contained in the silver fine particle-containing layer is preferably 1 to 10,000% by mass, more preferably 10 to 1000% by mass, and 20 to 500% by mass. Is particularly preferred.
  • the refractive index n of the binder resin is preferably 1.4 to 1.7.
  • the antireflection film of the present invention may have a layer other than the above layers.
  • the antireflection film of the present invention may have an infrared absorbing compound-containing layer containing a compound having absorption in the infrared region in order to shield heat rays.
  • the layer containing a compound having absorption in the infrared region is also referred to as an infrared absorbing compound-containing layer.
  • the infrared absorbing compound-containing layer may serve as another functional layer.
  • the antireflection film of the present invention may have an adhesive layer (hereinafter also referred to as an adhesive layer).
  • the material that can be used for forming the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • PVB polyvinyl butyral
  • acrylic resin acrylic resin
  • styrene / acrylic resin acrylic resin
  • urethane resin polyester resin
  • Silicone resin natural rubber, synthetic rubber and the like.
  • An adhesive layer made of these materials can be formed by coating or laminating.
  • you may add an antistatic agent, a lubricant, an antiblocking agent, etc. to the adhesion layer.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m to 50 ⁇ m.
  • the antireflection film may have a backcoat layer on the surface of the transparent substrate opposite to the surface on which the antireflection layer is formed.
  • a backcoat layer There is no restriction
  • it is also suitable to use the easily bonding layer of PET film as a backcoat layer.
  • the antireflection film of the present invention may contain at least one kind of metal oxide particles in order to shield heat rays.
  • the material of the metal oxide particles is not particularly limited and can be appropriately selected depending on the purpose.
  • tin-doped indium oxide hereinafter abbreviated as “ITO”
  • ITO antimony-doped tin oxide
  • ATO zinc oxide, zinc antimonate, titanium oxide, indium oxide, tin oxide, antimony oxide, glass ceramics, lanthanum hexaboride (LaB 6 ), cesium tungsten oxide (Cs 0.33 WO 3 , hereinafter abbreviated as “CWO”).
  • ITO, ATO, CWO, and lanthanum hexaboride (LaB 6 ) are more preferable in that they have excellent heat ray absorption ability and can produce an antireflection structure having a wide range of heat ray absorption ability when combined with tabular grains.
  • ITO is particularly preferable in that infrared rays of 200 nm or more are shielded by 90% or more and the visible light transmittance is 90% or more.
  • the volume average particle size of the primary particles of the metal oxide particles is preferably 0.1 ⁇ m or less in order not to reduce the visible light transmittance.
  • a shape of a metal oxide particle According to the objective, it can select suitably, For example, spherical shape, needle shape, plate shape, etc. are mentioned.
  • the formation process of the antireflection layer in the production method of the antireflection film of the present invention will be described.
  • the antireflection layer is formed on the side of the ultraviolet absorbing layer opposite to the transparent substrate. Another layer may be interposed between the ultraviolet absorbing layer.
  • the process of forming the antireflection layer having the laminated structure shown in FIG. 2 will be described as an example.
  • the high refractive index layer 32 is formed on the ultraviolet absorbing layer 20.
  • a coating method is preferable.
  • a coating solution for forming a high refractive index layer is prepared, and a method for coating with a dip coater, die coater, slit coater, bar coater, gravure coater or the like is used to form a high refractive index layer on the ultraviolet absorbing layer 20. Apply the coating solution.
  • the high refractive index layer 32 is obtained by curing by light irradiation or heating according to the binder resin of the high refractive index layer.
  • a silver fine particle-containing layer 36 is formed on the high refractive index layer 32.
  • a dispersion (tabular grain dispersion) containing silver tabular grains as a coating liquid for forming a silver fine particle-containing layer is applied by a dip coater, a die coater, a slit coater, a bar coater, a gravure coater or the like.
  • the silver fine particle-containing layer is obtained by curing by light irradiation or heating according to the binder resin of the silver fine particle-containing layer.
  • the silver fine particle-containing layer is obtained by curing by light irradiation or heating according to the binder resin of the silver fine particle-containing layer.
  • a low refractive index layer 38 is formed on the silver fine particle-containing layer 36.
  • a coating method is preferable.
  • a coating solution for forming a low refractive index layer is prepared and used for forming a low refractive index layer on the silver fine particle-containing layer 36 by using a dip coater, die coater, slit coater, bar coater, gravure coater or the like. Apply the coating solution.
  • the low refractive index layer 38 is obtained by curing by light irradiation or heating according to the binder resin of the low refractive index layer.
  • an adhesive is laminated and adhered to the outdoor side of the window glass, preferably both sides of the window glass.
  • an adhesive layer is provided by coating or laminating, and a surfactant (mainly nonionic) is included on the surface of the window glass and the adhesive layer of the antireflection film in advance.
  • a surfactant mainly nonionic
  • an antireflection film is preferably installed on the window glass through the adhesive layer. Until the moisture evaporates, the adhesive force of the pressure-sensitive adhesive layer is reduced, so that the position of the antireflection film can be adjusted on the glass surface.
  • the moisture remaining between the window glass and the anti-reflection film is swept away from the center of the glass toward the edge using a squeegee to prevent reflection on the window glass surface.
  • the film can be fixed. In this way, it is possible to install an antireflection film on the window glass.
  • the functional addition to the window glass can also be achieved by a method of heating or pressure laminating in which an antireflection film is mechanically attached to a glass plate using a laminator facility.
  • a laminator is prepared in which a glass plate passes through a slit area sandwiched between a metal roll or a heat-resistant rubber roll heated from the top and a room-temperature or heated heat-resistant rubber roll from the bottom. Place the antireflection film on the glass plate so that the adhesive surface is in contact with the glass surface, set the laminator's upper roll to press the antireflection film, and pass the laminator.
  • the pressure-sensitive adhesive strength is increased and the air-bubbles can be stuck so as not to be mixed.
  • the antireflection film can be supplied in roll form, it is better to supply the tape-like film continuously from the top to the heating roll so that the heating roll has a wrap angle of about 90 degrees. Is easy to be affixed by receiving preheating, and it is possible to achieve both the elimination of bubbles and the increase in adhesive strength at a high level.
  • Coating solution for forming UV absorbing layer (Preparation of coating solutions A-1 to A-19 and A-22 for forming an ultraviolet absorbing layer)
  • the coating solutions A-1 to A-19 and A-22 for forming the ultraviolet absorbing layer were prepared by combining the materials shown in Table 1 and Table 2 with the binder resin, the ultraviolet absorber, and the mixing ratio shown in Table 1 and Table 2, respectively. It was prepared by mixing a surfactant, a film-forming aid and water.
  • quaternary ammonium salt copolymer E was prepared. 60 parts by mass of dimethylaminoethyl acrylate base methyl quaternary represented by the following formula (1) which is a compound having a quaternary ammonium base, and 40 parts by mass of butyl methacrylate which is a compound having one ethylenically unsaturated group A quaternary ammonium salt copolymer E was obtained by copolymerization at a ratio.
  • the coating liquid A-20 for forming the UV absorbing layer corresponds to the UV absorbing hard coat layer coating liquid HC1-1 described in the paragraphs [0048]-[0051] of the specification of Patent Document 2.
  • the coating liquid B-1 for the high refractive index layer was prepared by mixing the materials shown in Table 4 and the mixing ratio.
  • the batch dispersion treatment was performed at 9000 rpm for 120 minutes on the crude dispersion mixture in the tank.
  • the liquid temperature during dispersion was kept at 50 ° C.
  • the temperature was lowered to 25 ° C.
  • single-pass filtration was performed using a profile II filter (manufactured by Nippon Pole Co., Ltd., product type MCY1001Y030H13).
  • the dispersion c1 was subjected to desalting treatment and redispersion treatment to prepare a silver tabular grain dispersion c2.
  • the silver tabular grain dispersion c2 was dropped on a silicon substrate and dried, and the individual thicknesses of the tabular grains were measured by the FIB-TEM method. Ten tabular grains in the silver tabular grain dispersion c2 were measured, and the average thickness was 8 nm. That is, the aspect ratio expressed by diameter / thickness was 15.0.
  • the coating liquid C-1 for the silver fine particle-containing layer was prepared by mixing at the material mixing ratio shown in Table 5.
  • the silver fine particle-containing layer coating liquid C-1 corresponds to the metal fine particle-containing layer coating liquid C1C described in the paragraphs [0093]-[0103] of the specification of Patent Document 1.
  • the low refractive index layer coating solution D-1 corresponds to the dielectric layer coating solution D1 described in paragraph [0103] of the specification of Patent Document 1.
  • the coating solution D-2 for the low refractive index layer corresponds to the coating solution L1-1 for the low refractive index layer described in paragraph [0052] of the specification of Patent Document 2.
  • Example 1 Using a wire bar, the coating liquid A-1 for the ultraviolet absorbing layer is applied on one surface of a transparent substrate PET (polyethylene terephthalate) film (U403, film thickness 50 ⁇ m, manufactured by Toray Industries, Inc.). Then, it was applied so that the average thickness after drying was 0.9 ⁇ m, and dried at 150 ° C. for 2 minutes to form an ultraviolet absorbing layer. Thereafter, the coating solution B-1 for the high refractive index layer is applied using a wire bar so that the average thickness after drying is 25 nm, heated at 150 ° C. for 1 minute, dried and cured. A refractive index layer was formed.
  • PET polyethylene terephthalate
  • Example 1 an antireflection film of Example 1 obtained by laminating an ultraviolet absorption layer and an antireflection layer composed of a high refractive index layer and a low refractive index layer on a transparent substrate composed of a PET film was obtained. .
  • Example 2-17, Comparative Example 3 On one surface of the PET film, in Example 1, the coating liquid A-1 for the ultraviolet absorbing layer was changed to the coating liquid and coating thickness shown in the table, respectively, and the coating time was changed according to the thickness of the coating liquid.
  • An antireflection film of Example 2-17 and Comparative Example 3 was obtained in the same manner as in Example 1 except for the above.
  • the ultraviolet absorbing layer coating solution A-1 was applied using a wire bar so that the average thickness after drying was 0.9 ⁇ m, and dried at 150 ° C. for 2 minutes to obtain ultraviolet rays. An absorbent layer was formed. Thereafter, the coating liquid B-1 for the high refractive index layer is applied using a wire bar so that the average thickness after drying is 25 nm, heated at 150 ° C. for 1 minute, dried and cured to increase the thickness. A refractive index layer was formed. Next, coating liquid C-1 for silver fine particle-containing layer was applied to the surface of the high refractive index layer using a wire bar so that the average thickness after drying was 30 nm.
  • Example 18 obtained by laminating an antireflection layer composed of an ultraviolet absorbing layer, a high refractive index layer, a silver fine particle-containing layer, and a low refractive index layer on a transparent substrate made of a PET film by the above process. An antireflection film was obtained.
  • Example 19 and Example 19 were performed in the same manner as in Example 18 except that the coating liquid A-18 for the ultraviolet absorbing layer in Example 18 was changed to the coating liquid shown in the table. 20 antireflection films were obtained.
  • Example 21 On one surface of the PET film, Example 21 was carried out in the same manner as in Example 18, except that the coating liquid D-1 for the low refractive index layer was changed to the coating liquid shown in the table in Example 18. An antireflection film of -23 was obtained.
  • the average thickness after drying the coating solution A-20 for the ultraviolet absorbing layer on one side of a PET film with an easy adhesion layer (A4100, film thickness 100 ⁇ m, manufactured by Toyobo Co., Ltd.) using a wire bar is 1.
  • An ultraviolet absorbing layer was formed by applying the film to 0 ⁇ m and irradiating it with an ultraviolet ray of 200 mJ / cm 2 using a 120 W high pressure mercury lamp. Thereafter, the coating liquid D-2 for the low refractive index layer was applied using a wire bar so that the average thickness after drying was 80 nm, and irradiated with ultraviolet rays of 400 mJ / cm 2 with a 120 W high-pressure mercury lamp.
  • the low refractive index layer was formed by curing. Through the above steps, an antireflection film of Comparative Example 1 obtained by laminating an ultraviolet absorption layer and an antireflection layer comprising a low refractive index layer on a transparent substrate made of a PET film was obtained.
  • Comparative Example 2 On the surface of the PET film, the antireflection film of Comparative Example 2 was prepared by the method of Comparative Example 1 except that the coating liquid A-20 for the ultraviolet absorbing layer in Comparative Example 1 was changed to the coating liquid A-21. Obtained.
  • the chromaticity b * represented by coordinates in the CIE1976 (L * a * b * ) color space, which is an international standard, is calculated with a 10 ° field of view, a D65 light source, and an average of three times as measurement conditions.
  • the yellow color increases as the chromaticity b * increases.
  • ⁇ b * (b * value after test) ⁇ (b * value before test) It can be said that the smaller the difference ⁇ b * between the b * values before and after the test represented by the above formula, the smaller the yellowing. The smaller the discoloration, the higher the light resistance.
  • the table shows the results of evaluation on the following evaluation criteria for ⁇ b * for each example and comparative example.
  • a to C are practically acceptable levels, and D is a level that cannot be practically used.
  • the reflectance at wavelengths from 300 nm to 800 nm was measured when light was incident perpendicularly to the film surface from one antireflection film side.
  • the reflectance at a wavelength of 550 nm and the “1.0% bandwidth” defined by the wavelength bandwidth at which the reflectance is 1.0% or less in the measurement region range from 300 nm to 800 nm
  • the following criteria were evaluated. .
  • B Reflectance ⁇ 1.0% at 550 nm and 1.0% bandwidth is less than 100 nm.
  • the gaze concentration rate was obtained as follows. Antireflection films were attached to both sides of a building window glass (width 1120 mm, height 2100 mm). A sample of a product was placed in front of the window glass inside and outside the building. On a sunny day afternoon, under the conditions of outdoor illuminance of 90,000 lux and indoor illuminance of 2,000 lux, the digital camera was An image in which both the reflection image from the sample outside and the transmission image of the sample inside the building coexisted was taken. The acquired image was displayed on the entire surface of a 24-inch liquid crystal monitor (G2410t) manufactured by DELL Computer for 10 seconds and presented to the subject.
  • G2410t liquid crystal monitor
  • the place observed by the subject in the image was acquired as time series data of coordinates using an eye tracker (Tobii X2-30) manufactured by Tobii.
  • the time series data of the acquired coordinates is analyzed using the numerical calculation software MALAB manufactured by Masworks, and the time during which the image is displayed within the rectangular area including the sample inside the building within 10 seconds is displayed.
  • t was calculated. Similar measurements were performed on 10 men and women in their 20s to 50s, and the average value of t / 10 was calculated as the gaze concentration rate.
  • the gaze concentration rate was evaluated according to the following evaluation criteria.
  • a to B are practically acceptable levels, and C is a level that cannot be practically used.
  • Table 10 shows the evaluation results regarding the above-described evaluation items for each of the examples and comparative examples.
  • the average absorbance at a wavelength of 320 to 330 nm in the antireflection laminated film was 1.5 or more, and all of weather resistance, haze, reflectance, and film hardness were all measured.
  • the evaluation result was one of evaluation results A to C that could withstand practical use.
  • Comparative Examples 1 and 3 a sufficient average absorbance could not be obtained, and in Comparative Example 2, an average absorbance of 1.5 or more was obtained similarly to the Examples, and yellowing was suppressed. The result was that the haze was large and unsuitable for practical use.
  • Example 1 From a comparison between Example 1 and Example 2, it was found that even if the amount of UV absorber applied was the same, if the thickness of the UV absorbing layer was thin, haze increased and film hardness decreased. Further, from Examples 2 to 4, it was found that even if the coating amount of the ultraviolet absorber was the same, the haze increased when the thickness of the ultraviolet absorbing layer was increased to some extent. Further, in Examples 6 and 7, in which the coating amount of the ultraviolet absorber was small compared to Example 1-4, the absorbance decreased compared to Example 1-4, and the yellowing suppression effect decreased. On the other hand, when the coating amount of the ultraviolet absorber was large as in Example 9, the haze increased as compared with other examples in which the coating amount was 3000 mg / m 2 or less.
  • Examples 18-23 are A evaluations in all the evaluation items, and it is clear that this is a particularly preferable form.

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Abstract

Le problème décrit par la présente invention concerne un film antireflet hautement durable dans lequel la coloration (décoloration) est réduite au minimum même lorsqu'il est exposé à la lumière solaire en extérieur pendant une longue période ; et un procédé de production du film antireflet. La solution selon l'invention porte sur un film antireflet (1) pourvu : d'un substrat transparent (10) ; et d'un stratifié antireflet (40) comprenant une couche antireflet (30) disposée sur un côté du substrat transparent (10), et une couche d'absorption d'UV (20) qui est disposée entre le substrat transparent (10) et la couche antireflet (30) et comprend une résine liante (22) et un agent d'absorption d'UV (21). La résine liante (22) est constituée à partir du produit durci d'une composition de résine à base d'eau ; la teneur de l'agent d'absorption d'UV (21) est réglée pour ne pas être inférieure à 290 mg/m2 ; et l'absorbance moyenne dans le stratifié antireflet (40) par rapport à la lumière présentant une longueur d'onde de 320 nm à 330 nm n'est pas inférieure à 1,5.
PCT/JP2016/004647 2015-10-21 2016-10-21 Film antireflet et son procédé de production WO2017068788A1 (fr)

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TWI688464B (zh) * 2018-11-14 2020-03-21 國立虎尾科技大學 仿生增亮膜、其製法及其應用的光學元件

Citations (2)

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Publication number Priority date Publication date Assignee Title
JP2011065139A (ja) * 2009-08-19 2011-03-31 Fujifilm Corp 光拡散シート
JP2015129909A (ja) * 2013-12-03 2015-07-16 富士フイルム株式会社 反射防止光学部材

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011065139A (ja) * 2009-08-19 2011-03-31 Fujifilm Corp 光拡散シート
JP2015129909A (ja) * 2013-12-03 2015-07-16 富士フイルム株式会社 反射防止光学部材

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