WO2024122489A1 - 反射防止フィルム - Google Patents

反射防止フィルム Download PDF

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Publication number
WO2024122489A1
WO2024122489A1 PCT/JP2023/043235 JP2023043235W WO2024122489A1 WO 2024122489 A1 WO2024122489 A1 WO 2024122489A1 JP 2023043235 W JP2023043235 W JP 2023043235W WO 2024122489 A1 WO2024122489 A1 WO 2024122489A1
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Prior art keywords
meth
acrylate
layer
refractive index
fluorine
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PCT/JP2023/043235
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English (en)
French (fr)
Japanese (ja)
Inventor
卓彌 胡桃澤
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Higashiyama Film Co Ltd
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Higashiyama Film Co Ltd
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Priority to JP2024562756A priority Critical patent/JPWO2024122489A1/ja
Priority to CN202380083925.4A priority patent/CN120322705A/zh
Publication of WO2024122489A1 publication Critical patent/WO2024122489A1/ja
Anticipated expiration legal-status Critical
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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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • 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

Definitions

  • the present invention relates to an anti-reflective film, and more specifically, to an anti-reflective film suitable for use on the surfaces of displays such as liquid crystal displays, organic electroluminescence displays, and touch panels for smartphones and the like.
  • Anti-reflective film is sometimes placed on the surface of displays such as liquid crystal displays, organic electroluminescence displays, and touch panels on smartphones and other devices to prevent external light from being reflected on the screen.
  • the characteristics required of anti-reflective film include optical properties such as low reflectance and high transmittance, as well as physical and chemical properties such as high hardness, scratch resistance, chemical resistance, and stain resistance.
  • optical properties such as low reflectance and high transmittance
  • physical and chemical properties such as high hardness, scratch resistance, chemical resistance, and stain resistance.
  • fingerprints and other stains must be removed by wiping with a cloth or similar, and in recent years, there has been a demand for improved resistance to rubbing of anti-reflective films against cloth or felt, particularly for anti-reflective films used in such displays.
  • Patent Document 1 discloses an anti-reflective film that has antifouling properties and is resistant to scratches even when repeatedly wiped or wiped with a hard cotton cloth, by using a specific amount of alumina particles, hollow silica fine particles, and a fluorine-containing compound in the low refractive index layer placed on the outermost surface of the anti-reflective film.
  • the low refractive index layer placed on the outermost surface is composed of low refractive index nanoparticles such as hollow silica, a binder such as a multifunctional acrylate, and a fluorine-based additive.
  • a low refractive index layer having such a composition has low strength, and is prone to scratches and peeling of the coating when tested for abrasion resistance.
  • strength can be improved by using a layer composed of inorganic oxide particles and a multifunctional acrylate, which can have high strength, as the outermost low refractive index layer, but in that case, the reflectance of the resulting anti-reflection film will be high due to the high refractive index of these substances.
  • an anti-stain layer containing a substance with anti-stain properties such as a fluorine-based additive
  • a form in which an anti-stain layer containing a substance with anti-stain properties, such as a fluorine-based additive, is provided on the surface of the low refractive index layer as a layer independent of the low refractive index layer is also used.
  • an anti-stain layer is provided, there are cases in which a sufficiently high level of anti-stain properties is not obtained, or the surface is worn away by repeated contact with fingers or wiping with a cloth, etc., resulting in a decrease in anti-stain properties.
  • Anti-reflective films that are frequently exposed to contact with fingers or wiping are required to have high anti-reflective and anti-stain properties as well as high durability against repeated wiping. In terms of durability against wiping, it is important that the film not only resists scratches during wiping, but also has high abrasion resistance in the sense that wear marks are unlikely to form due to changes in the reflective properties at
  • the problem that this invention aims to solve is to provide an anti-reflective film that has excellent anti-reflective and anti-fouling properties, as well as high abrasion resistance that is resistant to wear marks and scratches even when repeatedly wiped.
  • the anti-reflection film according to the present invention has the following configuration.
  • the anti-reflection film according to the present invention has a base film, a hard coat layer formed on a surface of the base film, a low refractive index layer formed on the surface of the hard coat layer, and an anti-fouling layer formed on the surface of the low refractive index layer, the anti-fouling layer being composed of a cured product of a composition containing a fluorinated (meth)acrylate, the content of the fluorinated (meth)acrylate in the anti-fouling layer being 90 mass% or more based on the total solid content of the anti-fouling layer, and 50 mass% or more of the solid content of the fluorinated (meth)acrylate contained in the anti-fouling layer is a fluorinated (meth)acrylate having a polar component ⁇ p of surface free energy of 18 mN/m or more.
  • the entire amount of the resin component constituting the antifouling layer may be a fluorine-containing (meth)acrylate.
  • the fluorine-containing (meth)acrylate contained in the antifouling layer in which the polar component ⁇ p of the surface free energy is 18 mN/m or more, may have a hydrogen bond component ⁇ h of the surface free energy of 8 mN/m or less, and a dispersion component ⁇ d of 8 mN/m or more and 40 mN/m or less.
  • the anti-reflection film according to the present invention having the above-mentioned configuration [1] comprises a substrate film, a hard coat layer formed on the surface of the substrate film, a low refractive index layer formed on the surface of the hard coat layer, and an anti-fouling layer formed on the surface of the low refractive index layer, the anti-fouling layer being composed of a cured product of a composition containing a fluorine-containing (meth)acrylate, the content of the fluorine-containing (meth)acrylate in the anti-fouling layer being 90 mass% or more based on the total solid content of the anti-fouling layer, and 50 mass% or more of the solid content of the fluorine-containing (meth)acrylate contained in the anti-fouling layer being a fluorine-containing (meth)acrylate having a polar component ⁇ p of the surface free energy of 18 mN/m or more, thereby providing excellent anti-reflection and anti-fouling properties, as well as high
  • the total amount of the resin components constituting the antifouling layer is fluorine-containing (meth)acrylate. Adding a binder resin that does not contain fluorine to the antifouling layer may increase the adhesion of the antifouling layer to the low refractive index layer, thereby increasing the abrasion resistance of the antireflection film.
  • the antireflection film according to the present invention has sufficiently high abrasion resistance because the antifouling layer contains 90 mass% or more of fluorine-containing (meth)acrylate as in the above embodiment [1], and 50 mass% or more of the fluorine-containing (meth)acrylate is fluorine-containing (meth)acrylate with a polar component ⁇ p of the surface free energy of 18 mN/m or more. Therefore, there is no need to add a binder resin that does not contain fluorine to the antifouling layer for the purpose of improving abrasion resistance.
  • the fluorine-containing (meth)acrylate contained in the antifouling layer has a surface free energy polar component ⁇ p of 18 mN/m or more, a hydrogen bond component ⁇ h of the surface free energy of 8 mN/m or less, and a dispersion component ⁇ d of 8 mN/m or more and 40 mN/m or less.
  • the hydrogen bond component ⁇ h as described above enhances the antifouling effect of the antifouling layer.
  • the dispersion component ⁇ d as described above suppresses aggregation of the fluorine-containing (meth)acrylate, making it easier to form the antifouling layer as a uniform coating film.
  • FIG. 1 is a cross-sectional view of an antireflection film according to a first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of an antireflection film according to a second embodiment of the present invention.
  • FIG. 4 is a cross-sectional view of an antireflection film according to a third embodiment of the present invention.
  • FIG. 11 is a cross-sectional view of an antireflection film according to a fourth embodiment of the present invention.
  • the present invention will be described in detail below.
  • various physical properties refer to values at room temperature in the atmosphere unless otherwise specified.
  • the refractive index of a substance and a substance layer refers to the refractive index at a measurement wavelength of 589.3 nm unless otherwise specified.
  • Fig. 1 is a cross-sectional view of an anti-reflection film 10 according to a first embodiment of the present invention.
  • the anti-reflection film 10 according to the first embodiment of the present invention has a substrate film 12, a hard coat layer 14 formed on the surface of the substrate film 12, a low refractive index layer 16 formed on the surface of the hard coat layer 14, and an anti-stain layer 18 formed on the surface of the low refractive index layer 16.
  • the above-mentioned layers are laminated in order without any other layer therebetween.
  • the anti-stain layer 18 is the layer exposed on the outermost surface of the entire anti-reflection film 10.
  • the base film 12 is not particularly limited as long as it has transparency.
  • Examples of the base film 12 include a transparent polymer film and a glass film.
  • Transparency refers to a total light transmittance of 50% or more in the visible light wavelength region, and the total light transmittance is more preferably 85% or more.
  • the total light transmittance can be measured in accordance with JIS K7361-1 (1997).
  • the thickness of the base film 12 is not particularly limited, but is preferably in the range of 2 ⁇ m to 500 ⁇ m in terms of excellent handleability. More preferably, it is in the range of 2 ⁇ m to 200 ⁇ m.
  • film generally refers to a film having a thickness of less than 0.25 mm, even if the thickness is 0.25 mm or more, it is included in the “film” even if the thickness is 0.25 mm or more, as long as it can be wound into a roll.
  • the polymeric material of the base film 12 may be a polyester resin such as polyethylene terephthalate resin or polyethylene naphthalate resin, a polycarbonate resin, a poly(meth)acrylate resin, a polystyrene resin, a polyamide resin, a polyimide resin, a polyacrylonitrile resin, a polyolefin resin such as polypropylene resin, polyethylene resin, polycycloolefin resin, or cycloolefin copolymer resin, a cellulose-based resin such as triacetyl cellulose resin or diacetyl cellulose resin, a polyphenylene sulfide resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, or a polyvinyl alcohol resin.
  • a polyester resin such as polyethylene terephthalate resin or polyethylene naphthalate resin, a polycarbonate resin, a poly(meth)acrylate resin, a polystyrene resin,
  • the polymeric material of the base film 12 may be composed of only one of these materials, or may be composed of a combination of two or more of these materials.
  • polyethylene terephthalate resin, polyimide resin, polycarbonate resin, poly(meth)acrylate resin, polycycloolefin resin, cycloolefin copolymer resin, or triacetyl cellulose resin is more preferable.
  • the substrate film 12 may be composed of a single layer containing one or more of the above polymeric materials, or may be composed of two or more layers, such as a layer containing one or more of the above polymeric materials and a layer containing one or more of a different polymeric material.
  • the hard coat layer 14 contributes to improving the scratch resistance of the anti-reflection film 10.
  • the hard coat layer 14 is composed of a cured product of an ionizing radiation curable composition containing a (meth)acrylate compound having a reactive group.
  • the ionizing radiation means electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Examples of the ionizing radiation include ultraviolet rays (UV), X-rays, gamma rays, and other electromagnetic waves, electron beams (EB), alpha rays, ion beams, and other charged particle beams. Among these, ultraviolet rays (UV) are particularly preferred from the viewpoint of productivity.
  • the ionizing radiation curable composition may be simply referred to as a curable composition.
  • (meth)acrylate means “at least one of acrylate and methacrylate”.
  • (meth)acryloyl means “at least one of acryloyl and methacryloyl”.
  • (meth)acrylic means “at least one of acrylic and methacrylic”.
  • the "(meth)acrylate compound” is a compound having a (meth)acryloyl group, and examples of such compounds include monomers, oligomers, prepolymers, etc.
  • the (meth)acrylate compound may be simply referred to as "(meth)acrylate.”
  • the (meth)acrylate may be a monofunctional (meth)acrylate or a polyfunctional (meth)acrylate. Alternatively, it may be a combination of a monofunctional (meth)acrylate and a polyfunctional (meth)acrylate. From the viewpoint of improving curability, etc., it is more preferable that the curable composition contains a polyfunctional (meth)acrylate as the (meth)acrylate.
  • Methodacrylates include urethane (meth)acrylates, silicone (meth)acrylates, alkyl (meth)acrylates, and aryl (meth)acrylates. Of these, urethane (meth)acrylates, particularly urethane (meth)acrylate oligomers, are preferred. Specific examples of urethane (meth)acrylates include those obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylate compound and, if necessary, a polyol compound.
  • polyisocyanate compounds include diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, as well as their nurate modified products, adduct modified products, and biuret modified products.
  • diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, as well as their nurate modified products, adduct modified products, and biuret modified products.
  • hydroxyl group-containing (meth)acrylate compounds include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane diacrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and polyoxyalkylene modified products and polylactone modified products thereof.
  • polyol compounds include ethylene glycol, propylene glycol, butanediol, hexanediol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, biphenol, bisphenol, etc.
  • the hard coat layer 14 When the curable composition for forming the hard coat layer 14 contains urethane (meth)acrylate as the UV-curable resin, the hard coat layer 14 has a suitable flexibility, so that the anti-reflection film 10 has high bending resistance and can be suitably used for flexible displays that are repeatedly bent, such as foldable displays and rollable displays.
  • the substrate film 12 is made of, for example, polycycloolefin or cycloolefin copolymer, which is relatively prone to cracking, cracking of the substrate film 12 is easily suppressed.
  • the (meth)acrylate constituting the curable composition further contains a pentaerythritol (meth)acrylate compound.
  • pentaerythritol (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and tripentaerythritol octa(meth)acrylate.
  • the curable composition contains pentaerythritol tri(meth)acrylate,
  • the curable composition forming the hard coat layer 14 may or may not contain a non-UV curable resin in addition to the UV curable resin.
  • the curable composition forming the hard coat layer 14 may also contain a photopolymerization initiator. If necessary, it may also contain additives that can be generally added to curable compositions. Examples of additives include dispersants, leveling agents, defoamers, thixotropic agents, antifouling agents, antibacterial agents, flame retardants, slip agents, antistatic agents, inorganic particles, and resin particles. If necessary, it may also contain a solvent.
  • Non-UV curable resins include thermoplastic resins and thermosetting resins.
  • Thermoplastic resins include polyester resins, polyether resins, polyolefin resins, and polyamide resins.
  • Thermosetting resins include unsaturated polyester resins, epoxy resins, alkyd resins, and phenolic resins.
  • photopolymerization initiators examples include alkylphenone-based, acylphosphine oxide-based, and oxime ester-based photopolymerization initiators.
  • alkylphenone-based photopolymerization initiators include 2,2'-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one, and 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one.
  • acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc.
  • examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc.
  • oxime ester photopolymerization initiators examples include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), etc.
  • the photopolymerization initiator may be used alone or in combination of two or more of these.
  • the content of the photopolymerization initiator is preferably in the range of 0.1% by mass to 10% by mass based on the total solid content of the curable composition. More preferably, it is 1% by mass or more and 5% by mass or less.
  • Inorganic particles and resin particles may be added to the hard coat layer 14 for the purpose of, for example, preventing blocking of the hard coat layer 14, adjusting the refractive index of the hard coat layer 14, imparting anti-glare properties, etc.
  • the inorganic particles or resin particles added form fine surface irregularities in the hard coat layer 14, which makes it easier to prevent blocking, which occurs when the hard coat film consisting of the base film 12 and the hard coat layer 14 before the low refractive index layer 16 is formed, is wound into a roll.
  • Inorganic particles capable of adjusting the refractive index of the hard coat layer 14 include metal oxide particles made of oxides of metals such as titanium, zirconium, tin, zinc, silicon, niobium, aluminum, chromium, magnesium, germanium, gallium, antimony, and platinum. These may be used alone as optically adjustable inorganic particles, or in combination of two or more types. Among these, titanium oxide and zirconium oxide are particularly preferred from the viewpoint of achieving both a high refractive index and excellent transparency.
  • resin particles include resin particles made of resins such as (meth)acrylic resin, styrene resin, styrene-(meth)acrylic resin, urethane resin, polyamide resin, silicone resin, epoxy resin, phenolic resin, polyethylene resin, and cellulose. These may be used alone as resin particles, or in combination of two or more types.
  • the thickness of the hard coat layer 14 is not particularly limited, but from the viewpoint of having sufficient hardness, it is preferably 0.5 ⁇ m or more. More preferably, it is 0.75 ⁇ m or more. Furthermore, from the viewpoint of easily suppressing curling due to the difference in thermal shrinkage with the base film 12, it is preferably 20 ⁇ m or less. More preferably, it is 10 ⁇ m or less.
  • the thickness of the hard coat layer 14 is the thickness of a relatively smooth portion in the thickness direction that does not have irregularities due to inorganic particles or resin particles.
  • the refractive index of the hard coat layer 14 is preferably within the range of 1.49 to 1.56.
  • the arithmetic mean roughness Ra of the surface of the hard coat layer 14 on which the surface irregularities are formed is preferably within a range of 0.3 nm or more and 20 nm or less from the viewpoint of suppressing blocking, etc., and more preferably 0.5 nm or more and 10 nm or less.
  • Solvents used in the curable composition that forms the hard coat layer 14 include alcohol-based solvents such as ethanol, isopropyl alcohol (IPA), n-butyl alcohol (NBA), ethylene glycol monomethyl ether (EGM), ethylene glycol monoisopropyl ether (IPG), propylene glycol monomethyl ether (PGM), and diethylene glycol monobutyl ether; ketone-based solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, and acetone; aromatic solvents such as toluene and xylene; ester-based solvents such as ethyl acetate (EtAc), propyl acetate, isopropyl acetate, and butyl acetate (BuAc); and amide-based solvents such as N-methylpyrrolidone, acetamide, and dimethylformamide. These may be used alone or in combination
  • the solids concentration of the curable composition may be appropriately determined taking into consideration the coatability, film thickness, etc. For example, it may be 1% by mass or more and 90% by mass or less, 1.5% by mass or more and 80% by mass or less, or 2% by mass or more and 70% by mass or less, etc.
  • a low refractive index layer 16 is provided as an antireflection layer on the surface of the hard coat layer 14.
  • the low refractive index layer 16 has a refractive index lower than that of the hard coat layer 14, and exerts an antireflection effect due to the difference in refractive index between the low refractive index layer 16 and the hard coat layer 14.
  • the low refractive index layer 16 is not particularly limited in composition, but is preferably made of a cured product of a composition containing a binder resin and hollow silica particles. In particular, it is preferably made of a cured product of an ionizing radiation curable composition containing these components.
  • a suitable composition is described below.
  • the binder resin is preferably a thermosetting compound or an ionizing radiation curable compound such as an ultraviolet curable compound. From the viewpoint of the productivity of the anti-reflection film 10, the binder resin is preferably made of an ultraviolet curable compound.
  • Examples of ultraviolet-curable resins include monomers, oligomers, and prepolymers having ultraviolet-reactive reactive groups.
  • Examples of ultraviolet-reactive reactive groups include radical polymerization type reactive groups having ethylenically unsaturated bonds, such as acryloyl groups, methacryloyl groups, allyl groups, and vinyl groups, and cationic polymerization type reactive groups, such as oxetanyl groups.
  • acryloyl groups, methacryloyl groups, and oxetanyl groups are more preferred, and acryloyl groups and methacryloyl groups are particularly preferred. In other words, it is particularly preferred to use a (meth)acrylate compound.
  • the ultraviolet-curable resin may be composed of one type of (meth)acrylate, including those listed below, or may be composed of two or more types.
  • Examples of (meth)acrylate compounds include urethane (meth)acrylate, silicone (meth)acrylate, alkyl (meth)acrylate, and aryl (meth)acrylate.
  • the (meth)acrylate may be composed of only monofunctional (meth)acrylate, may be composed of only polyfunctional (meth)acrylate, or may be composed of a combination of monofunctional (meth)acrylate and polyfunctional (meth)acrylate. It is more preferable that the (meth)acrylate contains a polyfunctional (meth)acrylate.
  • Monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, and deci aryl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate
  • polyfunctional (meth)acrylates examples include difunctional (meth)acrylates, trifunctional (meth)acrylates, and tetrafunctional (meth)acrylates. More specifically, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate.
  • pentaerythritol tri(meth)acrylate pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, etc.
  • the (meth)acrylate compound may contain a fluorine-containing (meth)acrylate having an acryloyloxy group.
  • the fluorine-containing (meth)acrylate may be composed of only a fluorine-containing monofunctional (meth)acrylate, may be composed of only a fluorine-containing polyfunctional (meth)acrylate, or may be composed of a combination of a fluorine-containing monofunctional (meth)acrylate and a fluorine-containing polyfunctional (meth)acrylate. From the viewpoint of improving scratch resistance, it is more preferable that the fluorine-containing (meth)acrylate contains a fluorine-containing polyfunctional (meth)acrylate.
  • fluorine-containing monofunctional (meth)acrylates include 1-(meth)acryloyloxy-1-perfluoroalkylmethane and 1-(meth)acryloyloxy-2-perfluoroalkylethane.
  • Perfluoroalkyl groups include linear, branched, and cyclic perfluoroalkyl groups having 1 to 8 carbon atoms.
  • fluorine-containing polyfunctional (meth)acrylate a fluorine-containing difunctional (meth)acrylate, a fluorine-containing trifunctional (meth)acrylate, or a fluorine-containing tetrafunctional (meth)acrylate is preferred.
  • fluorine-containing bifunctional (meth)acrylates include 1,2-di(meth)acryloyloxy-3-perfluoroalkylbutane, 2-hydroxy-1H,1H,2H,3H,3H-perfluoroalkyl-2',2'-bis ⁇ (meth)acryloyloxymethyl ⁇ propionate, and ⁇ , ⁇ -di(meth)acryloyloxymethylperfluoroalkane.
  • the perfluoroalkyl group is preferably a straight-chain, branched, or cyclic group having 1 to 11 carbon atoms, and the perfluoroalkane group is preferably a straight-chain group having 1 to 11 carbon atoms.
  • fluorine-containing bifunctional (meth)acrylates can be used alone or as a mixture.
  • fluorine-containing trifunctional (meth)acrylates include 2-(meth)acryloyloxy-1H,1H,2H,3H,3H-perfluoroalkyl-2',2'-bis ⁇ (meth)acryloyloxymethyl ⁇ propionate, etc.
  • the perfluoroalkyl group is preferably a linear, branched or cyclic group having 1 to 11 carbon atoms.
  • Preferred examples of fluorine-containing tetrafunctional (meth)acrylates include ⁇ , ⁇ , ⁇ , ⁇ -tetrakis ⁇ (meth)acryloyloxy ⁇ - ⁇ H, ⁇ H, ⁇ H, ⁇ H, ⁇ H, ⁇ H, ⁇ H, ⁇ H, ⁇ H, ⁇ H, ⁇ H, ⁇ H-perfluoroalkane, etc.
  • the perfluoroalkane group is preferably a straight-chain group having 1 to 14 carbon atoms. When used, the fluorine-containing tetrafunctional (meth)acrylates can be used alone or as a mixture.
  • the content of the fluorine-containing (meth)acrylate is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of solids in the binder resin, and may be the total amount. This makes it easier to obtain good anti-reflection properties by making the low refractive index layer 16 have a low refractive index.
  • the low refractive index layer 16 contains a fluorine-containing (meth)acrylate
  • the value of the surface free energy and the magnitude of each component of the surface free energy are not specified, as is the case with the fluorine-containing (meth)acrylate contained in the antifouling layer 18 described later.
  • a fluorine-containing (meth)acrylate with a large surface free energy is unlikely to provide high water and oil repellency and therefore high antifouling properties, but in the anti-reflection film 10 according to this embodiment, the low refractive index layer 16 is not exposed to the outermost surface, and antifouling properties are guaranteed by the antifouling layer 18 on the outermost surface, so the low refractive index layer 16 does not need to exhibit high water and oil repellency.
  • the fluorine-containing (meth)acrylate contained in the low refractive index layer 16 has a large surface free energy from the viewpoint of increasing the adhesion of the antifouling layer 18 to the low refractive index layer 16.
  • the surface free energy of the fluorine-containing (meth)acrylate contained in the low refractive index layer 16 exceeds 60 mN/m.
  • the surface free energy is particularly preferably 80 mN/m or more, and more preferably 90 mN/m or more.
  • the fluorine-containing (meth)acrylate contained in the low refractive index layer 16 preferably has a surface free energy ( ⁇ ) and a polar component ( ⁇ p) greater than the large polar component fluorine-containing (meth)acrylate contained in the antifouling layer 18 described later.
  • Hollow silica particles are particles with an average particle diameter smaller than the average thickness d of the low refractive index layer 16, and do not substantially contribute to the formation of surface irregularities in the low refractive index layer 16.
  • Hollow silica particles are particles that have cavities inside them, and the proportion of cavities is 5% or more of the volume. Hollow refers to a state in which the particle has a shell structure consisting of an outer shell and a cavity inside it, or a porous structure with many cavities.
  • the hollow structure of hollow silica particles can lower the refractive index of the low refractive index layer 16 and reduce light reflection.
  • the shape of hollow silica particles is not particularly limited, but is preferably spherical, spindle-shaped, egg-shaped, flat, cubic, or amorphous. Of these, spherical, flat, cubic, and other shapes are particularly preferred.
  • the proportion of cavities is preferably 10% or more and 80% or less by volume. If the proportion of cavities is 10% or more by volume, the refractive index can be lowered and light reflection can be reduced. More preferably, it is 20% or more by volume, and even more preferably, it is 30% or more by volume. On the other hand, if the proportion of cavities is 80% or less by volume, it is possible to prevent a decrease in the dispersibility of the hollow silica particles. More preferably, it is 60% or less by volume.
  • the average particle diameter of the hollow silica particles depends on the thickness d of the low refractive index layer 16, but is preferably 5 nm or more and 100 nm or less. It is more preferably 20 nm or more, and even more preferably 40 nm or more. It is more preferably 80 nm or less, and even more preferably 70 nm or less. When the average particle diameter of the hollow silica particles is within these preferred ranges, excellent anti-reflection effect and transparency can be obtained in the low refractive index layer 16.
  • the average particle diameter is a volume-based average arithmetic value obtained by a laser diffraction/scattering method according to JIS Z8825. It includes not only the primary particle diameter but also the secondary particle diameter, which is an aggregate of particles.
  • the refractive index of the hollow silica particles is preferably in the range of 1.01 to 1.45. More preferably, it is in the range of 1.15 to 1.38, and even more preferably, it is in the range of 1.15 to 1.35. When the refractive index of the hollow silica particles is within this range, an excellent anti-reflection effect can be obtained.
  • the content of hollow silica particles in the low refractive index layer 16 is preferably 6.0% by mass or more and 60% by mass or less with respect to 100% by mass of the solid content of the low refractive index layer 16.
  • the content of hollow silica particles in the low refractive index layer 16 is 6.0% by mass or more with respect to 100% by mass of the solid content of the low refractive index layer 16, excellent anti-reflection properties can be obtained.
  • the content of hollow silica particles in the low refractive index layer 16 is more preferably 15% by mass or more, and even more preferably 30% by mass or more with respect to 100% by mass of the solid content of the low refractive index layer 16.
  • the content of hollow silica particles in the low refractive index layer 16 is 60% by mass or less with respect to 100% by mass of the solid content of the low refractive index layer 16, the deterioration of scratch resistance is suppressed.
  • the content of hollow silica particles in the low refractive index layer 16 is more preferably 55% by mass or less, and even more preferably 50% by mass or less with respect to 100% by mass of the solid content of the low refractive index layer 16.
  • the solid content of the low refractive index layer 16 here refers to components excluding those that are not fixed to the binder resin in the low refractive index layer 16 and are liquid at room temperature.
  • the solid content of the low refractive index layer 16 includes hollow silica particles, binder resin, etc. It does not include oil components as additives or surfactants that are not fixed to the binder resin.
  • the low refractive index layer 16 may contain inorganic oxide particles in addition to hollow silica particles. When inorganic oxide particles are contained in the low refractive index layer 16, convex portions are formed on the surface of the low refractive index layer 16. The inorganic oxide particles form convex portions on the surface of the low refractive index layer 16, which allows the low refractive index layer 16 to have good scratch resistance.
  • the inorganic oxide particles may be solid or hollow. It is preferable that the inorganic oxide particles are solid.
  • a solid particle is a particle that does not have a cavity inside the particle, and the cavity ratio is less than 5% of the volume of the solid particle.
  • a hollow particle is a particle that has a cavity inside the particle, and the cavity ratio is 5% or more of the volume of the hollow particle.
  • the cavity ratio is preferably 10% or more and 80% or less of the volume of the hollow particles.
  • the cavity ratio is 10% or more, the refractive index can be lowered to reduce light reflection. It is more preferable that the cavity ratio is 20% or more, and even more preferable that the cavity ratio is 30% or more.
  • the cavity ratio is 80% or less, the decrease in dispersibility of the inorganic oxide particles can be suppressed. More preferably, it is 60% or less.
  • inorganic oxide particles include metal oxide particles made of oxides of metals such as zirconium, silicon, aluminum, and calcium. These may be used alone as inorganic oxide particles, or two or more may be used in combination. Among these, silica particles and alumina particles are preferred, with alumina particles being particularly preferred, from the standpoints of low refractive index, excellent transparency, and high hardness.
  • the shape of the inorganic oxide particles is not particularly limited, and may be spherical, needle-like, scaly, rod-like, fibrous, amorphous, etc. Of these, spherical is preferred.
  • the difference (r-d) between the average particle diameter r of the inorganic oxide particles and the average thickness d of the low refractive index layer 16 is 10 nm or more.
  • the difference (r-d) is more preferably 15 nm or more, and even more preferably 18 nm or more.
  • the difference (r-d) is 300 nm or less. More preferably, it is 200 nm or less, and even more preferably 100 nm or less.
  • the average particle diameter r of the inorganic oxide particles depends on the thickness d of the low refractive index layer 16, but is preferably in the range of 60 nm to 400 nm. It is more preferably 70 nm or more, and even more preferably 90 nm or more. It is more preferably 300 nm or less, and even more preferably 200 nm or less.
  • the average particle diameter r of the inorganic oxide particles is a volume-based average arithmetic value obtained by a laser diffraction/scattering method in accordance with JIS Z8825, and includes not only the primary particle diameter but also the secondary particle diameter, which is a particle aggregate.
  • the content of inorganic oxide particles in the low refractive index layer 16 is preferably 0.1% by mass or more and 4.0% by mass or less with respect to 100% by mass of the solid content of the low refractive index layer 16.
  • the content of inorganic oxide particles in the low refractive index layer 16 is 0.1% by mass or more with respect to 100% by mass of the solid content of the low refractive index layer 16, excellent scratch resistance can be obtained.
  • the content of inorganic oxide particles in the low refractive index layer 16 is more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more with respect to 100% by mass of the solid content of the low refractive index layer 16.
  • the content of inorganic oxide particles in the low refractive index layer 16 is 4.0% by mass or less with respect to 100% by mass of the solid content of the low refractive index layer 16, high transparency can be obtained.
  • the content of inorganic oxide particles in the low refractive index layer 16 is more preferably 3.5% by mass or less, and even more preferably 3.2% by mass or less with respect to 100% by mass of the solid content of the low refractive index layer 16.
  • the total amount of inorganic oxide particles and hollow silica particles in the low refractive index layer 16 is preferably 10% by mass or more and 50% by mass or less with respect to 100% by mass of the solid content of the low refractive index layer 16.
  • the total amount of inorganic oxide particles and hollow silica particles in the low refractive index layer 16 is 10% by mass or more with respect to 100% by mass of the solid content of the low refractive index layer 16, excellent scratch resistance can be obtained.
  • the total amount of inorganic oxide particles and hollow silica particles in the low refractive index layer 16 is more preferably 15% by mass or more, and even more preferably 20% by mass or more with respect to 100% by mass of the solid content of the low refractive index layer 16.
  • the total amount of inorganic oxide particles and hollow silica particles in the low refractive index layer 16 is 50% by mass or less with respect to 100% by mass of the solid content of the low refractive index layer 16, the inorganic oxide particles and hollow silica particles can be sufficiently retained in the low refractive index layer 16, and therefore excellent scratch resistance can be obtained.
  • the total amount of inorganic oxide particles and hollow silica particles in the low refractive index layer 16 is more preferably 45% by mass or less, and even more preferably 40% by mass or less, relative to 100% by mass of the solid content of the low refractive index layer 16.
  • the low refractive index layer 16 can be formed using a composition containing hollow silica particles, a binder resin, and, if necessary, inorganic oxide particles.
  • the binder resin is preferably one having a reactive group reactive to ultraviolet light (ultraviolet curing resin), such as one containing a (meth)acrylate compound.
  • the binder resin has a reactive group reactive to ultraviolet light
  • the scratch resistance of the low refractive index layer 16 is improved, and the scratch resistance of the anti-reflection film 10 is improved.
  • the composition for forming the low refractive index layer 16 preferably further contains a photopolymerization initiator.
  • the composition for forming the low refractive index layer 16 may contain a solvent as necessary.
  • the binder resin of the low refractive index layer 16 may be composed of only an ultraviolet curing resin, or may be composed of a combination of an ultraviolet curing resin and a non-ultraviolet curing resin.
  • the non-ultraviolet curing resin, the photopolymerization initiator, and the solvent the chemical species listed above as specific examples of those that can be contained in the composition for forming the hard coat layer 14 can also be suitably applied to the composition for forming the low refractive index layer 16.
  • the content of the photopolymerization initiator is preferably in the range of 0.1% by mass or more and 10% by mass or less, based on the total solid content of the composition for forming the low refractive index layer 16. More preferably, it is 1% by mass or more and 5% by mass or less.
  • the low refractive index layer 16 may contain additives, etc., as necessary.
  • additives include dispersants, leveling agents, defoamers, thixotropic agents, antibacterial agents, flame retardants, slip agents, refractive index adjusters, etc.
  • the average thickness d of the low refractive index layer 16 is preferably in the range of 60 to 160 nm, more preferably in the range of 70 to 140 nm, and even more preferably in the range of 80 to 120 nm. Within this range, the luminous reflectance is good and light reflection can be reduced.
  • the thickness of the low refractive index layer 16 is the thickness of a relatively smooth portion in the thickness direction that is free of irregularities caused by inorganic particles.
  • the refractive index of the low refractive index layer 16 is not particularly limited as long as it is lower than that of the hard coat layer 14, but is preferably 1.26 or more and 1.50 or less. If the refractive index is 1.26 or more, the strength of the low refractive index layer 16 can be made sufficient, and good scratch resistance can be obtained. On the other hand, if the refractive index is 1.50 or less, the anti-reflection film 10 can have a lower reflectance. From the above viewpoints, the refractive index of the low refractive index layer 16 is more preferably 1.28 or more and 1.40 or less, and even more preferably 1.30 or more and 1.37 or less.
  • an anti-soiling layer 18 is provided on the surface of the low refractive index layer 16.
  • the anti-soiling layer 18 enhances the anti-soiling properties of the anti-reflection film 10.
  • the stain-resistant layer 18 is composed of a cured product of a composition containing a fluorinated (meth)acrylate.
  • the antifouling layer 18 is composed of a cured product of an ionizing radiation-curable composition containing a fluorinated (meth)acrylate, particularly an ultraviolet-curable composition.
  • the antifouling layer 18 is made of a cured product of a composition containing a fluorine-containing (meth)acrylate, and thus the antireflection film 10 having the antifouling layer 18 on its surface has excellent antifouling properties and abrasion resistance.
  • fluorine-containing (meth)acrylates include (meth)acrylates containing a perfluoropolyether group.
  • the perfluoropolyether group refers to a polyether such as polyethylene glycol or polypropylene glycol in which all hydrogen atoms are replaced with fluorine atoms, and examples thereof include fluoropolyether groups having a repeating structure of any one of perfluoromethylene oxide (-CF 2 O-), perfluoroethylene oxide (-CF 2 CF 2 O-), perfluoropropylene oxide (-CF 2 CF 2 CF 2 O-), and perfluoroisopropylene oxide (-CF(CF 3 )CF 2 O-), or a combination of a plurality of these.
  • the number of repeating units of the repeating structure is preferably 1 to 100.
  • the fluorine-containing (meth)acrylate preferably has a polar site such as a hydroxy group at the end of the perfluoroether group, etc.
  • a polar site such as a hydroxy group at the end of the perfluoroether group, etc.
  • Specific examples of the compound include “KY-1203", “KY-1207”, “KY-1211”, “KY-1216”, and “KY-1240” manufactured by Shin-Etsu Chemical Co., Ltd., “Megafac RS-75” manufactured by DIC, “Optool DAC-HP” and “Optool DAC-100” manufactured by Daikin Industries, Ltd., and "Ftergent 601AD” and "Ftergent 601ADH2" manufactured by Neos.
  • the fluorine-containing (meth)acrylate may contain, at least in part, one having a urethane bond in its molecular structure.
  • the content of the fluorine-containing (meth)acrylate having a urethane bond is preferably less than 15 parts by mass per 100 parts by mass of the fluorine-containing (meth)acrylate not having a urethane bond.
  • the content is more preferably less than 10 parts by mass, and even more preferably less than 5 parts by mass. It is particularly preferable that the fluorine-containing (meth)acrylate does not contain a fluorine-containing (meth)acrylate having a urethane bond.
  • the content of the fluorine-containing (meth)acrylate is 90% by mass or more based on the total solid content of the antifouling layer 18. This makes it possible to obtain a high antifouling effect by the fluorine-containing (meth)acrylate.
  • the content of the fluorine-containing (meth)acrylate in the antifouling layer 18 is more preferably 92% by mass or more based on the total solid content of the antifouling layer 18.
  • the total amount of the resin components constituting the antifouling layer 18, excluding unavoidable components is the fluorine-containing (meth)acrylate.
  • the antifouling layer 18 contains a fluorine-containing (meth)acrylate with a high polar component ⁇ p of the surface free energy, and therefore exhibits high adhesion to the low refractive index layer 16, and therefore the effect of improving adhesion to the low refractive index layer 16 and the resulting improvement in abrasion resistance can be sufficiently obtained. Therefore, in order to obtain these effects, it is not necessary to add a binder resin that does not contain fluorine, such as a fluorine-free (meth)acrylate compound, to the stain-resistant layer 18.
  • the solid content of the stain-resistant layer 18 here refers to the components in the stain-resistant layer 18 that are not fixed to the curable component and are liquid at room temperature.
  • the solid content of the stain-resistant layer 18 includes fluorine-containing (meth)acrylate and the like.
  • the anti-fouling layer 18 contains, as at least a portion of the fluorine-containing (meth)acrylate, a fluorine-containing (meth)acrylate having a polar component ⁇ p of the surface free energy of 18 mN/m or more (hereinafter, sometimes referred to as a large polarity component fluorine-containing (meth)acrylate). And, the content of the large polarity component fluorine-containing (meth)acrylate (proportion to the total fluorine-containing (meth)acrylate) in the solid content of the fluorine-containing (meth)acrylate contained in the anti-fouling layer 18 is 50 mass% or more.
  • Surface free energy refers to the molecular energy of the surface of a solid itself, and indicates how easily it wets a liquid or another solid.
  • the surface free energy of a substance can be divided into three components: a dispersion component ( ⁇ d), a polar component ( ⁇ p), and a hydrogen bond component ( ⁇ h).
  • the dispersion component ( ⁇ d) indicates the effect of dispersion forces
  • the polar component ( ⁇ p) indicates the effect of dipole-dipole forces
  • the hydrogen bond component ( ⁇ h) indicates the effect of hydrogen bond forces, and can be calculated based on the Kitazaki-Hata theory. It is expressed in units of mN/m.
  • the antifouling layer 18 of the antireflection film 10 contains, as at least a part of the fluorine-containing (meth)acrylate, a large polarity component fluorine-containing (meth)acrylate having a polar component ⁇ p of the surface free energy of 18 mN/m or more. This makes it possible to obtain excellent abrasion resistance. This is believed to be because the large polarity component fluorine-containing (meth)acrylate improves the adhesion of the antifouling layer 18 to the low refractive index layer 16 below.
  • the fluorine-containing (meth)acrylate has a large polarity component ⁇ p of the surface free energy
  • the fluorine-containing (meth)acrylate contains a polar site such as a hydroxyl group in its molecular structure, and it is presumed that the contribution of the polar site can improve the adhesion to the low refractive index layer 16.
  • the antifouling layer 18 contains a large polarity component fluorine-containing (meth)acrylate, the abrasion resistance is improved, and wear marks (changes in the reflection characteristics at the friction points) and scratches are less likely to occur even if the surface of the antireflection film 10 is wiped with a cloth, felt, or the like.
  • the polar component ⁇ p of the surface free energy of the large polar component fluorine-containing (meth)acrylate contained in the stain-resistant layer 18 is preferably 19 mN/m or more, and more preferably 20 mN/m or more, from the viewpoint of further enhancing the effect of improving abrasion resistance.
  • the upper limit of ⁇ p is not particularly specified, but from the viewpoint of improving stain resistance, it is preferably 35 mN/m or less, more preferably 30 mN/m or less, and even more preferably 25 mN/m or less.
  • the abrasion resistance of the antifouling layer 18 can be effectively improved by having the content of the large polarity component fluorine-containing (meth)acrylate be 50 mass% or more of the solid content of the fluorine-containing (meth)acrylate in the antifouling layer 18.
  • the content of the large polarity component fluorine-containing (meth)acrylate is more preferably 55 mass% or more, and even more preferably 60 mass% or more, calculated based on the total amount of the solid content of the fluorine-containing (meth)acrylate in the antifouling layer 18. It is particularly preferable that the total amount of the fluorine-containing (meth)acrylate contained in the antifouling layer 18, excluding unavoidable impurities, is the large polarity component fluorine-containing (meth)acrylate.
  • the hydrogen bond component ⁇ h of the surface free energy of the large polar component fluorine-containing (meth)acrylate is not particularly limited, but is preferably 8 mN/m or less, more preferably 6 mN/m or less, and even more preferably 3 mN/m or less. If ⁇ h is 8 mN/m or less, the antifouling effect of the antifouling layer 18 will be good. On the other hand, the lower ⁇ h is the more preferable, and the lower limit may be 0.
  • the dispersion component ⁇ d of the surface free energy of the large polarity component fluorine-containing (meth)acrylate is not particularly limited, but is preferably 8 mN/m or more and 40 mN/m or less, more preferably 10 mN/m or more and 35 mN/m or less, and even more preferably 11 mN/m or more and 32 mN/m or less. If ⁇ d is in this range, aggregation of the fluorine-containing (meth)acrylate is suppressed, making it easier to obtain a uniform coating film.
  • the surface free energy ⁇ of the large polarity component fluorine-containing (meth)acrylate is not particularly limited, but is preferably 26 mN/m or more and 60 mN/m or less, more preferably 28 mN/m or more and 50 mN/m or less, and even more preferably 30 mN/m or more and 40 mN/m or less. If ⁇ is within these ranges, the antifouling properties of the antifouling layer 18 can be made good.
  • the anti-stain layer 18 can be formed using a composition containing a fluorinated (meth)acrylate.
  • the composition for forming the anti-stain layer 18 can be arranged in a layer on the surface of the low refractive index layer 16 and then cured.
  • the anti-stain layer 18 is formed as a cured product of a composition having ultraviolet curing properties, it is preferable that the composition for forming the anti-stain layer 18 further contains a photopolymerization initiator. It may also contain a solvent as necessary.
  • the photopolymerization initiator and the solvent the chemical species given above as specific examples of those that can be contained in the composition for forming the hard coat layer 14 can also be suitably applied to the composition for forming the antifouling layer 18.
  • the content of the photopolymerization initiator is preferably in the range of 0.1% by mass or more and 15% by mass or less, based on the total solid content of the composition for forming the antifouling layer 18. More preferably, it is 3% by mass or more and 10% by mass or less.
  • the antifouling layer 18 may contain additives, etc., as necessary.
  • additives include antifouling agents other than fluorinated (meth)acrylates, dispersants, leveling agents, defoamers, thixotropic agents, antibacterial agents, flame retardants, slip agents, and refractive index adjusters.
  • the antifouling layer 18 does not contain solid particles, including hollow silica particles and metal acid particles.
  • the particle size of the solid particles is kept to 10 nm or less, and the content of the solid particles is kept to 1 mass % or less relative to 100 mass % of the solid content of the antifouling layer 18.
  • the thickness of the antifouling layer 18 is preferably 1 nm or more. This allows the antifouling layer 18 to have a high effect of improving the antifouling properties. More preferably, the thickness of the antifouling layer 18 is 3 nm or more, or even 5 nm or more. On the other hand, the thickness of the antifouling layer 18 is preferably 20 nm or less. This allows the antireflection properties and abrasion resistance of the antireflection film 10 to be maintained at a high level. More preferably, the thickness of the antifouling layer 18 is 15 nm or less, or even 10 nm or less.
  • the refractive index of the anti-stain layer 18 is preferably 1.6 or less. If the refractive index is 1.6 or less, the anti-reflection properties of the anti-reflection film 10 can be maintained at a high level. More preferably, the refractive index of the anti-stain layer 18 is 1.55 or less, and even more preferably 1.50 or less. On the other hand, the refractive index of the anti-stain layer 18 is not particularly limited as long as the thickness of the anti-stain layer 18 is within the above range, but is preferably 1.3 or more, and more preferably 1.35 or more.
  • the hard coat layer 14, the low refractive index layer 16, and the antifouling layer 18 may be formed in this order.
  • a composition for forming each layer may be applied, dried as necessary, and then cured by a method according to the curing property of the composition, such as irradiation with ionizing radiation including ultraviolet rays.
  • a composition for forming the next layer may be applied, dried as necessary, and then cured.
  • wet methods can be suitably used to apply the compositions that form each layer.
  • various coating methods such as reverse gravure coating, direct gravure coating, die coating, bar coating, wire bar coating, roll coating, spin coating, dip coating, spray coating, knife coating, and kiss coating, as well as various printing methods such as inkjet printing, offset printing, screen printing, and flexographic printing can be used.
  • the drying process for each layer is not particularly limited as long as it can remove the solvents used in the coating liquid, but it is preferable to perform the process at a temperature of 50 to 150°C for about 10 to 180 seconds.
  • a high pressure mercury lamp, an electrodeless (microwave type) lamp, a xenon lamp, a metal halide lamp, or any other ultraviolet light irradiation device can be used.
  • the ultraviolet light irradiation may be performed under an inert gas atmosphere such as nitrogen, if necessary.
  • the amount of ultraviolet light irradiation is not particularly limited, but is preferably 50 to 800 mJ/ cm2 , and more preferably 100 to 300 mJ/ cm2 .
  • the surface of the substrate film 12 may be subjected to a surface treatment before coating in order to improve the adhesion between the substrate film 12 and the hard coat layer 14.
  • surface treatments include corona treatment, plasma treatment, hot air treatment, ozone treatment, and ultraviolet treatment.
  • a primer layer having an adhesion improving effect such as a layer made of a non-fluorine-containing (meth)acrylate resin, may be formed on the surface of the low refractive index layer 16 before the anti-fouling layer 18 is formed.
  • the anti-fouling layer 18 contains a predetermined amount or more of a large polar component fluorine-containing (meth)acrylate and therefore exhibits high adhesion to the low refractive index layer 16, it is not necessary to provide a primer layer for the purpose of improving the adhesion of the anti-fouling layer 18 and thereby improving its abrasion resistance. Not providing a primer layer is preferable in that the structure of the anti-reflection film 10 can be simplified.
  • the anti-reflection film 10 having the above configuration has a base film 12, a hard coat layer 14 formed on the surface of the base film 12, a low refractive index layer 16 formed on the surface of the hard coat layer 14, and an anti-fouling layer 18 formed on the surface of the low refractive index layer 16, wherein the anti-fouling layer 18 is composed of a cured product of a composition containing a fluorinated (meth)acrylate, the content of the fluorinated (meth)acrylate in the anti-fouling layer 18 is 90 mass% or more based on the total solid content of the anti-fouling layer 18, and 50 mass% or more of the solid content of the fluorinated (meth)acrylate contained in the anti-fouling layer is a fluorinated (meth)acrylate having a polar component ⁇ p of the surface free energy of 18 mN/m or more.
  • the anti-reflection film 10 has excellent anti-
  • the anti-reflection film 10 has high antifouling properties, so that stains such as fingerprints are less likely to adhere to the surface of the anti-reflection film 10, and even if they do adhere, they can be easily removed.
  • the anti-reflection film 10 according to this embodiment has particularly excellent fingerprint wiping properties.
  • the high antifouling properties are believed to be due to the fact that the anti-fouling layer 18 contains 90 mass% or more of fluorine-containing (meth)acrylate based on the total solid content.
  • the high abrasion resistance is believed to be due to the high adhesion between the low refractive index layer 16 and the antifouling layer 18, which is due to the fact that 50 mass% or more of the solid content of the fluorine-containing (meth)acrylate is a large polar component fluorine-containing (meth)acrylate with a polar component ⁇ p of the surface free energy of 18 mN/m or more.
  • the anti-reflection film 10 according to this embodiment has high anti-reflection properties and antifouling properties as well as high scratch resistance and abrasion resistance, and is therefore particularly suitable for applications that are frequently contacted by fingers, including those placed on the surface of a touch panel.
  • the antireflection film 10 preferably has a water contact angle of 100° or more, and more preferably 105° or more.
  • the oleic acid contact angle is preferably 73° or more, and more preferably 75° or more.
  • the oleic acid sliding angle is preferably 25° or less, and more preferably 20° or less.
  • Oleic acid is a substance that simulates sebum, and the larger the oleic acid contact angle, the less likely organic dirt such as sebum will adhere to the antireflection film 10.
  • the surface free energy of the surface of the antireflection film 10 (the surface in the state in which each constituent layer is laminated and cured) is preferably 30 mN/m or less, more preferably 20 mN/m or less, and particularly preferably 15 mN/m or less. This provides the surface of the anti-reflection film 10 with high water and oil repellency and stain resistance.
  • the antireflection film according to the present invention is a film in which the hard coat layer 14, the low refractive index layer 16, and the antifouling layer 18 are laminated in this order on the surface of the substrate film 12, and is not limited to the configuration of the antireflection film 10 according to the first embodiment described above, so long as the antifouling layer 18 has a predetermined composition.
  • Other embodiments of the antireflection film according to the present invention will be exemplified below.
  • Second Embodiment 2 shows an anti-reflection film 20 according to the second embodiment.
  • the anti-reflection film 20 according to the second embodiment has a base film 12, a hard coat layer 14 formed on the surface of the base film 12, a high refractive index layer 15 formed on the surface of the hard coat layer 14, a low refractive index layer 16 formed on the surface of the high refractive index layer 15, and an antifouling layer 18 formed on the surface of the low refractive index layer 16.
  • the anti-reflection film 20 according to the second embodiment differs from the anti-reflection film 10 according to the first embodiment in that it has a high refractive index layer 15 between the hard coat layer 14 and the low refractive index layer 16. Other than this, it is similar to the anti-reflection film 10 according to the first embodiment, and a description of the similar configuration will be omitted.
  • the high refractive index layer 15 is a layer having a higher refractive index than the hard coat layer 14 and the low refractive index layer 16. By providing the high refractive index layer 15 between the hard coat layer 14 and the low refractive index layer 16, the anti-reflection film 20 exhibits a higher anti-reflection effect.
  • the refractive index of the high refractive index layer 15 is preferably in the range of 1.55 or more and 1.80 or less. More preferably, it is 1.60 or more and 1.70 or less.
  • the material constituting the high refractive index layer 15 is not particularly limited, and any known material conventionally used in anti-reflection films and the like may be used so as to obtain the desired refractive index.
  • the material may be appropriately selected from the materials described above as usable in the hard coat layer 14 and the low refractive index layer 16.
  • the refractive index of the high refractive index layer 15 can be adjusted by the selection and amount of binder resin, inorganic oxide particles, and resin particles. For example, by adding a sufficient amount of inorganic oxide particles such as titanium oxide particles, a high refractive index layer 15 having a higher refractive index than the low refractive index layer 16 can be formed.
  • the average thickness of the high refractive index layer 15 varies depending on the refractive index setting, but by setting it to, for example, 50 nm or more and 200 nm or less, the anti-reflection function can be further improved.
  • the high refractive index layer 15 may be provided by stacking two or more layers having mutually different refractive indices.
  • Third Embodiment 3 shows an anti-reflection film 30 according to a third embodiment.
  • the anti-reflection film 30 according to the third embodiment has a base film 12, a hard coat layer 14 formed on one side of the base film 12, a low refractive index layer 16 formed on the surface of the hard coat layer 14, and an antifouling layer 18 formed on the surface of the low refractive index layer 16.
  • the base film 12 also has a transparent adhesive layer 22 on the other side.
  • a release film 24 is disposed on the surface of the transparent adhesive layer 22 as necessary. The release film 24 functions as a protective layer for the transparent adhesive layer 22 before use of the anti-reflection film 30, and is peeled off from the transparent adhesive layer 22 when the anti-reflection film 30 is used.
  • the anti-reflection film 30 according to the third embodiment differs from the anti-reflection film 10 according to the first embodiment in that it has a transparent adhesive layer 22 on the other side of the base film 12, but is otherwise similar to the anti-reflection film 10 according to the first embodiment, and a description of the similar configuration will be omitted.
  • the transparent adhesive layer 22 is for attaching the anti-reflection film 30 to the surface of a display or the like with good adhesion. Furthermore, by having the transparent adhesive layer 22, the anti-reflection film 30 has the effect of preventing the glass of a display or the like from shattering. In other words, the anti-reflection film 30 also functions as a shatterproof film.
  • the adhesive composition forming the transparent adhesive layer 22 can contain known adhesive resins such as acrylic adhesives, silicone adhesives, and urethane adhesives. Among them, acrylic adhesives are preferred from the viewpoint of optical transparency and heat resistance.
  • the adhesive composition preferably contains a crosslinking agent to increase the cohesive strength of the transparent adhesive layer 22. Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, and chelate crosslinking agents.
  • the adhesive composition may contain additives as necessary.
  • additives include known additives such as plasticizers, silane coupling agents, surfactants, antioxidants, fillers, hardening accelerators, and hardening retarders. From the standpoint of productivity, the adhesive composition may be diluted with an organic solvent.
  • the thickness of the transparent adhesive layer 22 is not particularly limited, but is preferably in the range of 5 ⁇ m to 100 ⁇ m. More preferably, it is 10 ⁇ m or more and 50 ⁇ m or less.
  • the transparent adhesive layer 22 can be formed by a method of directly applying an adhesive composition onto the other side of the base film 12, a method of applying an adhesive composition onto the surface of a release film 24 and then transferring it onto the other side of the base film 12, or a method of applying an adhesive composition onto the surface of a first release film and then laminating a second release film, peeling off one of the release films, and transferring it onto the other side of the base film 12.
  • the adhesive strength of the transparent adhesive layer 22 to glass is 4 N/25 mm or more. More preferably, it is 6 N/25 mm or more, and even more preferably, it is 10 N/25 mm or more.
  • the anti-reflection film 40 according to the fourth embodiment has a base film 12, a hard coat layer 14 formed on one surface of the base film 12, a low refractive index layer 16 formed on the surface of the hard coat layer 14, an antifouling layer 18 formed on the surface of the low refractive index layer 16, and a protective film 28 arranged on the surface of the antifouling layer 18 via an adhesive layer 26.
  • the other surface of the base film 12 also has a transparent adhesive layer 22.
  • a release film 24 is arranged on the surface of the transparent adhesive layer 22 as necessary.
  • the anti-reflection film 40 according to the fourth embodiment differs from the anti-reflection film 30 according to the third embodiment in that it has a protective film 28 on the surface of the anti-fouling layer 18 via an adhesive layer 26, but is otherwise similar to the anti-reflection film 30 according to the third embodiment, and a description of the similar configuration will be omitted.
  • the protective film 28 prevents the surface of the antifouling layer 18 from being scratched when the antireflection film 40 is handled, for example, when it is continuously processed by a roll process or attached to a display or the like.
  • the protective film 28 is attached to the surface of the antifouling layer 18 via the adhesive layer 26.
  • the protective film 28 is peeled off from the surface of the antifouling layer 18 together with the adhesive layer 26 after processing of the antireflection film 40.
  • the adhesive layer 26 is adjusted so that the adhesive strength between the protective film 28 and the adhesive layer 26 is stronger than the adhesive strength between the antifouling layer 18 and the adhesive layer 26, and the adhesive strength between the antifouling layer 18 and the adhesive layer 26 is capable of being peeled off at the interface.
  • the material constituting the protective film 28 can be appropriately selected from the materials exemplified as the material constituting the base film 12.
  • the thickness of the protective film 28 is not particularly limited, but can be in the range of 2 ⁇ m to 500 ⁇ m, or in the range of 2 ⁇ m to 200 ⁇ m.
  • the adhesive layer 26 the one described in International Publication No. 2021/020504 filed by the applicant can be suitably applied.
  • the adhesive forming the adhesive layer 26 is not particularly limited, and an acrylic adhesive, a silicone adhesive, a urethane adhesive, etc. can be suitably used.
  • an acrylic adhesive is suitable because of its excellent transparency and heat resistance.
  • the acrylic adhesive is preferably formed from an adhesive composition containing a (meth)acrylic polymer and a crosslinking agent.
  • (Meth)acrylic polymers are homopolymers or copolymers of (meth)acrylic monomers.
  • Examples of (meth)acrylic monomers include alkyl group-containing (meth)acrylic monomers, carboxyl group-containing (meth)acrylic monomers, and hydroxyl group-containing (meth)acrylic monomers.
  • crosslinking agents examples include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, metal chelate-based crosslinking agents, metal alkoxide-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, and melamine-based crosslinking agents. These crosslinking agents may be used alone or in combination of two or more.
  • the adhesive composition may contain other additives in addition to the (meth)acrylic polymer and crosslinking agent.
  • additives include crosslinking accelerators, crosslinking retarders, tackifier resins, antistatic agents, silane coupling agents, plasticizers, peeling aids, pigments, dyes, wetting agents, thickeners, UV absorbers, preservatives, antioxidants, metal deactivators, alkylating agents, and flame retardants. These are selected and used appropriately depending on the application and purpose of the adhesive.
  • the thickness of the adhesive layer 26 is not particularly limited, but is preferably in the range of 1 ⁇ m to 10 ⁇ m. More preferably, it is 2 ⁇ m or more and 7 ⁇ m or less.
  • the surface of the base film 12 may be subjected to a surface treatment, but instead of the surface treatment, an easy-adhesion layer may be provided on the surface of the base film 12.
  • the transparent adhesive layer 22 and release film 24 in the third embodiment are shown as being added to the anti-reflection film 10 of the first embodiment shown in FIG. 1, as shown in FIG. 3, but may also be added to the anti-reflection film 20 of the second embodiment shown in FIG. 2.
  • the adhesive layer 26 and protective film 28 in the fourth embodiment are shown as being added to the anti-reflection film 30 of the third embodiment shown in FIG. 3, as shown in FIG. 4, but may also be added to the anti-reflection film 10 of the first embodiment shown in FIG. 1 or the anti-reflection film 20 of the second embodiment shown in FIG. 2.
  • various functional layers such as a gas barrier improving layer, an antistatic layer, and an oligomer block layer may be provided on the surface of the base film 12 before each layer is formed.
  • a gas barrier improving layer such as a gas barrier improving layer, an antistatic layer, and an oligomer block layer may be provided on the surface of the base film 12 before each layer is formed.
  • an antistatic layer those described in the above-mentioned WO 2021/020504 can be suitably applied.
  • the fluorine-containing compounds 1 to 3 and binder resin 1 listed below were each applied to a polyethylene terephthalate film "Lumirror U403" (manufactured by Toray, thickness 100 ⁇ m) using a wire bar so that the thickness after drying would be 0.5 ⁇ m, and then dried at 80°C for 180 seconds to obtain a sample for measuring surface free energy.
  • Fluorine-containing compounds 1 to 3 are used for the formation of the antifouling layer, and binder resin 1 is used for the formation of the low refractive index layer.
  • Fluorine-containing compound 1 "KY-1203" manufactured by Shin-Etsu Chemical Co., Ltd., perfluoropolyether group-containing (meth)acrylate, methyl ethyl ketone, solid content concentration 20% by mass Fluorine-containing compound 2: "KY-1211” manufactured by Shin-Etsu Chemical Co., Ltd., perfluoropolyether group-containing (meth)acrylate, methyl ethyl ketone, solid content concentration 20% by mass Fluorine-containing compound 3: "KY-1216” manufactured by Shin-Etsu Chemical Co., Ltd., perfluoropolyether group-containing (meth)acrylate, methyl ethyl ketone, solid content concentration 20% by mass Binder resin 1: A fluorine-containing binder resin prepared by the method described below.
  • the evaluation results are shown in Table 1.
  • the table also shows the surface free energy ( ⁇ ) calculated using formula (1).
  • fluorine-containing compound 1 has a polar component ⁇ p of the surface free energy of 18 mN/m or more.
  • fluorine-containing compounds 2 and 3 have a polar component ⁇ p of the surface free energy of less than 18 mN/m.
  • binder resin 1 has a larger surface free energy ⁇ and a larger polar component ⁇ p.
  • a composition for forming a hard coat layer was prepared by adding solvents (ethyl acetate, propylene glycol monomethyl ether) to an ultraviolet-curable resin composition "Lioduras LAS-13030NL” (manufactured by Toyochem, urethane acrylate resin, photopolymerization initiator, solvent (ethyl acetate), solid content concentration 50% by mass) so that the solid content concentration was 45% by mass.
  • solvents ethyl acetate, propylene glycol monomethyl ether
  • UV-curable resin composition "Shiko UV-7600B” manufactured by Mitsubishi Chemical, urethane acrylate resin, solid content concentration 100% by mass to 54% by mass
  • Zinc antimonate microparticle dispersion Nissan Chemical's "Celnax CX-Z603M-F2", zinc antimonate microparticles, solvent (methanol), solid content 60% by mass to 44% by mass
  • Photopolymerization initiator "Omnirad 184" manufactured by IGM Resins B.V., 1-hydroxycyclohexyl phenyl ketone-3% by mass
  • the obtained solid was dissolved in diethyl ether, poured into perfluorohexane, separated, and vacuum dried to obtain a colorless and transparent polymer that is a fluorine-containing allyl ether polymer containing a hydroxyl group.
  • composition for forming low refractive index layer Preparation of composition for forming low refractive index layer
  • binder resin 1 hollow silica particles, a fluorine-containing compound different from binder resin 1 (only Comparative Example 4), and a photopolymerization initiator were blended to obtain the blending composition (mass % of the total solid content) shown in Table 2, and the solid content concentration was adjusted to the solid content concentration shown in Table 2 using isopropyl alcohol, thereby preparing a composition for forming a low refractive index layer.
  • Binder resin Binder resin 1 Hollow silica particles: “Sururia 4320” manufactured by JGC Catalysts and Chemicals, average particle size 60 nm, solvent: MIBK, solid content concentration: 20% by mass
  • Photopolymerization initiator "Omnirad 127" manufactured by IGM Resins B.V., 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one, solid content concentration 100% by mass Fluorine-containing compound: the above-mentioned "KY-1203"
  • a hard coat layer-forming composition was applied to a substrate film (FUJIFILM Corporation's "TG60UL", a cellulose triacetate film, thickness 60 ⁇ m) using a wire bar, and the composition was dried at 80°C for 60 seconds, followed by irradiation with ultraviolet light at a light intensity of 200 mJ/ cm2 using a high-pressure mercury lamp to form a hard coat layer.
  • the film thickness was as shown in Table 2.
  • ⁇ Preparation of high refractive index layer> For each of Examples 1 to 3 and Comparative Examples 1 to 5, a composition for forming a high refractive index layer was applied onto the surface of the hard coat layer using a #3 wire bar, and dried at 80°C for 60 seconds. After that, a high refractive index layer (film thickness 160 nm) was formed by irradiating the composition with ultraviolet light at a light intensity of 200 mJ/ cm2 using a high pressure mercury lamp under a nitrogen atmosphere.
  • ⁇ Preparation of low refractive index layer> For each of Examples 1 to 3 and Comparative Examples 1 to 5, a composition for forming a low refractive index layer was applied onto the surface of the high refractive index layer using a #3 wire bar, and after drying at 100°C for 60 seconds, a low refractive index layer was formed by irradiating ultraviolet light with a light amount of 200 mJ/ cm2 using a high pressure mercury lamp in a nitrogen atmosphere. The film thickness was as shown in Table 2.
  • the water contact angle and oleic acid contact angle of the anti-reflection film were measured using a contact angle meter (DropMaster DMo-502, manufactured by Kyowa Interface Science Co., Ltd.). Specifically, 4 ⁇ L of pure water and oleic acid were dropped onto the surface of the anti-fouling layer in an atmosphere of room temperature 23° C. and relative humidity 50%, and the water contact angle and oleic acid contact angle were measured 30 seconds after the dropping. If the water contact angle is 100° or more and the oleic acid contact angle is 73° or more, it can be considered that the anti-fouling property is high.
  • the sliding angle of oleic acid of the anti-reflection film was measured using a contact angle meter (DropMaster DMo-502, manufactured by Kyowa Interface Science Co., Ltd.). Specifically, 5 ⁇ L of oleic acid was dropped onto the surface of the antifouling layer in an atmosphere of room temperature 23° C. and relative humidity 50%, and the inclination was increased from a horizontal (0°) state to 90° at 1° per second, and the inclination angle at which the droplet began to slide down was taken as the sliding angle of oleic acid. If the sliding angle of oleic acid is 25° or less, it can be considered that the film has high antifouling properties.
  • Luminous reflectance The back surface of the prepared anti-reflection film (the surface opposite to the antifouling layer) was roughened with #400 sandpaper and painted over with black paint. Then, using an ultraviolet-visible-near infrared spectrophotometer (Shimadzu Corporation's "UV-3600"), the 5° regular reflectance of the surface of the antifouling layer at wavelengths of 380 nm to 780 nm was measured, and the measured value was multiplied by the relative luminous efficiency value to calculate the luminous reflectance. If the luminous reflectance is 2.0% or less, the antireflection properties can be considered to be sufficient.
  • UV-3600 ultraviolet-visible-near infrared spectrophotometer
  • the abrasion resistance of each sample was evaluated.
  • a flat surface abrasion tester (Daiei Scientific Instruments Manufacturing Co., Ltd. "DAS-400") was used, and a felt stick (TABER, abrasive stick H1 (Felt), diameter 9 mm) was placed on the surface of the anti-reflective film of each sample, and the sample was moved back and forth.
  • the stroke length of the test stand was 50 mm
  • the test stand reciprocation speed was 25 reciprocations/min
  • the applied load was 5.0 N.
  • the anti-reflective film after 5000 reciprocation tests was visually observed, and the abrasion resistance was evaluated according to the following criteria.
  • the abrasion marks refer to areas that have not caused physical damage to the sample surface, but look different from the surrounding areas due to changes in optical properties.
  • A The artificial fingerprint liquid can be wiped off until it is no longer visible within 5 strokes, and the stain resistance is very high.
  • B The artificial fingerprint liquid can be wiped off until it is no longer visible within 5 strokes or more but within 10 strokes, and the stain resistance is satisfactory for practical use.
  • C The artificial fingerprint liquid cannot be wiped off even after 10 strokes, and the stain resistance is poor.
  • Table 2 shows the component compositions (unit: mass % of the total solid content of each layer) of the low refractive index layer and the antifouling layer, the layer structure of the antireflection film, and the evaluation results for Examples 1 to 3 and Comparative Examples 1 to 5.
  • the antifouling layer formed on the surface of the low refractive index layer is composed of a cured product of a composition containing a fluorine-containing (meth)acrylate, and an antifouling layer containing 90 mass% or more of the fluorine-containing (meth)acrylate is formed based on the total solid content. Furthermore, 50 mass% or more of the solid content of the fluorine-containing (meth)acrylate is a fluorine-containing (meth)acrylate (fluorine-containing compound 1) having a polar component ⁇ p of the surface free energy of 18 mN/m or more.
  • Examples 1 to 3 a water contact angle of 100° or more, an oleic acid contact angle of 73° or more, an oleic acid sliding angle of 25° or less, a surface free energy of 30 mN/m or less, and a visual reflectance of 2.0% or less are obtained, as well as high antifouling properties and high abrasion resistance, each of which is rated as A or B. It should be noted that Examples 1 and 2 differ only in the thickness of the antifouling layer, but Example 1, in which the antifouling layer is formed thinner, is superior in abrasion resistance.
  • the anti-stain layer is made of only fluorinated (meth)acrylates with a polar component of the surface free energy ⁇ p of less than 18 mN/m, which corresponds to low abrasion resistance (C). This is thought to be because the adhesion between the low refractive index layer and the anti-stain layer is low, and the surface of the anti-stain layer is worn away when rubbed by the felt, causing wear marks and scratches accompanied by changes in the reflection characteristics.
  • the content of fluorine-containing (meth)acrylate in the antifouling layer is less than 90 mass%, which corresponds to low abrasion resistance (C). From this result, it can be said that sufficient abrasion resistance cannot be obtained unless the antifouling layer contains 90 mass% or more of fluorine-containing (meth)acrylate based on the total solid content, and that even if a binder resin that does not contain fluorine is added instead, it is not possible to improve adhesion with the low refractive index layer and thereby improve abrasion resistance.
  • Comparative Example 5 no antifouling layer containing a fluorine-containing compound is provided on the surface of the low refractive index layer.
  • the water contact angle is less than 100°
  • the oleic acid contact angle is less than 73°
  • the oleic acid sliding angle is large, exceeding 25°.
  • the measured value of the surface free energy on the surface of the produced film also exceeds 30 mN/m.
  • the evaluation result of the antifouling property is also low (C).
  • the surface slipperiness is insufficient, and the abrasion resistance is low (C).
  • Comparative Example 4 As in Comparative Example 5, no anti-stain layer is provided on the surface of the low refractive index layer, but instead a fluorine-containing compound is added to the low refractive index layer.
  • the addition of a fluorine-containing compound to the low refractive index layer improves the anti-stain properties compared to Comparative Example 5 (B), but does not reach those of Examples 1 to 3.
  • Abrasion resistance remains low (C). This shows that even if a fluorine-containing compound is added to the low refractive index layer instead of an anti-stain layer, it is not possible to obtain the same effect as an anti-stain layer provided as an independent layer on the surface of the low refractive index layer.
  • the anti-reflection film has a substrate film, a hard coat layer formed on the surface of the substrate film, a low refractive index layer formed on the surface of the hard coat layer, and an anti-fouling layer formed on the surface of the low refractive index layer, the anti-fouling layer is composed of a cured product of a composition containing a fluorinated (meth)acrylate, the content of the fluorinated (meth)acrylate in the anti-fouling layer is 90 mass% or more based on the total solid content of the anti-fouling layer, and 50 mass% or more of the solid content of the fluorinated (meth)acrylate is a fluorinated (meth)acrylate having a polar component ⁇ p of the surface free energy of 18 mN/m or more, so that the anti-reflection film has high anti-fouling properties and abrasion resistance.

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  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Laminated Bodies (AREA)
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006068200A1 (ja) * 2004-12-24 2006-06-29 Matsushita Electric Works, Ltd. 液晶表示装置用光学積層フィルム
WO2012157682A1 (ja) * 2011-05-16 2012-11-22 大日本印刷株式会社 反射防止フィルムの製造方法、反射防止フィルム、偏光板、及び画像表示装置
JP2013109169A (ja) * 2011-11-21 2013-06-06 Panasonic Corp 反射防止部材
JP2017054125A (ja) * 2015-09-11 2017-03-16 キヤノン株式会社 光学部材及び光学部材の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006068200A1 (ja) * 2004-12-24 2006-06-29 Matsushita Electric Works, Ltd. 液晶表示装置用光学積層フィルム
WO2012157682A1 (ja) * 2011-05-16 2012-11-22 大日本印刷株式会社 反射防止フィルムの製造方法、反射防止フィルム、偏光板、及び画像表示装置
JP2013109169A (ja) * 2011-11-21 2013-06-06 Panasonic Corp 反射防止部材
JP2017054125A (ja) * 2015-09-11 2017-03-16 キヤノン株式会社 光学部材及び光学部材の製造方法

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