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WO2016017816A1 - 防眩フィルムおよび画像表示装置 - Google Patents

防眩フィルムおよび画像表示装置 Download PDF

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Publication number
WO2016017816A1
WO2016017816A1 PCT/JP2015/071875 JP2015071875W WO2016017816A1 WO 2016017816 A1 WO2016017816 A1 WO 2016017816A1 JP 2015071875 W JP2015071875 W JP 2015071875W WO 2016017816 A1 WO2016017816 A1 WO 2016017816A1
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WO
WIPO (PCT)
Prior art keywords
antiglare
layer
particles
antiglare layer
film
Prior art date
Application number
PCT/JP2015/071875
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English (en)
French (fr)
Japanese (ja)
Inventor
雅之 南方
岸　敦史
貴之 足立
浩貴 倉本
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020177001750A priority Critical patent/KR20170040198A/ko
Priority to CN201580041849.6A priority patent/CN106574991B/zh
Priority to KR1020237019131A priority patent/KR20230086816A/ko
Publication of WO2016017816A1 publication Critical patent/WO2016017816A1/ja

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    • 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
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133502—Antiglare, refractive index matching layers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H10K59/8792—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. black layers

Definitions

  • the present invention relates to an antiglare film and an image display device.
  • an anti-glare film is sometimes used in an image display device for the purpose of preventing a decrease in contrast due to reflection of external light, reflection of an image, and the like.
  • an antiglare film occurs. Specifically, when a conventional anti-glare film is applied to a high-definition image display device, luminance variations existing in pixels are emphasized, and glare is likely to occur.
  • an in-vehicle image display device requiring heat resistance for example, a car navigation monitor, an instrument panel monitor, etc.
  • the glare problem is more noticeable.
  • an antiglare film capable of suppressing glare while maintaining antiglare property and transparency is required.
  • the present invention has been made to solve the above-described problems, and the object of the present invention is to maintain anti-glare and transparency even in an image display device that requires high definition and heat resistance. Furthermore, it is providing the anti-glare film which can suppress glare.
  • the antiglare film of the present invention comprises a transparent substrate and an antiglare layer disposed on at least one surface of the transparent substrate, and the surface of the antiglare layer opposite to the transparent substrate is
  • the uneven surface has an average interval Sm of 150 ⁇ m to 350 ⁇ m, an average inclination angle ⁇ a of the uneven surface of 0.1 ° to 2.5 °, and an arithmetic average surface roughness of the uneven surface
  • the thickness Ra is 0.05 ⁇ m to 0.5 ⁇ m.
  • the average interval Sm of the irregularities on the irregular surface, the average inclination angle ⁇ a, and the arithmetic average surface roughness Ra of the irregular surface have a relationship of 0 ⁇ Ra / Sm ⁇ ⁇ a ⁇ 1000 ⁇ 4. Show.
  • the antiglare layer includes a binder resin and particles, and the particles have a weight average particle diameter of 1 ⁇ m to 10 ⁇ m. In one embodiment, the content ratio of the particles is 1 to 9 parts by weight with respect to 100 parts by weight of the binder resin.
  • the said glare-proof layer contains a cohesive filler. In one embodiment, the cohesive filler is an organoclay.
  • the antiglare layer has a thickness of 3 ⁇ m to 15 ⁇ m. In one embodiment, the antiglare film of the present invention is formed between the transparent substrate and the antiglare layer, and at least a part of the material constituting the transparent substrate and / or the binder resin.
  • An intermediate layer including at least a part of the intermediate layer, and the thickness of the intermediate layer is 0.1% to 123% with respect to the thickness of the antiglare layer.
  • an image display device includes the antiglare film and an image display cell, and a gap between the antiglare film and the image display cell is 100 ⁇ m to 700 ⁇ m.
  • an antiglare layer having an uneven surface is provided, and the uneven surface has a specific average interval Sm, an average inclination angle ⁇ a, and an arithmetic average surface roughness Ra, thereby maintaining antiglare properties and transparency.
  • an antiglare film that can further suppress glare can be provided.
  • the antiglare film of the present invention is particularly useful in an image display device that requires high definition and heat resistance.
  • FIG. 1 is a schematic cross-sectional view of an antiglare film according to one embodiment of the present invention.
  • the antiglare film 100 includes a transparent substrate 10 and an antiglare layer 20 disposed on at least one surface of the transparent substrate 10.
  • the transparent substrate 10 is composed of a resin film.
  • the antiglare layer 30 is typically formed by coating a resin film with a composition for forming an antiglare layer.
  • the antiglare layer-forming composition contains a binder resin (or a binder resin precursor) and particles, and the antiglare layer 30 formed from such an antiglare layer-forming composition comprises binder resin and particles.
  • the surface of the antiglare layer 20 opposite to the transparent substrate 10 is an uneven surface, and has a specific surface shape as described later.
  • the antiglare film may further include an antireflection layer on the surface of the antiglare layer opposite to the transparent substrate.
  • the antireflection layer can be formed by any appropriate method.
  • FIG. 2 is a schematic cross-sectional view of an antiglare film according to another embodiment of the present invention.
  • the antiglare film 100 ′ includes a transparent base material 10 and an antiglare layer 30 disposed on at least one side of the transparent base material 10, and an intermediate layer is provided between the transparent base material 10 and the antiglare layer 30. 1 is formed.
  • the transparent substrate 10 is made of a resin film.
  • the antiglare layer 30 is typically formed by coating a resin film with a composition for forming an antiglare layer.
  • the antiglare layer-forming composition contains a binder resin (or a binder resin precursor) and particles, and the antiglare layer 30 formed from such an antiglare layer-forming composition comprises binder resin and particles. Including.
  • the intermediate layer 1 is typically formed by penetrating the resin film with a composition for forming an antiglare layer.
  • the material constituting the resin film may be eluted into the antiglare layer forming composition.
  • the part formed by elution of the material constituting the resin film also corresponds to the intermediate layer 1.
  • the intermediate layer 1 can include at least a part of the material constituting the transparent substrate 10 and at least a part of the binder resin included in the antiglare layer 30.
  • the intermediate layer 1 may be a layer formed by mixing the material constituting the transparent substrate 10 and the binder resin contained in the antiglare layer 30.
  • the intermediate layer 1 is a layer that is in contact with both the transparent substrate 10 and the antiglare layer 20.
  • the thickness of the antiglare film is preferably 15 ⁇ m to 500 ⁇ m, more preferably 25 ⁇ m to 300 ⁇ m, and further preferably 30 ⁇ m to 100 ⁇ m.
  • one surface of the antiglare layer is an uneven surface.
  • the average spacing Sm between the concavo-convex surfaces is 150 ⁇ m to 350 ⁇ m, preferably 160 ⁇ m to 300 ⁇ m, and more preferably 180 ⁇ m to 250 ⁇ m.
  • the average inclination angle ⁇ a of the concavo-convex surface is 0.1 ° to 2.5 °, preferably 0.2 ° to 2.0 °, more preferably 0.3 ° to 1.5 °. .
  • the arithmetic average surface roughness Ra of the uneven surface is 0.05 ⁇ m to 0.5 ⁇ m, preferably 0.08 ⁇ m to 0.3 ⁇ m, and more preferably 0.1 ⁇ m to 0.25 ⁇ m.
  • tilt angle (theta) a, and arithmetic surface roughness Ra is based on JISB0601 (1994 edition). These characteristic values can be measured with a stylus type surface roughness measuring instrument (for example, Kosaka Laboratory, high-precision fine shape measuring instrument, trade name “Surfcoder ET4000”).
  • the antiglare film of the present invention is provided with an antiglare layer having the above surface shape (average interval Sm of uneven surfaces, average inclination angle ⁇ a, arithmetic surface roughness Ra), and thus has excellent antiglare properties and transparency.
  • the glare can be suppressed while maintaining the properties.
  • a relatively thick optical member eg, glass, polarizing plate, retardation film
  • a glare-suppressing effect can also be obtained for an image display device that is arranged and has a long distance between the viewing surface and an image display cell (for example, a liquid crystal cell).
  • the surface shape of the antiglare layer includes, for example, the type, particle size and / or content of particles contained in the antiglare layer, the relationship between the antiglare layer and the particle size of particles, the type of cohesive filler (described later) and / or Alternatively, the content can be controlled by the solid content concentration of the composition for forming an antiglare layer.
  • the average spacing Sm ( ⁇ m), the average inclination angle ⁇ a (°) and the arithmetic surface roughness Ra ( ⁇ m) of the uneven surfaces show a relationship of 0 ⁇ Ra / Sm ⁇ ⁇ a ⁇ 1000 ⁇ 4, more preferably A relationship of 0.1 ⁇ Ra / Sm ⁇ ⁇ a ⁇ 1000 ⁇ 3 is shown, and a relationship of 0.15 ⁇ Ra / Sm ⁇ ⁇ a ⁇ 1000 ⁇ 2 is more preferable.
  • the effect of the present invention becomes more prominent when the relationship between the average interval Sm ( ⁇ m), the average inclination angle ⁇ a (°), and the arithmetic surface roughness Ra ( ⁇ m) is the above specific relationship.
  • the thickness of the antiglare layer is preferably 3 ⁇ m to 15 ⁇ m, more preferably 4 ⁇ m to 13 ⁇ m, and still more preferably 5 ⁇ m to 12 ⁇ m. If it is such a range, the anti-glare film which cannot easily inhibit the visibility of an image display apparatus can be obtained. Moreover, it can be set as a glare-proof layer with favorable uneven
  • the haze of the antiglare layer is preferably less than 40%, more preferably 35% or less, and further preferably 10% to 30%.
  • the antiglare film has an excellent antiglare property and an excellent glare suppressing effect without impairing the transparency of the antiglare layer, that is, without increasing the haze of the antiglare layer. Can be obtained. Haze can be measured according to JIS K 7136 (2000 version).
  • the refractive index of the binder resin is preferably 1.2 to 2.0, more preferably 1.3 to 1.9, still more preferably 1.3 to 1.8, and particularly preferably 1 .4 to 1.7. If it is such a range, the glare-proof layer which has a preferable external haze can be formed in relation to the refractive index (after-mentioned) of particle
  • the “refractive index of the binder resin” means the refractive index of the region formed of the binder resin in the antiglare layer, and corresponds to the refractive index of the antiglare layer when it is assumed that no particles are present.
  • the antiglare layer preferably contains a binder resin and particles.
  • the antiglare layer is formed, for example, by applying a composition for forming an antiglare layer on a resin film constituting a transparent substrate, and then curing the composition.
  • the composition for forming an antiglare layer may contain a curable compound, the above particles, and the like.
  • the binder resin is a resin derived from a curable compound, and examples of the resin include a thermosetting resin and an active energy ray curable resin.
  • the composition for forming an antiglare layer contains a polyfunctional monomer, an oligomer derived from a polyfunctional monomer and / or a prepolymer derived from a polyfunctional monomer as a curable compound serving as a main component.
  • the polyfunctional monomer include polyfunctional acrylic monomers.
  • tricyclodecane dimethanol diacrylate pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropanthate tetraacrylate, Dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, dipropylene glycol diacrylate, isocyanuric acid tri (meth) acrylate, ethoxylated glycerin triacrylate, Toxylated pentaerythritol te
  • the polyfunctional monomer may have a hydroxyl group. If the composition for forming an antiglare layer containing a polyfunctional monomer having a hydroxyl group is used, the adhesion between the transparent substrate and the antiglare layer can be improved.
  • the polyfunctional monomer having a hydroxyl group include pentaerythritol tri (meth) acrylate and dipentaerythritol pentaacrylate.
  • the content ratio of the polyfunctional monomer, the oligomer derived from the polyfunctional monomer, and the prepolymer derived from the polyfunctional monomer is preferably 10% with respect to the total amount of the monomer, oligomer and prepolymer in the composition for forming an antiglare layer. % To 100% by weight, more preferably 30% to 100% by weight, still more preferably 40% to 95% by weight, and particularly preferably 50% to 95% by weight.
  • the antiglare layer forming composition may further contain a monofunctional monomer.
  • monofunctional monomers include ethoxylated o-phenylphenol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isooctyl acrylate, and isostearyl acrylate.
  • the monofunctional monomer may have a hydroxyl group.
  • the monofunctional monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxyacrylate, 1,4 -Hydroxyalkyl (meth) acrylates such as cyclohexane methanol monoacrylate; N- (2-hydroxyalkyl) (meth) acrylamides such as N- (2-hydroxyethyl) (meth) acrylamide, N-methylol (meth) acrylamide, etc. Can be mentioned. Of these, 4-hydroxybutyl acrylate and N- (2-hydroxyethyl) acrylamide are preferable.
  • the antiglare layer forming composition may contain an oligomer of urethane (meth) acrylate and / or urethane (meth) acrylate.
  • Urethane (meth) acrylate can be obtained, for example, by reacting hydroxy (meth) acrylate obtained from (meth) acrylic acid or (meth) acrylic acid ester and polyol with diisocyanate.
  • Urethane (meth) acrylates and urethane (meth) acrylate oligomers may be used alone or in combination.
  • Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.
  • polyol examples include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1, 6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, neopentyl hydroxypivalate Glycol ester, tricyclodecane dimethylol, 1,4-cyclohexanediol, spiroglycol, hydrogenated bisphenol A, ethylene oxide added bisphenol A, propylene oxide added bisphenol A, trimethylol ethane, trimethylol Propane, glycerin, 3-methylpentane-1,3,5-triol, pentaeryth
  • diisocyanate for example, various aromatic, aliphatic or alicyclic diisocyanates can be used. Specific examples of the diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,4. -Diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, and hydrogenated products thereof.
  • the antiglare layer contains particles. By including the particles, the surface of the antiglare layer can be made uneven. In addition, the haze value of the antiglare layer can be controlled.
  • the particles include inorganic particles and organic particles. Specific examples of the inorganic particles include, for example, silicon oxide particles, titanium oxide particles, aluminum oxide particles, zinc oxide particles, tin oxide particles, calcium carbonate particles, barium sulfate particles, talc particles, kaolin particles, calcium sulfate particles, and the like. It is done.
  • organic particles include, for example, polymethyl methacrylate resin particles (PMMA particles), silicone resin particles, polystyrene resin particles, polycarbonate resin particles, acrylic styrene resin particles, benzoguanamine resin particles, melamine resin particles, polyolefin resin particles, and polyester.
  • PMMA particles polymethyl methacrylate resin particles
  • silicone resin particles silicone resin particles
  • polystyrene resin particles polycarbonate resin particles
  • acrylic styrene resin particles acrylic styrene resin particles
  • benzoguanamine resin particles acrylic styrene resin particles
  • benzoguanamine resin particles acrylic styrene resin particles
  • benzoguanamine resin particles melamine resin particles
  • polyolefin resin particles polyolefin resin particles
  • polyester polyester.
  • resin particles polyamide resin particles
  • grains may be used independently and may be used in combination of multiple.
  • the weight average particle diameter of the particles is preferably 1 ⁇ m to 10 ⁇ m, more preferably 2 ⁇ m to 7 ⁇ m. If it is such a range, the anti-glare film which is more excellent in anti-glare property and can prevent white blurring can be obtained.
  • the weight average particle diameter of the particles can be measured by a Coulter counting method.
  • the particles In the antiglare layer or the composition for forming an antiglare layer, the particles may exist in the form of primary particles and / or in the form of aggregated primary particles.
  • the “average particle diameter” means the weight average particle diameter measured by the Coulter counting method for the particles in the composition for forming an antiglare layer regardless of the particle form.
  • the ratio of the thickness of the antiglare layer to the weight average particle size of the particles is preferably 0.3 to 0.9, more preferably 0.00. 35 to 0.8. If it is such a range, an anti-glare layer with a larger glare suppression effect can be formed.
  • the refractive index of the particles is preferably 1.1 to 1.9, more preferably 1.2 to 1.7.
  • the particles having such a refractive index include silicone particles, polystyrene particles, polymethyl methacrylate, a copolymer of styrene and methacrylic acid, and the like.
  • the difference (n1 ⁇ n2) between the refractive index (n1) of the particles and the refractive index (n2) of the binder resin is preferably 0.5 or less, more preferably 0.3 or less.
  • the lower limit of (n1-n2) is preferably ⁇ 0.9 or more, more preferably ⁇ 0.8 or more. If it is such a range, the anti-glare film excellent in transparency can be obtained.
  • the ratio (n1 / n2) of the refractive index (n1) of the particles to the refractive index (n2) of the binder resin is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. It is. If it is such a range, the anti-glare film which is excellent in transparency and a glare suppression effect can be obtained.
  • the shape of the particles is not particularly limited, and may be, for example, a substantially spherical shape such as a bead shape or an indefinite shape such as a powder. Preferably, it is a substantially spherical particle having an aspect ratio of 1.5 or less, more preferably a spherical particle.
  • the content ratio of the particles is preferably 0.2 to 12 parts by weight, more preferably 0.5 to 12 parts by weight with respect to 100 parts by weight of the binder resin. More preferred is 1 to 9 parts by weight, and particularly preferred is 1 to 7 parts by weight. If it is such a range, the anti-glare film which is more excellent in anti-glare property and can prevent white blurring can be obtained.
  • the particles are preferably present with good dispersibility (with little aggregation).
  • the dispersibility (dispersion degree) of the particles can be evaluated from particle size distribution measurement by a laser diffraction / scattering particle size distribution measurement method, a dynamic light scattering method, a static light scattering method, or the like. Further, it can be measured by microscopic observation with a scanning electron microscope or the like.
  • D 50 particle size at 50% cumulative volume
  • volume cumulative particle size D 90 volume
  • the absolute value of the difference from the particle size at 90% cumulative is preferably 5 ⁇ m or less, more preferably less than 3 ⁇ m, further preferably less than 1 ⁇ m, and particularly preferably from 0 ⁇ m to less than 1 ⁇ m. preferable. If it is such a range, the glare-proof layer which has a suitable surface shape can be formed.
  • the content ratio of particles having a particle size of 1 ⁇ m or more and less than 5 ⁇ m is determined by The total amount is preferably more than 50% by weight, more preferably 70% by weight or more, and further preferably 80% by weight to 100% by weight. If it is such a range, the glare-proof layer which has a suitable surface shape can be formed.
  • the antiglare layer forming composition may further contain a cohesive filler. That is, the antiglare layer may further contain a cohesive filler.
  • the uneven shape on the surface of the antiglare layer can be controlled more strictly. More specifically, the concavo-convex surface having the average interval Sm, the average inclination angle ⁇ a, and the arithmetic surface roughness Ra in the above range can be easily obtained by adjusting the aggregation state of the cohesive filler.
  • the aggregation state of the aggregating filler is the properties of the filler (for example, the chemical modification state of the surface, the affinity for the binder resin, the affinity for the solvent contained in the antiglare layer forming composition), the antiglare layer forming composition. It can adjust with the kind etc. of the solvent contained in a thing.
  • Examples of the aggregating filler include organic clay, oxidized polyolefin, and modified urea. Of these, organic clay is preferable.
  • organic clay examples include smectite, talc, bentonite, montmorillonite, and kaolinite. Of these, smectite is preferable.
  • Commercial products may be used as the organic clay.
  • examples of commercially available organic clays include trade name “Lucentite SAN”, trade name “Lucentite STN”, trade name “Lucentite SEN”, trade name “Lucentite SPN”, trade name “ Somasif ME-100, product name “Somasif MAE”, product name “Somasif MTE”, product name “Somasif MEE”, product name “Somasif MPE”; product name “Esven”, product name “Esven C” manufactured by Hojun Co.
  • oxidized polyolefin examples include trade name “Disparon 4200-20” manufactured by Enomoto Kasei Co., Ltd., and trade name “Flownon SA300” manufactured by Kyoeisha Chemical Co., Ltd.
  • the modified urea is a reaction product of an isocyanate monomer or its adduct and an organic amine.
  • examples of the modified urea include a trade name “BYK410” manufactured by Big Chemie.
  • the content of the aggregating filler is preferably 0.2 to 5 parts by weight, more preferably 0.4 to 4 parts by weight with respect to 100 parts by weight of the binder resin.
  • the antiglare layer-forming composition preferably contains any appropriate photopolymerization initiator.
  • the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, benzoinpropyl ether, benzyldimethyl Ketals, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, thioxanthone compounds, etc. Can be mentioned.
  • the antiglare layer forming composition may or may not contain a solvent.
  • the composition for forming an antiglare layer contains a solvent.
  • the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and 2-methoxyethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; methyl acetate, ethyl acetate, butyl acetate, and the like.
  • Esters such as diisopropyl ether and propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; cellosolves such as ethyl cellosolve and butyl cellosolve; aliphatic hydrocarbons such as hexane, heptane and octane; benzene and toluene And aromatic hydrocarbons such as xylene. These may be used alone or in combination. When using the composition for forming an antiglare layer containing the organic clay, it is preferable to use toluene, cyclopentanone and / or xylene as a solvent.
  • a mixed solvent containing cyclopentanone and / or methyl ethyl ketone for example, a mixed solvent containing cyclopentanone and toluene, or a mixed solvent containing methyl ethyl ketone and toluene
  • the thickness of the intermediate layer can be adjusted by the content ratio of cyclopentanone or methyl ethyl ketone.
  • the content of cyclopentanone or methyl ethyl ketone in the mixed solvent is preferably 1% by weight to 50% by weight, more preferably 3% by weight to 50% by weight, based on the total amount of the mixed solvent.
  • it is a mixed solvent of cyclopentanone and toluene, and a mixed solvent having a cyclopentanone content of 1 wt% to 50 wt% is used.
  • a mixed solvent having a cyclopentanone content of 1 wt% to 50 wt% is used. If the composition for forming an antiglare layer containing such a mixed solvent is used, an intermediate layer having a preferable thickness is formed on a resin film (for example, a triacetylcellulose film) suitable as a transparent substrate for the antiglare film. In addition, an antiglare layer can be formed.
  • the SP value of the solvent is preferably 7 to 12 (cal / cm 3 ) 1/2 , more preferably 8 to 11 (cal / cm 3 ) 1/2 .
  • an antiglare layer can be formed while an intermediate layer having a preferred thickness is formed on a resin film (for example, a triacetyl cellulose film) suitable as a transparent substrate for the antiglare film.
  • the SP value is a solubility parameter calculated by the Small formula.
  • the SP value can be calculated by a method described in a known document (for example, Journal of Applied Chemistry, 3, 71, 1953., etc.).
  • the SP value of the mixed solvent can be calculated based on the mole fraction of each solvent constituting the mixed solvent.
  • the solid content concentration of the composition for forming an antiglare layer is preferably 20% by weight to 80% by weight, more preferably 25% by weight to 60% by weight, and further preferably 30% by weight to 50% by weight. is there. If it is such a range, the uneven surface which has the average space
  • the antiglare layer forming composition may further contain any appropriate additive.
  • additives include leveling agents, anti-blocking agents, dispersion stabilizers, thixotropic agents, antioxidants, UV absorbers, antifoaming agents, thickeners, dispersants, surfactants, catalysts, lubricants, and electrification. An inhibitor etc. are mentioned.
  • the antiglare layer can be obtained by applying the antiglare layer forming composition to a transparent substrate and then curing it. Any appropriate method can be adopted as a method for applying the composition for forming an antiglare layer. Examples thereof include a bar coating method, a roll coating method, a gravure coating method, a rod coating method, a slot orifice coating method, a curtain coating method, a fountain coating method, and a comma coating method.
  • the transparent substrate on which the coating layer is formed is inclined or Rotate.
  • the composition for forming an antiglare layer contains a cohesive filler
  • the contact between the cohesive fillers is promoted, and the cohesive filler can be appropriately aggregated (shear aggregation).
  • the aggregation state of the cohesive filler can be controlled by adjusting the inclination angle or the rotation speed in the above inclination or rotation.
  • Arbitrary appropriate hardening processing may be employ
  • the curing process is performed by ultraviolet irradiation.
  • the integrated light quantity of ultraviolet irradiation is preferably 50 mJ / cm 2 to 500 mJ / cm 2 .
  • the transparent substrate may be formed from a resin film. Any appropriate substrate (resin film) may be used as the transparent substrate (resin film) as long as it has visible light transmittance. Examples of the material constituting the transparent substrate (resin film) include triacetyl cellulose (TAC), polycarbonate, acrylic polymer, cyclic polyolefin, polyolefin having a norbornene structure, and polyethylene terephthalate.
  • TAC triacetyl cellulose
  • polycarbonate acrylic polymer
  • cyclic polyolefin polyolefin having a norbornene structure
  • polyethylene terephthalate polyethylene terephthalate
  • the thickness of the transparent substrate is preferably 10 ⁇ m to 500 ⁇ m, more preferably 20 ⁇ m to 300 ⁇ m, and still more preferably 30 ⁇ m to 100 ⁇ m.
  • the thickness of a transparent base material is equivalent to the thickness of the said resin film.
  • the thickness of a transparent base material is equivalent to the thickness of the part in which the intermediate
  • the SP value of the resin constituting the resin film is preferably 10 (cal / cm 3 ) 1/2 or more, more preferably 15 (cal / cm 3 ) 1/2 or more, and even more preferably 20 ( cal / cm 3 ) 1/2 or more. Within such a range, an intermediate layer having an appropriate thickness can be formed.
  • the upper limit of the SP value of the resin is, for example, 30 (cal / cm 3 ) 1/2 or less, preferably 28 (cal / cm 3 ) 1/2 or less, more preferably 25 (cal / cm 3). ) 1/2 or less.
  • the difference between the SP value of the solvent contained in the antiglare layer forming composition and the SP value of the resin constituting the resin film is preferably ⁇ 10 to 20 (cal / cm 3 ) 1/2 , more preferably 5 to 20 (cal / cm 3 ) 1/2 , and 10 to 15 (cal / cm 3 ) 1/2 .
  • the refractive index of the transparent substrate is preferably 1.30 to 1.80.
  • an intermediate layer may be formed between the transparent substrate and the antiglare layer.
  • the thickness of the intermediate layer is preferably 0.1% to 123% with respect to the thickness of the antiglare layer (thickness a in FIG. 2).
  • the lower limit of the thickness ratio of the intermediate layer to the thickness of the antiglare layer is preferably 1%, more preferably 3%.
  • the upper limit of the thickness ratio of the intermediate layer to the thickness of the antiglare layer is preferably 100%, more preferably 85%, and further preferably 65%.
  • the thickness of the intermediate layer, the antiglare layer and the transparent substrate is measured by observing the cross section of the antiglare film with a microscope (for example, TEM) and specifying the interface between the intermediate layer, the resin layer and the adhesive layer. obtain.
  • a predetermined analysis method for example, time-of-flight secondary ion mass spectrometry may be used for specifying the interface.
  • an antiglare film having a higher glare-suppressing effect can be obtained by controlling the ratio so that the thickness of the intermediate layer formed when the antiglare layer is formed does not become too thick. . Even when the antiglare film of the present invention is applied to a high-definition image display device, it can exhibit an excellent glare-suppressing effect. In addition, the antiglare film of the present invention hardly causes glare even if the internal haze of the antiglare layer is relatively small, and therefore has excellent transparency. Furthermore, when the ratio of the thickness of the intermediate layer to the thickness of the antiglare layer is 123% or less, an antiglare layer having excellent scratch resistance can be formed.
  • the ratio of the thickness of the intermediate layer to the thickness of the antiglare layer is 3% or more (more preferably 10% or more), the above particles are present in the antiglare layer with good dispersibility (in a state of less aggregation). As a result, an antiglare film capable of suppressing glare can be obtained.
  • the thickness of the intermediate layer is preferably 0.1 ⁇ m to 30 ⁇ m, more preferably 0.3 ⁇ m to 20 ⁇ m, still more preferably 1 ⁇ m to 10 ⁇ m, and particularly preferably 1.5 ⁇ m to 5 ⁇ m.
  • FIG. 3 is a schematic cross-sectional view showing a part (viewing side) of an image display device according to one embodiment of the present invention.
  • the image display device 200 includes an antiglare film 100 and an image display cell 30.
  • the antiglare film 100 is disposed with the transparent substrate 10 facing the image display cell 30 side.
  • Any appropriate optical member A can be disposed between the antiglare film 100 and the image display cell 30, and a predetermined gap X is formed between the antiglare layer 10 and the image display cell 30.
  • the optical member A include a glass substrate, a polarizing plate, a retardation film, an adhesive layer, and a pressure-sensitive adhesive layer.
  • a single optical member may be disposed between the antiglare film 100 and the image display cell 30, or a plurality of types of optical members may be disposed.
  • any appropriate image display cell can be used as the image display cell.
  • a liquid crystal cell corresponds to the image display cell
  • an organic EL element corresponds to the image display cell.
  • a liquid crystal cell typically has a pair of substrates and a liquid crystal layer as a display medium disposed between the substrates.
  • the gap X between the antiglare layer and the image display cell in the antiglare film is preferably 100 ⁇ m to 700 ⁇ m. If a relatively thick glass substrate is provided and the gap X is 100 ⁇ m or more, an image display device having excellent heat resistance and strength can be obtained.
  • the lower limit of the gap X is more preferably 150 ⁇ m or more. By increasing the thickness of the glass substrate, the effect of improving heat resistance and strength becomes remarkable. Since the antiglare film of the present invention can suppress glare even when the gap X is large, if the antiglare film is used, both heat resistance and strength can be improved and glare can be suppressed.
  • the optical member that defines the gap X is not limited to a glass substrate, and any appropriate member may be disposed.
  • the effect of increasing the gap X is not limited to the improvement of heat resistance and strength. According to the present invention, since the restriction on the thickness is small, it is possible to provide an image display device with a high degree of design freedom. On the other hand, when the gap X is 700 ⁇ m or less, an image display device with less glare can be obtained.
  • the upper limit of the gap X is more preferably 650 ⁇ m or less. If the gap X is 650 ⁇ m or less, an image display device with less glare can be obtained.
  • the gap X between the antiglare layer and the image display cell in the antiglare film is the back surface of the antiglare layer (surface on the image display cell side) and the viewing side surface (surface on the antiglare film side) of the image display cell. It means the distance to make. Therefore, the gap X includes the total thickness of the optical member A (for example, the total thickness of the polarizing plate, the glass substrate and / or the pressure-sensitive adhesive layer) disposed between the antiglare film 100 and the image display cell 30, and the antiglare. This corresponds to the total thickness of the transparent substrate (a transparent substrate and an intermediate layer when an intermediate layer is formed) in the film. Further, when the image display cell is a liquid crystal cell, the gap X is the distance between the viewing side surface of the viewing side substrate provided in the liquid crystal cell and the back surface of the antiglare layer.
  • the optical member A for example, the total thickness of the polarizing plate, the glass substrate and / or the pressure-sensitive adhesive layer
  • the antiglare film of the present invention is suitably used for an image display device including a relatively thick glass substrate (for example, a glass substrate having a thickness of 100 ⁇ m to 700 ⁇ m).
  • a relatively thick glass substrate for example, a glass substrate having a thickness of 100 ⁇ m to 700 ⁇ m.
  • the heat resistance is increased by increasing the thickness of the glass substrate.
  • the inventors of the present invention have found that as the glass substrate is made thicker, that is, as the gap X is made thicker, the glare that occurs when an antiglare film is applied increases. . That is, the anti-glare film of the present invention can solve the problem and can be suitably used for an image display device for in-vehicle use.
  • the effect of using the anti-glare film of this invention becomes more remarkable with respect to a high-definition image display apparatus.
  • the image display device may further include any appropriate member.
  • it may further include a polarizing plate, an optical film, a backlight and the like provided on the back side of the image display cell.
  • the weight average particle diameter of the particles was measured by the Coulter counting method. Specifically, for a composition for forming an antiglare layer, a particle size distribution measuring device using a pore electrical resistance method (Beckman Coulter, trade name “Coulter Multisizer”) is used, and the particles pass through the pores. The number and volume of the particles were measured by measuring the electric resistance of the electrolytic solution corresponding to the volume of the particles at the time, and the weight average particle size was calculated.
  • ” of the particle is D 50 (particle size at 50% cumulative volume) obtained by a laser diffraction scattering type particle size distribution measuring method using “MicrotracUPA (model number)” manufactured by Nikkiso Co., Ltd. And the absolute value of the difference between the volume cumulative particle diameter D 90 (particle diameter at 90% volume cumulative).
  • the thickness of each layer was measured by observing the cross section with an optical microscope (trade name “VHX-700F” manufactured by Keyence Corporation) or TEM (trade name “H-7650” manufactured by Hitachi Ltd.). At the time of observation with an optical microscope, the antiglare film embedded with resin was cut with a microtome to produce an observation sample.
  • the sample was produced by the ultrathin section method including a heavy metal dyeing process.
  • the refractive index is an Abbe refractometer (trade name: DR-M2 / 1550) manufactured by Atago Co., Ltd., monobromonaphthalene is selected as an intermediate solution, and measurement light is incident on the measurement surface to be measured.
  • the measurement was performed by the specified measurement method shown in the apparatus.
  • Example 1 50 parts by weight of pentaerythritol triacrylate (trade name “Biscoat # 300” manufactured by Osaka Organic Chemical Co., Ltd.) as a binder resin and urethane acrylate prepolymer (trade name “UA-53H-80BK” manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 Part by weight and silicone particles (Momentive Performance Materials Japan G.K., trade name “Tospearl 130”, weight average particle size: 3 ⁇ m,
  • the above composition for forming an antiglare layer is applied to a triacetyl cellulose (TAC) film (trade name “KC4UA”, manufactured by Konica Minolta Opto, Inc., thickness: 40 ⁇ m) as a transparent substrate using a comma coater (registered trademark). Then, after heating at 80 ° C. for 1 minute, the antiglare layer (thickness: 6.3 ⁇ m) was formed on the transparent substrate by irradiating ultraviolet rays with an integrated light quantity of 300 mJ / cm 2 with a high-pressure mercury lamp. A film was obtained. In addition, a 1.7 ⁇ m intermediate layer was formed between the transparent substrate of the antiglare film and the antiglare layer.
  • TAC triacetyl cellulose
  • Example 2 50 parts by weight of pentaerythritol triacrylate (trade name “Biscoat # 300” manufactured by Osaka Organic Chemical Co., Ltd.) as a binder resin and urethane acrylate prepolymer (trade name “UA-53H-80BK” manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 Parts by weight and 5 parts by weight of polystyrene particles (manufactured by Sekisui Plastics Co., Ltd., trade name “Techpolymer”, weight average particle diameter: 3 ⁇ m,
  • 2 parts by weight of synthetic clay smectite (trade name “Lucentite SAN” manufactured by Corp Chemical Co.), 3 parts by weight of a photopolymerization initiator (trade name “Irgacure 907” manufactured by BASF), and a leveling agent (Made by DIC, trade name “PC4100”,
  • the above composition for forming an antiglare layer was applied to a triacetylcellulose film (trade name “KC4UA”, manufactured by Konica Minolta Opto, Inc., thickness: 40 ⁇ m) as a transparent substrate using a comma coater (registered trademark), and 80 After heating at a temperature of 1 ° C.
  • KC4UA triacetylcellulose film
  • comma coater registered trademark
  • an anti-glare film in which an anti-glare layer (thickness: 6.3 ⁇ m) is formed on a transparent substrate is obtained by irradiating UV light with an integrated light quantity of 300 mJ / cm 2 with a high-pressure mercury lamp It was.
  • a 1.7 ⁇ m intermediate layer was formed between the transparent substrate of the antiglare film and the antiglare layer.
  • the blending amount of the particles is 5 parts by weight, the blending amount of synthetic smectite (trade name “Lucentite SAN” manufactured by Co-op Chemical Co., Ltd.), which is an organic clay, is 1.5 parts by weight, and the composition for forming an antiglare layer is solid.
  • An antiglare film was obtained in the same manner as in Example 1 except that the concentration was 42% by weight.
  • Example 3 An antiglare film was obtained in the same manner as in Example 1 except that synthetic smectite (trade name “Lucentite SAN” manufactured by Co-op Chemical Co., Ltd.), which is an organic clay, was not used.
  • synthetic smectite trade name “Lucentite SAN” manufactured by Co-op Chemical Co., Ltd.
  • Example 6 An antiglare film was obtained in the same manner as in Example 1 except that the amount of synthetic smectite (trade name “Lucentite SAN” manufactured by Co-op Chemical Co., Ltd.), which is an organic clay, was 10 parts by weight.
  • synthetic smectite trade name “Lucentite SAN” manufactured by Co-op Chemical Co., Ltd.
  • Example 7 An antiglare film was obtained in the same manner as in Example 1 except that the amount of synthetic smectite (trade name “Lucentite SAN” manufactured by Co-op Chemical Co., Ltd.), which is an organic clay, was 0.2 parts by weight.
  • synthetic smectite trade name “Lucentite SAN” manufactured by Co-op Chemical Co., Ltd.
  • Example 8 An antiglare film was obtained in the same manner as in Example 1 except that the solid content concentration of the composition for forming an antiglare layer was 85% by weight.
  • Example 9 An antiglare film was obtained in the same manner as in Example 1 except that the solid content concentration of the composition for forming an antiglare layer was 15% by weight.
  • Example 13 An antiglare film was obtained in the same manner as in Example 1 except that the thickness of the antiglare layer was 15.9 ⁇ m.
  • a glass plate (thickness: 700 ⁇ m) is placed on a backlight (trade name “Light Viewer 5700” manufactured by Hakuba Photo Industry Co., Ltd.), and a black matrix is formed on the surface of the glass plate opposite to the backlight.
  • An evaluation table was prepared by arranging patterns. On this evaluation table, four TAC films (thickness: 80 ⁇ m) and four pressure-sensitive adhesive layers (thickness: 20 ⁇ m) are alternately laminated as a member A constituting a part of the gap X, and further a TAC film. (Thickness: 40 ⁇ m) and an adhesive layer (thickness: 20 ⁇ m) were laminated.
  • the antiglare films obtained in Examples and Comparative Examples were placed with the transparent base material facing down (that is, the pressure-sensitive adhesive layer and the transparent base material facing each other).
  • the glare produced in the antiglare film was evaluated according to the following criteria by irradiating the antiglare film with light.
  • the definition of the black matrix pattern was 105 ppi, 200 ppi, and 267 ppi, and the above evaluation was performed for each definition.
  • ⁇ There is almost no glare
  • ⁇ There is glare, but there is no practical problem
  • ⁇ Glitter with practical problem was seen
  • Haze value The haze value was measured using a haze meter (trade name “HM-150”, manufactured by Murakami Color Research Laboratory) in accordance with the haze (cloudiness) of JIS K 7136 (2000 version).
  • Anti-glare property An evaluation that suppresses the influence of back surface reflection by bonding a black acrylic plate (Mitsubishi Rayon Co., Ltd., thickness: 2 mm) to the surface opposite to the anti-glare layer of the transparent substrate with an adhesive.
  • a sample was prepared. In an environment with an illuminance of 1000 Lx (corresponding to a general office environment using a display), the evaluation sample is illuminated with a fluorescent lamp (three-wavelength light source), and the antiglare property of the antiglare film is visually evaluated according to the following evaluation criteria. did.
  • ⁇ Image reflection that affects visibility does not occur.
  • ⁇ Image reflection to the extent that there is no problem in practical use.
  • ⁇ Image reflection occurs, causing practical problem.
  • the antiglare film of the present invention is excellent in antiglare property and transparency because the uneven surface has a specific average interval Sm, average inclination angle ⁇ a and arithmetic average surface roughness Ra. And glare can be suppressed.
  • the antiglare films obtained in Examples and Comparative Examples were placed with the transparent base material facing down (that is, the pressure-sensitive adhesive layer and the transparent base material facing each other).
  • the image display device of the present invention exhibits a remarkable glare suppression effect when the gap X is in a specific range (700 ⁇ m or less).
  • An image display device having a thick glass substrate and a gap X of 100 ⁇ m or more is excellent in durability.

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