WO2016017817A1 - 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
WO2016017817A1
WO2016017817A1 PCT/JP2015/071876 JP2015071876W WO2016017817A1 WO 2016017817 A1 WO2016017817 A1 WO 2016017817A1 JP 2015071876 W JP2015071876 W JP 2015071876W WO 2016017817 A1 WO2016017817 A1 WO 2016017817A1
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Prior art keywords
antiglare
layer
film
glare
particles
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PCT/JP2015/071876
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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
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Priority to CN201580041861.7A priority Critical patent/CN106574992B/zh
Priority to KR1020177001749A priority patent/KR20170040197A/ko
Publication of WO2016017817A1 publication Critical patent/WO2016017817A1/ja

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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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an antiglare film.
  • 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 image display device having a configuration in which a relatively thick glass or the like is disposed on the back side of an antiglare film for example, an in-vehicle image display device that requires heat resistance (for example, a car navigation monitor, an instrument panel monitor, etc.)
  • a relatively thick glass or the like 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 in order to solve the above-mentioned problems, and an object of the present invention is to provide an anti-glare film that can suppress glare while maintaining anti-glare properties and transparency. is there.
  • 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 has an external haze of ⁇ 5% to 0.7%.
  • the antiglare film of the present invention has an overall haze of 5% to 40%.
  • the antiglare film of the present invention has an internal haze of 10% to 40%.
  • the surface of the antiglare layer opposite to the transparent substrate is an uneven surface, and the average interval Sm of the unevenness on the uneven surface, the average inclination angle ⁇ a, and the arithmetic average of the uneven surface
  • the surface roughness Ra indicates a relationship of 0 ⁇ Ra / Sm ⁇ ⁇ a ⁇ 1000 ⁇ 2.
  • the antiglare layer includes a binder resin and particles, and the difference (n1 ⁇ n2) between the refractive index n1 of the particles and the refractive index n2 of the binder resin is ⁇ 0.5. It is as follows.
  • the said glare-proof layer contains a cohesive filler.
  • the cohesive filler is an organoclay.
  • 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 antiglare film that includes an antiglare layer, and that can control glare while maintaining antiglare properties and transparency by controlling the external haze of the antiglare layer to a specific range.
  • the anti-glare film of the present invention has an image display device (for example, a personal computer) in which a thin glass substrate is provided on the back side of the anti-glare film, and an image having a structure in which relatively thick glass or the like is disposed as described above. An excellent antiglare effect can be exerted on a display device, and glare can be suppressed.
  • 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. Including.
  • 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. It should be noted that the size of the unevenness with respect to the thickness of each layer in the illustrated example is shown differently from the actual one for the sake of clarity.
  • 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.
  • the antiglare film has an external haze of ⁇ 5% to 0.7%, more preferably ⁇ 5% to 0.5%, and further preferably ⁇ 2.5% to 0.4%. Particularly preferably, it is -2% or more and less than 0%.
  • the total haze can be measured according to JIS K-7136.
  • the measurement of a haze is performed by making the surface on the opposite side to the transparent substrate of a glare-proof layer into a light-projection surface.
  • the internal haze refers to the haze measured in a state where the influence on the haze on the surface of the antiglare layer (light emission side during haze measurement) is eliminated.
  • a triacetyl cellulose (TAC) film is attached to the surface on the light emission side, whereby the surface unevenness of the antiglare layer is crushed to produce an evaluation sample that is a flat layer, and the haze of the evaluation sample Can be an internal haze. That is, the evaluation sample having a flat surface has no internal haze and no haze due to surface irregularities. Therefore, the haze of this evaluation sample can be measured to determine the internal haze.
  • TAC triacetyl cellulose
  • a resin for example, pentaerythritol triacrylate
  • a solution having a solid content of 60% by weight was applied to a dry film thickness of 8 ⁇ m.
  • An evaluation sample may be used.
  • the antiglare film is preliminarily saponified (2 mol / l NaOH (or KOH)
  • the solution is preferably immersed in 55 ° C. for 3 minutes, washed with water, and then completely removed, and then dried in a 50 ° oven for 1 minute).
  • the anti-glare film of the present invention can suppress glare while maintaining excellent anti-glare properties and transparency by providing an anti-glare layer with an external haze in the above range.
  • the antiglare film of the present invention includes an image display device (for example, a personal computer) in which a thin glass substrate is provided on the back side of the antiglare film, and an image display device having a configuration in which relatively thick glass or the like is disposed (for example, an excellent anti-glare effect can be exhibited for in-vehicle use) and glare can be suppressed.
  • the external haze value can be controlled by the refractive index of particles (described later) contained in the antiglare layer, the refractive index of the binder resin constituting the antiglare property, the uneven shape of the surface of the antiglare layer, and the like.
  • the overall haze of the antiglare film is preferably 40% or less, more preferably 5% to 40%, and further preferably 15% 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.
  • the internal haze of the antiglare film is preferably 10% to 40%, more preferably 20% to 32%.
  • one surface (surface opposite to the transparent substrate) of the antiglare layer is an uneven surface.
  • the average spacing Sm between the uneven surfaces is preferably 150 ⁇ m to 350 ⁇ m, more preferably 160 ⁇ m to 300 ⁇ m, and still more preferably 180 ⁇ m to 250 ⁇ m.
  • the average inclination angle ⁇ a of the uneven surface is preferably 0.1 ° to 2.5 °, more preferably 0.2 ° to 2.0 °, and further preferably 0.3 ° to 1.5 °. °.
  • the arithmetic average surface roughness Ra of the irregular surface is preferably 0.05 ⁇ m to 0.5 ⁇ m, more preferably 0.08 ⁇ m to 0.3 ⁇ m, and further 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 anti-glare film of the present invention can have an external haze having a preferable value by including an anti-glare layer having the above-described surface shape (average interval Sm of uneven surfaces, average inclination angle ⁇ a, arithmetic surface roughness Ra). As a result, it is possible to suppress glare while maintaining excellent antiglare properties and transparency.
  • 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 Or it can control by content etc.
  • 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 ⁇ 2, more preferably The relationship 0.1 ⁇ Ra / Sm ⁇ ⁇ a ⁇ 1000 ⁇ 2 is shown, and the relationship 0.15 ⁇ Ra / Sm ⁇ ⁇ a ⁇ 1000 ⁇ 2 is more preferable.
  • the external haze can easily obtain an antiglare layer in the above range. it can.
  • 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 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 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 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.
  • 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 n1 of the particles is preferably 1.1 to 1.9, more preferably 1.2 to 1.7.
  • the particles having such a refractive index n1 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.
  • the glare-proof layer which has a preferable external haze can be formed.
  • 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 preferably, it 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. If it is such a range, the glare-proof layer which has a suitable surface shape can be formed.
  • the content ratio of particles of 1 ⁇ m or more and less than 5 ⁇ m is based on the total amount of particles in the composition. On the other hand, it 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, a concavo-convex surface having a preferable shape can be easily obtained by adjusting the aggregation state of the aggregating 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., Ltd.
  • 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 molar 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
  • 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 an example of an image display device using the antiglare film 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 50 ⁇ m to 800 ⁇ m. In one embodiment, the gap X of the image display device is 100 ⁇ m or more.
  • the antiglare film of the present invention can suppress glare even when the gap X is large.
  • 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.
  • 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 includes not only an image display device having a small gap X but also an image display device having a large gap X (for example, a relatively thick glass substrate (for example, a glass substrate having a thickness of 100 ⁇ m to 800 ⁇ m)). ) Is also preferably used. Conventionally, in applications that require heat resistance, strength, and the like (for example, in-vehicle applications), the heat resistance is increased by increasing the thickness of the glass substrate. However, 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. .
  • 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. Moreover, 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.
  • 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.).
  • an optical microscope trade name “VHX-700F” manufactured by Keyence Corporation
  • TEM trade name “H-7650” manufactured by Hitachi Ltd.
  • 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, 3.5 parts by weight of silicone particles (Momentive Performance Materials Japan G.K., trade name “Tospearl 130”, weight average particle size: 3 ⁇ m, refractive index: 1.42), and organic clay 2 parts by weight of a certain synthetic smectite (trade name “Lucentite SAN” manufactured by Co-op Chemical Co., Ltd.), 3 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name “Irgacure 907”), (Product name “PC4100”, solid content 10%) 0.2 part by weight is mixed with toluene /
  • the organic clay was diluted with toluene so that the solid content was 6% by weight.
  • 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. for 1 minute, 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. In addition, a 1.7 ⁇ m intermediate layer was formed between the transparent substrate of the antiglare film and the antiglare layer.
  • 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, silicone particles (Momentive Performance Materials Japan G.K., trade name “Tospearl 130”, weight average particle size: 3 ⁇ m, refractive index: 1.42) 1.7 parts by weight, polystyrene particles ( Sekisui Plastics Co., Ltd., trade name “Techpolymer”, 2.3 parts by weight of weight average particle size: 3 ⁇ m, refractive index: 1.59) and synthetic smectite which is organic clay (trade name “Coop Chemical Co., Ltd.
  • BASF photopolymerization initiator
  • CPN cyclopentanone
  • 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. for 1 minute, 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. In addition, a 1.7 ⁇ m intermediate layer was formed between the transparent substrate of the antiglare film and the antiglare layer.
  • urethane acrylate made by DIC, trade name “Unidic 17-806” as a binder resin and polystyrene particles (trade name “SX-350H”, made by Soken Chemical Co., Ltd.), weight average particle diameter: 3.5 ⁇ m , Refractive index: 1.59) 15 parts by weight, photopolymerization initiator (manufactured by BASF, trade name “Irgacure 907”), leveling agent (manufactured by DIC, trade name “PC4100”, solid content 10 %) 0.2 parts by weight and mixed with a toluene / cyclopentanone (CPN) mixed solvent (weight ratio 70/30) to prepare a composition for forming an antiglare layer having a solid content concentration of 32% by weight.
  • CPN toluene / cyclopentanone
  • the organic clay was diluted with toluene so that the solid content was 6% by weight.
  • 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. for 1 minute, 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 glass plate (thickness: 700 ⁇ m) is placed on the backlight (made by Hakuba Photo Industry Co., Ltd., trade name “Light Viewer 5700”), and a black matrix pattern is placed on the surface of the glass plate opposite to the backlight.
  • An evaluation table was prepared.
  • a pressure-sensitive adhesive layer (thickness: 20 ⁇ m) was disposed as a member A constituting a part of the gap X.
  • 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 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
  • An evaluation table was prepared in the same manner as described above.
  • a black acrylic plate (Mitsubishi Rayon Co., Ltd., thickness: 2 mm) is bonded to the surface of the transparent substrate opposite to the anti-glare layer with an adhesive, and evaluation is performed while suppressing the influence of back surface reflection.
  • 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.
  • ⁇ The image of the reflected fluorescent lamp does not leave an outline image and is excellent in anti-glare properties.
  • ⁇ The fluorescent lamp outline is reflected in the image and inferior in anti-glare properties.
  • the antiglare film of the present invention can suppress glare regardless of the thickness of the member disposed on the back side, and is excellent in transparency and antiglare properties. The effect can also be exhibited in a high-definition image display device.

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  • Physics & Mathematics (AREA)
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