WO2016030738A1 - Stratifié anti-éblouissement - Google Patents

Stratifié anti-éblouissement Download PDF

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Publication number
WO2016030738A1
WO2016030738A1 PCT/IB2015/001433 IB2015001433W WO2016030738A1 WO 2016030738 A1 WO2016030738 A1 WO 2016030738A1 IB 2015001433 W IB2015001433 W IB 2015001433W WO 2016030738 A1 WO2016030738 A1 WO 2016030738A1
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WIPO (PCT)
Prior art keywords
fine particles
particle diameter
coat layer
hard coat
peaks
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PCT/IB2015/001433
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English (en)
Japanese (ja)
Inventor
賢 大久保
誠司 瀬口
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王子ホールディングス株式会社
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Priority to JP2016545078A priority Critical patent/JPWO2016030738A1/ja
Publication of WO2016030738A1 publication Critical patent/WO2016030738A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • 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

Definitions

  • the present invention relates to an antiglare laminate. This application claims the priority based on Japanese Patent Application No. 2014-171385 for which it applied on August 26, 2014, and uses the content here.
  • Liquid crystal display devices are widely used for flat panel displays such as personal computers, mobile phones, and portable game devices.
  • an antiglare film may be attached to the surface in order to prevent a decrease in visibility due to light reflected from the outside.
  • Patent Document 1 a film that scatters reflection of light by providing an uneven structure on the surface is known.
  • Patent Document 2 a hard coat layer mainly composed of particles having an average particle diameter of 0.6 to 20 ⁇ m, fine particles having an average particle diameter of 1 to 500 nm, and a hard coat resin is formed on a transparent substrate film.
  • An antiglare film is disclosed.
  • Patent Document 2 discloses an optical film including an antiglare layer containing a binder resin, organic fine particles, and inorganic fine particles on a light-transmitting substrate.
  • ppi is pixel / inch and means the number of pixels per inch.
  • the glare phenomenon is a phenomenon that occurs when an anti-glare film with a concavo-convex layer is attached to the surface of a liquid crystal display device, because the pixels of the liquid crystal are enlarged by the lens effect.
  • the antiglare film disclosed in Patent Document 1 is provided with a hard coat layer containing two types of particles, large and small. Such an anti-glare film is effective for anti-glare properties, but cannot be said to be effective for glare generated in a high-definition liquid crystal display device.
  • the optical film disclosed in Patent Document 2 is provided with an antiglare layer containing two kinds of particles, organic fine particles and inorganic fine particles. Such an optical film is effective for anti-glare properties, azimuth blur, and interference fringes, but cannot be said to be effective for glare generated in a high-definition liquid crystal display device.
  • An object of the present invention is to provide an antiglare laminate excellent in antiglare properties and glare prevention, a display device including the antiglare laminate, a curable resin composition therefor, and a coating film.
  • the present inventors have studied the uneven structure on the surface of the hard coat layer. As a result, it has been found that the degree of randomness of the concavo-convex structure on the surface of the hard coat layer can be appropriately controlled by using a combination of three or more kinds of fine particles having different average particle diameters.
  • the present invention has been achieved based on such knowledge. That is, the present invention has the following configuration.
  • An antiglare laminate having a transparent substrate and a hard coat layer provided on at least one outermost layer thereof,
  • the hard coat layer contains a curable resin and a fine particle component, and has irregularities on the surface by containing the fine particle component,
  • the fine particle component has at least three or more peaks in the particle size distribution, Of the at least three or more peaks, the average particle size of the fine particles belonging to the first peak region is A ( ⁇ m), and the average particle size of the fine particles belonging to the second peak region having a particle size smaller than A is B ( ⁇ m), and when the average particle diameter of fine particles belonging to the third peak region including m peaks smaller than A and larger than B is Cm ( ⁇ m), the following equation is satisfied:
  • An antiglare laminate 1 ⁇ A ⁇ 5, 0.001 ⁇ B ⁇ 0.3, (2 ⁇ B) ⁇ Cm ⁇ (0.5 ⁇ A),
  • m is an integer of 1 or more.
  • a display device comprising the antiglare laminate according to any one of (1) to (6).
  • a curable resin composition for forming an antiglare hard coat layer contains a curable resin and a fine particle component,
  • the fine particle component has at least three or more peaks in the particle size distribution, Of the at least three or more peaks, the average particle size of the fine particles belonging to the first peak region is A ( ⁇ m), and the average particle size of the fine particles belonging to the second peak region having a particle size smaller than A is B ( ⁇ m), and when the average particle diameter of fine particles belonging to the third peak region including m peaks smaller than A and larger than B is Cm ( ⁇ m), the following equation is satisfied:
  • a curable resin composition 1 ⁇ A ⁇ 5, 0.001 ⁇ B ⁇ 0.3, (2 ⁇ B) ⁇ Cm ⁇ (0.5 ⁇ A),
  • m is an integer of 1 or more.
  • the display device provided with the antiglare laminate of the present invention and the antiglare laminate is excellent in antiglare properties and glare prevention.
  • the curable resin composition and coating film of the present invention can provide a hard coat layer of an antiglare laminate excellent in antiglare property and glare prevention.
  • the high-definition display device in this embodiment refers to a display device of 200 ppi or more. Furthermore, it is more preferable that it is a display apparatus of 250 ppi or more.
  • the antiglare laminate of the present embodiment has a transparent substrate and a hard coat layer provided on the outermost layer on at least one side thereof.
  • a transparent substrate and a hard coat layer provided on the outermost layer on at least one side thereof.
  • other layers such as an anchor layer, a refractive index adjusting layer, and a protective layer may be laminated between the transparent substrate and the hard coat layer as necessary.
  • the hard coat layer may be formed on the outermost layer on the front side (external world side) of the transparent base material, or may be formed on the outermost layer on the back side (anti-external side) of the transparent base material. It may be formed in the outermost layer.
  • a transparent base material becomes a transparent base material which forms a hard-coat layer.
  • the material for forming the transparent substrate is preferably a material excellent in optical transparency, mechanical strength, solvent resistance, and the like.
  • the transparent substrate may be an organic material or an inorganic material.
  • organic materials include polypropylene resins, polyethylene resins, cyclic polyolefin resins, polyamide resins, polyester resins, polyacrylic resins, polyvinyl chloride resins, nylon resins, urethane resins, and triacetyl cellulose.
  • Cellulosic resins such as Among these, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polypropylene naphthalate, polytrimethylene terephthalate, and polybutylene terephthalate are preferable. Furthermore, it is more preferable to use polyethylene terephthalate from the viewpoints of transparency, weather resistance, solvent resistance, rigidity, and cost.
  • the organic material may be used by mixing or laminating two or more kinds of organic materials.
  • the inorganic material examples include soda lime glass, borosilicate glass, quartz glass, and tempered glass (aluminosilicate glass). Among these, tempered glass (aluminosilicate glass) is preferable.
  • the transparent base material may contain various additives.
  • the additive include an antioxidant, a heat stabilizer, an ultraviolet absorber, a pigment, a dye, an antistatic agent, a nucleating agent, and a coupling agent.
  • the transparent substrate may be subjected to a surface treatment.
  • the surface treatment include corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, and surface oxidation treatment such as ozone / ultraviolet irradiation treatment.
  • the thickness of the transparent substrate is preferably 1 to 1,000 ⁇ m, more preferably 5 to 500 ⁇ m, and more preferably 50 to 250 ⁇ m from the viewpoints of ensuring mechanical strength, curling prevention, workability, and the like. It is more preferable.
  • the transparent substrate preferably has a retardation of 3,000 to 30,000 for the reason of reducing the rainbow pattern described later.
  • the retardation is more preferably 5,000 to 25,000.
  • the hard coat layer is provided on the outermost layer on at least one side of the transparent substrate, contains a curable resin and a fine particle component, and has irregularities on the surface by containing the fine particle component.
  • a hard coat layer By forming a hard coat layer on the surface of the transparent substrate, scratch resistance and scratch resistance can be imparted.
  • the hard coat layer can impart antifouling properties, finger slipping properties, water repellency, and the like to sebum and cosmetics on the surface of the transparent substrate.
  • the curable resin may be a thermosetting type or an active energy ray curable type.
  • the active energy ray curable type is preferable.
  • Active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, visible rays, and ⁇ rays.
  • thermosetting resin examples include phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin, and the like.
  • the active energy ray-curable resin examples include acrylic curable resins and urethane curable resins. Moreover, as an active energy ray, an ultraviolet ray is preferable from the viewpoint of easy handling and processing.
  • the active energy ray-curable acrylic curable resin is a polymer of a curable composition comprising a monomer or oligomer having an acrylic polymerizable unsaturated group.
  • Monomers and oligomers having an acrylic polymerizable unsaturated group include monofunctional and polyfunctional ones.
  • the monofunctional monomer having an acrylic polymerizable unsaturated group examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (meta ) N-undecyl
  • the monofunctional oligomer having an acrylic polymerizable unsaturated group examples include ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol acrylate, phenoxypolyethylene glycol acrylate, and the like.
  • a polyfunctional (meth) acrylic ester is used as the monomer or oligomer having an acrylic polymerizable unsaturated group. It is preferable to contain.
  • polyfunctional (meth) acrylic acid esters include dipropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate.
  • Bifunctional (meth) acrylates such as propylene oxide modified neopentyl glycol di (meth) acrylate, modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, polyether tri (meth) acrylate , Trifunctional (meth) acrylates such as glycerin propoxytri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, propionic acid modified dipentaerythritol Examples include t
  • the active energy ray-curable urethane-based curable resin is a polymer of urethane acrylate monomer or oligomer.
  • a urethane acrylate oligomer a polyoxyalkylene segment and / or a saturated polyester segment are linked via a urethane bond, and acryloyl groups are present at both ends.
  • thermosetting or active energy ray-curable acrylic curable resin In order to obtain a thermosetting or active energy ray-curable acrylic curable resin, a polymerization initiator is added to the monomer or oligomer having the polymerizable unsaturated group, and the thermosetting or active energy ray curing is performed. It is necessary to make the composition of the nature.
  • thermal polymerization initiator known ones can be used. Examples thereof include peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide.
  • the addition amount of the thermal polymerization initiator is preferably 1 to 10% by mass relative to the monomer or oligomer having a polymerizable unsaturated group.
  • active energy ray polymerization initiator various known photopolymerization initiators can be used.
  • benzoin benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 -One, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, prop
  • One of these active energy ray polymerization initiators may be used alone, or two or more thereof may be used in combination.
  • the addition amount of the active energy ray polymerization initiator is preferably 1 to 10% by mass relative to the monomer or oligomer having a polymerizable unsaturated group.
  • a photosensitizer can be further contained.
  • the photosensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.
  • the hard coat layer may contain a flexible component as necessary.
  • a flexible component As the flexible component, (meth) acrylates having one or more polymerizable unsaturated groups in the molecule are preferable. Examples of (meth) acrylates include tricyclodecanemethylol di (meth) acrylate, ethylene oxide modified di (meth) acrylate of bisphenol F, ethylene oxide modified di (meth) acrylate of bisphenol A, and ethylene oxide modified of isocyanuric acid.
  • Bifunctional (meth) acrylates such as di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide modified tri (meth) acrylate of trimethylpropane , Trifunctional (meth) acrylates such as ethylene oxide modified tri (meth) acrylate of trimethylpropane, urethane (meth) acrylate, polyester (meth ) Acrylates, polyether (meth) acrylate.
  • trifunctional (meth) acrylate and urethane (meth) acrylate are more preferable.
  • These (meth) acrylates can be used singly or in combination of two or more.
  • the hard coat layer may contain components other than those described above as long as the effects of the present embodiment are not impaired.
  • Components that can be added to the hard coat layer include, for example, a dispersant, a flexible component, an antibacterial agent, a fluorine antifouling agent, a fluorine lubricant or a silicone lubricant, a leveling agent, an antistatic agent, an ultraviolet absorber, and a heat stabilizer. Agents, antioxidants and the like.
  • the dispersant includes those used to uniformly disperse fine particles described later in the coating liquid for forming the hard coat layer.
  • the thickness of the hard coat layer is preferably 0.5 to 8.0 ⁇ m.
  • the thickness of the hard coat layer is more preferably from 0.5 to 5.0 ⁇ m, further preferably from 1.0 to 4.0 ⁇ m, and most preferably from 1.0 to 3.5 ⁇ m.
  • the fine particle component contained in the hard coat layer has at least three or more peaks in the particle size distribution.
  • the peak is the particle size when the number of particles reaches a maximum value in a chart in which the horizontal axis represents the particle size and the vertical axis represents the number of particles.
  • the present inventors use a fine particle component having at least three or more peaks in the particle size distribution as the fine particle component contained in the hard coat layer, and when the particle diameter of each peak is in a specific numerical range, It has been found that the randomness of the concavo-convex structure on the surface of the hard coat layer can be appropriately controlled, and it is possible to achieve both the antiglare property and the glare prevention of the antiglare laminate.
  • the fine particle component has at least three or more peaks in the particle size distribution, and among the at least three or more peaks, the average particle diameter of the fine particles belonging to the first peak region is A ( ⁇ m). And the average particle diameter of the fine particles belonging to the second peak area is B ( ⁇ m), and the average particle diameter of the fine particles belonging to the third peak area including m peaks whose particle diameter is smaller than A and larger than B is
  • the diameter is Cm ( ⁇ m)
  • m is an integer of 1 or more.
  • the particle size distribution of the fine particles is measured by the following method. Using a transmission electron microscope, the surface layer of the hard coat layer is photographed to obtain a particle image. The maximum length (Dmax: maximum length at two points on the contour of the particle image) and the maximum vertical length (DV-max: two lines when the particle image is sandwiched between two straight lines parallel to the maximum length) ) Is measured, and the geometric mean value (Dmax ⁇ DV-max) 1/2 is defined as the particle diameter.
  • Dmax maximum length at two points on the contour of the particle image
  • DV-max maximum vertical length
  • the geometric mean value (Dmax ⁇ DV-max) 1/2 is defined as the particle diameter.
  • the peak area is a particle size distribution chart in which the vertical axis represents the number of fine particles and the horizontal axis represents the particle diameter of the fine particles, and one peak in the particle size distribution (the point where the number of fine particles protrudes) is horizontal. It means a certain region in the horizontal axis direction where fine particles exist as the center in the axial direction.
  • the peak area is a term that should be interpreted according to common general technical knowledge.
  • the peak area is, for example, from a minimum value (first minimum value) closest to the peak having a particle diameter smaller than the peak with a certain peak in the particle size distribution as the center in the horizontal axis direction.
  • the particle diameter is larger and the curve from the peak to the nearest minimum value (second minimum value), the horizontal axis of the particle size distribution diagram, the vertical axis with the first minimum value as a constant, It can be regarded as a region surrounded by a vertical axis having the second minimum value as a constant.
  • the distance or region from the maximum value to the minimum value is not clear, for example, one maximum value and an inflection point on the way from the maximum value to the minimum value. Twice the distance can be used as an approximate value of the distance from the maximum value to the minimum value.
  • the average particle size of the fine particles belonging to the first peak region is A ( ⁇ m)
  • the number of peaks having a particle diameter smaller than A and larger than B is one or more.
  • the average particle diameter of fine particles belonging to the peak region is defined as C1 ( ⁇ m).
  • the average particle diameters of the fine particles belonging to those peak regions are C1 ( ⁇ m) and C2 ( ⁇ m), respectively.
  • the average particle diameters of the fine particles belonging to those peak regions are respectively set to C3 ( ⁇ m) and C4 ( ⁇ m) etc.
  • the average particle diameter of peaks having a particle diameter smaller than A and larger than B is collectively expressed as Cm ( ⁇ m).
  • the average particle diameter A ( ⁇ m) of the fine particles whose particle diameter belongs to the first peak region is 1 ⁇ A ⁇ 5. Such fine particles are exclusively involved in imparting antiglare properties to the hard coat layer.
  • the average particle diameter B ( ⁇ m) of the fine particles belonging to the second peak region having a particle diameter smaller than A is 0.001 ⁇ B ⁇ 0.3. Such fine particles are exclusively involved in suppressing glare.
  • the average particle diameter Cm ( ⁇ m) of the fine particles belonging to the third peak region including m peaks smaller than A and larger than B is (2 ⁇ B) ⁇ Cm ⁇ (0.5 ⁇ A). It is. Such fine particles are exclusively involved in suppressing glare.
  • the fine particle component has N 1 as the number of fine particles belonging to the first peak region, and N 2 as the number of fine particles belonging to the second peak region whose particle size is smaller than A.
  • N 1 : N 2 : N 3 1: 30: 5 to 1:50 where N 3 is the number of fine particles belonging to the third peak region including m peaks smaller than A and larger than B. It is preferable to satisfy a ratio of 1,000,100. When the relative number of fine particles belonging to three or more kinds of peak regions is within the range of this ratio, it becomes possible to improve the antiglare property and glare prevention of the antiglare laminate at a higher level. .
  • the number of fine particles belonging to the peak region can be measured together with the particle size distribution of the fine particles by the method using the transmission electron microscope.
  • the fine particles may be inorganic fine particles or organic fine particles.
  • inorganic fine particles for example, metal oxide fine particles such as silicon dioxide, titanium dioxide, zirconium oxide, and aluminum oxide can be used, and those having high hardness are preferable.
  • organic fine particles for example, resin particles such as acrylic resin, polystyrene, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, cellulose acetate, polycarbonate, and polyamide can be used.
  • the surface of the fine particles may be surface-treated for the purpose of uniformly dispersing the fine particles in the hard coat layer.
  • the surface treatment method include methods such as imparting a functional group such as a hydroxyl group and a carboxylic acid in addition to imparting a surfactant.
  • the content of the fine particles in the hard coat layer depends on the thickness of the hard coat layer, but from the viewpoint of glare and antiglare properties, the total content is preferably 10 to 500% by mass, and 50 to 300% by mass. It is more preferable that
  • the difference in refractive index between the fine particles and the hard coat layer is preferably 0.1 or less, and more preferably 0.01 or less.
  • the average particle diameters A, B, and Cm of the fine particles satisfy the above formula, it is effective not only for preventing glare and glare, but also for preventing rainbow patterns and whiteness.
  • the rainbow pattern is an interference pattern that appears due to a difference in refractive index between the transparent substrate and the hard coat layer.
  • WHITE is a phenomenon that appears whitish when the transmitted light of the antiglare laminate is viewed. Unlike the antiglare property, which is evaluated by the diffused state of reflected light, it is evaluated by the diffused state of transmitted light. Whitiness can be reduced by appropriately controlling the degree of unevenness on the surface of the hard coat layer.
  • the skewness of the hard coat layer is 1.0 to 4.0.
  • the skewness is an index of the degree of uneven unevenness of the hard coat layer surface. It is measured according to JIS B0601-2001. This represents the degree of symmetry deviation of the height distribution with the average plane as the center. When the skewness is 0, it indicates that the height distribution of the surface irregularities is symmetric with respect to the average line. When the skewness is a positive numerical value, the height distribution is biased downward with respect to the average surface, indicating that the unevenness tends to be sharp.
  • the haze is preferably 2 to 10%, and more preferably 4 to 8%. By setting the haze in the range of 2 to 10%, the antiglare level can be made more effective.
  • the haze is an index related to the transparency of the laminate and is also referred to as haze. This is the ratio of diffuse transmitted light to total light transmitted. In general, when haze increases, it appears whitish and blurry. It can be controlled by appropriately changing the degree of unevenness on the surface of the hard coat layer.
  • the total light transmittance is preferably 88% or more and more preferably 90% or more from the viewpoint of improving the visibility of the display device.
  • the gloss is preferably 60 to 90%, and more preferably 60 to 80%. By making the glossiness in the range of 60 to 90%, the antiglare property can be further improved.
  • the glossiness is evaluated as a 60-degree specular reflectance.
  • a curable resin composition for forming an antiglare hard coat layer is applied on a transparent substrate, and then the hard coat layer is dried, and then the hard coat layer Can be cured to form a hard coat layer coating. That is, the hard coat layer of the antiglare laminate of this embodiment is a coating film obtained by curing a curable resin composition.
  • the manufacturing process can also be performed continuously in a roll-to-roll manner.
  • the curable resin composition of this embodiment contains a curable resin and a fine particle component, and the fine particle component has at least three or more peaks in the particle size distribution, and among the at least three or more peaks.
  • m is an integer of 1 or more.
  • the number of fine particles belonging to the first peak region where the particle size belongs to N 1 and the number of fine particles belonging to the second peak region where the particle size is smaller than A is defined as N 1.
  • an average It can be obtained by adding three or more kinds of fine particles having a particle diameter ( ⁇ m) in the numerical ranges of A, B, and Cm to the curable resin composition at a predetermined blending ratio. That is, the fine particle component contained in the curable resin composition can have the above-mentioned particle size distribution of the fine particle component by adding three or more kinds of fine particles having different average particle sizes at an appropriate blending ratio. .
  • the method for setting the ratio of the number of fine particles belonging to each peak region to the above ratio is also the same.
  • Examples of the solvent for the curable resin composition include methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, n-hexane, n-butyl alcohol, methyl isobutyl ketone, methyl butyl ketone, ethyl butyl ketone, cyclohexanone, ethyl acetate, Butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, N-methyl-2-pyrrolidone and the like are used. These may be used alone or in combination of two or more.
  • Examples of the coating method of the curable resin composition include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and a printing machine. The method used is mentioned.
  • the coating film is dried by heating the transparent substrate having the coating film. Usually, the heating is performed under conditions of a heating temperature of 60 to 100 ° C. and a heating time of 1 to 5 minutes. Drying is performed by a heat dryer or a vacuum dryer.
  • the uncured coating film is cured.
  • the uncured coating film contains a thermosetting resin, it is heated and cured using a heating furnace or an infrared lamp.
  • the uncured coating film contains an active energy ray-curable resin, it is cured by irradiation with active energy rays.
  • active energy ray ultraviolet rays are preferable from the viewpoint of versatility.
  • the ultraviolet light source for example, a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, or the like can be used.
  • Curing by irradiation with active energy rays is preferably performed in an environment filled with an inert gas such as nitrogen.
  • the curing process may be performed in two stages, a preliminary curing process and a main curing process.
  • the antiglare laminate of the present embodiment enables both antiglare properties and glare prevention in a display device including the laminate.
  • a display device including the laminate In particular, in a high-definition liquid crystal display device of 200 to 400 ppi, and further 250 to 400 ppi, the characteristics can be further exhibited.
  • the quantity of the silica described in Table 1 is a numerical value of the mass part as solid content. When actually used, it is used as a dispersion (30% by mass) dispersed in MEK.
  • PET film a manufactured by Toyobo Co., Ltd., A4100, film thickness 100 ⁇ m, retardation was 2,500 nm.
  • PET film b Polyethylene terephthalate was dissolved at 290 ° C., extruded through a film-forming die into a sheet, and then cooled with water. Then, it was made to contact
  • the film was stretched at a stretching ratio of 1.5 times in the direction of 90 degrees.
  • the obtained PET film b had a film thickness of 100 ⁇ m and a retardation of 9,000 nm.
  • retardation was measured using Oji Scientific Instruments company make, KOBURA-WPR.
  • Example 1 By applying the coating liquid HC1 for the hard coat layer having the composition shown in Table 1 to the surface of one side of the PET film a using a bar coater, drying, and then irradiating with 300 mJ / cm 2 of ultraviolet rays and curing.
  • the antiglare laminate 1 was obtained.
  • the number of fine particles, N 1 : N 2 : N 3 was 1:24, 355: 13.
  • the thickness of the hard coat layer after curing was 2.4 ⁇ m.
  • Example 2 After applying the coating liquid HC2 for hard coat layer having the composition described in Table 1 to the surface on one side of the PET film a using a bar coater, the antiglare laminate 2 was obtained in the same manner as in Example 1. .
  • the thickness of the hard coat layer after curing was 2.5 ⁇ m.
  • Example 3 After applying the hard coat layer coating solution HC3 having the composition shown in Table 1 to the surface of one side of the PET film b using a bar coater, the antiglare laminate 3 was obtained in the same manner as in Example 1. .
  • the number of fine particles, N 1 : N 2 : N 3 was 1:23, 587: 22.
  • the thickness of the hard coat layer after curing was 2.4 ⁇ m.
  • Example 4 After applying the coating liquid HC4 for hard coat layer having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 4 was obtained in the same manner as in Example 1. .
  • the thickness of the hard coat layer after curing was 2.5 ⁇ m.
  • Example 5 After applying the hard coat layer coating liquid HC5 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 5 was obtained in the same manner as in Example 1. .
  • the thickness of the hard coat layer after curing was 2.6 ⁇ m.
  • Example 6 After applying the hard coat layer coating liquid HC6 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 6 was obtained in the same manner as in Example 1. .
  • the number of fine particles, N 1 : N 2 : N 3 was 1:41, 474: 15.
  • the thickness of the hard coat layer after curing was 2.3 ⁇ m.
  • Example 7 After applying the hard coat layer coating solution HC7 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 7 was obtained in the same manner as in Example 1. .
  • the number of fine particles, N 1 : N 2 : N 3 was 1:43:11.
  • the thickness of the hard coat layer after curing was 2.6 ⁇ m.
  • Example 8 After applying the coating liquid HC8 for hard coat layer having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 8 was obtained in the same manner as in Example 1. .
  • the thickness of the hard coat layer after curing was 2.3 ⁇ m.
  • Example 9 After applying the coating liquid HC9 for hard coat layer having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 9 was obtained in the same manner as in Example 1. .
  • the thickness of the hard coat layer after curing was 2.4 ⁇ m.
  • Example 1 After applying the hard coat layer coating solution HC10 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 10 was obtained in the same manner as in Example 1. .
  • the thickness of the hard coat layer after curing was 2.7 ⁇ m.
  • Example 2 After applying the hard coat layer coating solution HC11 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 11 was obtained in the same manner as in Example 1. .
  • the thickness of the hard coat layer after curing was 2.5 ⁇ m.
  • Example 3 After applying the hard coat layer coating solution HC12 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 12 was obtained in the same manner as in Example 1. .
  • the thickness of the hard coat layer after curing was 2.4 ⁇ m.
  • Example 4 After applying the hard coat layer coating solution HC13 having the composition shown in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 13 was obtained in the same manner as in Example 1. .
  • the thickness of the hard coat layer after curing was 2.4 ⁇ m.
  • Example 5 After applying the hard coat layer coating solution HC14 having the composition described in Table 1 to the surface of one side of the PET film a using a bar coater, the antiglare laminate 14 was obtained in the same manner as in Example 1. .
  • the number of fine particles, N 1 : N 2 : N 3 was 1:12:10.
  • the thickness of the hard coat layer after curing was 2.6 ⁇ m.
  • Haze and total light transmittance were measured using a haze meter NDH4000 manufactured by Denshoku Co., Ltd.
  • the antiglare laminate 1 to the antiglare laminate 9 of Examples 1 to 9 all have good antiglare and antiglare properties, such as rainbow patterns and whitening. It was hard to produce a gap.
  • Example 3 since the retardation of the transparent substrate was as high as 9,000, the effect of suppressing the rainbow pattern was particularly excellent.
  • Example 8 since the skewness was small, the antiglare property and the glare were slightly better than those in the other examples.
  • Example 9 since the skewness was large, the glare was slightly better than in the other examples.
  • Comparative Example 1 the average particle diameter A of the fine particles having the maximum average particle diameter exceeded 5 ⁇ m, which was inferior to glare.
  • Comparative Example 2 the average particle diameter Cm of the fine particles having an average particle diameter between A and B does not exist, and the glare is inferior.
  • Comparative Example 5 the average particle diameter B of the fine particles having the smallest average particle diameter exceeded 0.3 ⁇ m, and the glare and whitish color were inferior.

Abstract

La présente invention concerne un stratifié anti-éblouissement qui présente d'excellentes propriétés anti-éblouissement et propriétés évitant l'éblouissement, un dispositif d'affichage pourvu du stratifié anti-éblouissement, une composition de résine durcissable pour celui-ci et un film de revêtement. Plus spécifiquement, la présente invention concerne un stratifié anti-éblouissement qui comprend un substrat transparent et une couche de revêtement dur qui est prévue sur la couche la plus à l'extérieur sur au moins un côté du substrat transparent, la couche de revêtement dur comprenant une résine durcissable et des composants de microparticules et ayant une surface irrégulière en raison de l'inclusion des composants de microparticules, les composants de microparticules ayant au moins trois crêtes dans la distribution de la taille des particules de ceux-ci et, pour les trois crêtes ou plus, lorsque la taille moyenne de particule des microparticules pour lesquelles la taille de particule appartient à la première zone de crête est A (µm), la taille moyenne de particule des microparticules pour lesquelles la taille de particule appartient à la deuxième zone de crête est B (µm) et la taille moyenne de particule des microparticules pour lesquelles la taille de particule est inférieure à A mais supérieure à B et appartient à la troisième zone de crête comprenant m pics est Cm (μm), la formule suivante est satisfaite. 1≤A≤5, 0,001≤B≤0,3, (2XB)≤Cm≤(0,5XA), m étant un nombre entier au moins égal à 1.
PCT/IB2015/001433 2014-08-26 2015-08-25 Stratifié anti-éblouissement WO2016030738A1 (fr)

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JP2018533067A (ja) * 2016-03-14 2018-11-08 エルジー・ケム・リミテッド 反射防止フィルムおよびディスプレイ装置
US10711142B2 (en) 2016-03-04 2020-07-14 Lg Chem, Ltd. Antireflection film and display device
WO2021193215A1 (fr) * 2020-03-26 2021-09-30 三菱瓦斯化学株式会社 Corps stratifié anti-reflet
CN115104045A (zh) * 2020-03-05 2022-09-23 株式会社Lg化学 防眩膜、偏光板和显示设备
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US10711142B2 (en) 2016-03-04 2020-07-14 Lg Chem, Ltd. Antireflection film and display device
JP2018533065A (ja) * 2016-03-14 2018-11-08 エルジー・ケム・リミテッド 反射防止フィルムおよびディスプレイ装置
JP2018533067A (ja) * 2016-03-14 2018-11-08 エルジー・ケム・リミテッド 反射防止フィルムおよびディスプレイ装置
JP2020079958A (ja) * 2016-03-14 2020-05-28 エルジー・ケム・リミテッド 反射防止フィルムおよびディスプレイ装置
JP2020079959A (ja) * 2016-03-14 2020-05-28 エルジー・ケム・リミテッド 反射防止フィルムおよびディスプレイ装置
US10689523B2 (en) 2016-03-14 2020-06-23 Lg Chem, Ltd. Antireflection film and display device
US11112599B2 (en) 2016-03-14 2021-09-07 Lg Chem, Ltd. Antireflection film having hard coating layer and display device including the same
JP7055436B2 (ja) 2016-03-14 2022-04-18 エルジー・ケム・リミテッド 反射防止フィルムおよびディスプレイ装置
CN115104045A (zh) * 2020-03-05 2022-09-23 株式会社Lg化学 防眩膜、偏光板和显示设备
WO2021193215A1 (fr) * 2020-03-26 2021-09-30 三菱瓦斯化学株式会社 Corps stratifié anti-reflet
JP7373456B2 (ja) 2020-04-30 2023-11-02 Ｊｆｅ鋼板株式会社 塗装鋼板

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