WO2012066743A1 - Film de revêtement dur et dispositif d'affichage d'images - Google Patents

Film de revêtement dur et dispositif d'affichage d'images Download PDF

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Publication number
WO2012066743A1
WO2012066743A1 PCT/JP2011/006200 JP2011006200W WO2012066743A1 WO 2012066743 A1 WO2012066743 A1 WO 2012066743A1 JP 2011006200 W JP2011006200 W JP 2011006200W WO 2012066743 A1 WO2012066743 A1 WO 2012066743A1
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Prior art keywords
film
hard coat
resin
polyester resin
mass
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PCT/JP2011/006200
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English (en)
Japanese (ja)
Inventor
岡野　賢
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コニカミノルタオプト株式会社
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Priority to KR1020137015338A priority Critical patent/KR101563794B1/ko
Priority to JP2012544093A priority patent/JP5783182B2/ja
Publication of WO2012066743A1 publication Critical patent/WO2012066743A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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

Definitions

  • the present invention relates to a hard coat film and an image display device, and more particularly to a hard coat film and an image display device that are improved in blocking and flexibility after a durability test.
  • hard coat films have been used for display devices such as displays, mobile phones, mobile games, touch panels, etc. to prevent damage and to prevent scattering of glass display surfaces such as CRT and PDP.
  • Polycarbonate films, polypropylene films, cycloolefin films, and polyester films are generally used as base films for hard coat films.
  • biaxially stretched films of polyester films are superior in mechanical properties. It is suitably used because it has properties, flame resistance or chemical resistance.
  • the interference color unevenness generally has a refractive index in the plane direction of the polyester film of about 1.66, and the ultraviolet curable acrylic resin layer suitably used for the hard coat layer of the hard coat film generally has a refractive index of 1.
  • This refractive index difference causes interference at the interface between the polyester film and the ultraviolet curable acrylic resin layer, resulting in color unevenness due to interference.
  • This interference color unevenness has been requested to be improved because the hard coat film is transparent and is detected under a special fluorescent lamp such as a three-wavelength fluorescent lamp rather than sunlight or an incandescent lamp.
  • the interlaminar adhesion between the hard coat layer and the substrate film was particularly markedly deteriorated under moisture-resistant conditions assuming a bathroom or a hot and humid area where a mobile phone or the like is used.
  • Patent Document 1 discloses a technique for providing an easy-adhesion layer on a polyester film.
  • the blocking described above was remarkable after the durability test assuming transportation and long-term storage of the hard coat film.
  • it is suitable for hard coat film because it is used by pressing with a pen or finger at the time of information input when used as a surface film for touch panel when processing a hard coat film in a display device.
  • flexibility is deteriorated after an endurance test assuming various use environments.
  • an object of the present invention is to provide a hard coat film and an image display device that are improved in blocking and flexibility after the durability test.
  • the easy-adhesion layer contains at least one selected from a polyester resin, an acrylic resin, and a urethane resin, and the hard coat layer has active energy.
  • a hard coat film comprising a line curable isocyanurate derivative.
  • the polyester resin of the easy-adhesion layer contains two components of polyester resins (X) and (Y), and the polyester resins (X) and (Y) each contain the following acids as acid components: 4.
  • the hard coat film as described in any one of 1 to 3 above.
  • Polyester resin (X) Sodium, sulfonate, and isophthalic acid are included in the acid component.
  • the hard coat layer contains an active energy ray-curable isocyanurate derivative (A) and an active energy ray-curable resin (B) other than the isocyanurate derivative, the active energy ray-curable isocyanurate derivative (A) and the 5.
  • the hard coat film as described in any one of 1 to 4 above, wherein the mass ratio of the active energy ray-curable resin (B) other than the isocyanurate derivative is 10:90 to 50:50 .
  • the image display device described in 7 is a liquid crystal display device including a touch panel, and the hard coat film described in any one of 1 to 6 is used as a constituent member of the touch panel. Image display device.
  • the present inventor has made extensive studies on the above problems, and is an easy-adhesion layer provided between the hard coat layer and the base film in order to prevent interlayer adhesion and interference color unevenness between the hard coat layer and the base film.
  • an active energy ray curable isocyanurate derivative for the hard coat layer, the surface energy of the easy adhesive layer and the hard coat layer is controlled, and the easy adhesive layer and the hard coat By forming a state with a low affinity with the layer, it is possible to obtain good performance in blocking properties after the durability test, and further, by configuring the hard coat film as described above, the elasticity of the hard coat film even after the durability test.
  • the present invention has been found that good flexibility can be obtained without deteriorating.
  • active energy ray-curable isocyanurate derivatives and active energy ray-curable resins other than isocyanurate derivatives are simply described as active energy ray-curable resins.
  • the active energy ray curable type refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams, and specifically, a resin having an ethylenically unsaturated group.
  • the active energy ray-curable isocyanurate derivative is not particularly limited as long as it is a compound having a structure in which one or more ethylenically unsaturated groups are bonded to an isocyanuric acid skeleton.
  • a compound having three or more ethylenically unsaturated groups and one or more isocyanurate rings in the same molecule shown is preferable from the viewpoint of the object effect of the present invention.
  • the kind of ethylenically unsaturated group is an acryloyl group, a methacryloyl group, a styryl group, and a vinyl ether group, more preferably a methacryloyl group or an acryloyl group, and particularly preferably an acryloyl group.
  • L 2 is a divalent linking group, preferably a substituted or unsubstituted alkyleneoxy group or polyalkyleneoxy group having 4 or less carbon atoms in which a carbon atom is bonded to the isocyanurate ring, Particularly preferred are alkyleneoxy groups, which may be the same or different.
  • R 2 represents a hydrogen atom or a methyl group, and may be the same or different.
  • Other compounds include isocyanuric acid diacrylate compounds, and isocyanuric acid ethoxy-modified diacrylate represented by the following general formula (2).
  • ⁇ -caprolactone-modified active energy ray-curable isocyanurate derivatives specifically, compounds represented by the following general formula (3).
  • R 1 to R 3 in the chemical structural formula is attached with a functional group represented by the following a, b, and c, and at least one of R 1 to R 3 is a functional group of b.
  • Examples of commercially available isocyanuric acid triacrylate compounds include A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Examples of commercially available isocyanuric acid diacrylate compounds include Aronix M-215 manufactured by Toagosei Co., Ltd.
  • Examples of the mixture of the isocyanuric acid triacrylate compound and the isocyanuric acid diacrylate compound include Aronix M-315 and Aronix M-313 manufactured by Toagosei Co., Ltd.
  • ⁇ -Caprolactone-modified active energy ray-curable isocyanurate derivatives include ⁇ -caprolactone-modified tris- (acryloxyethyl) isocyanurate, Shin-Nakamura Chemical Co., Ltd. A-9300-1CL, Toagosei Co., Ltd. Examples include Aronix M-327, but are not limited thereto.
  • Active energy ray curable resins other than isocyanurate derivatives include UV curable urethane acrylate resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, UV curable polyol acrylate resins, or UV curable resins. Epoxy resins and the like are preferably used. Of these, ultraviolet curable acrylate resins are preferred.
  • polyfunctional acrylate is preferable.
  • the polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
  • the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.
  • polyfunctional acrylate monomer examples include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate.
  • Monofunctional acrylates may be used as active energy ray-curable resins other than isocyanurate derivatives.
  • Monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl Examples thereof include acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and cyclohexyl acrylate.
  • Monofunctional acrylates can be obtained from Shin Nakamura Chemical Co., Ltd., Osaka Organic Chemical Industry Co., Ltd., and the like. These compounds are used alone or in admixture of two or more.
  • an active energy ray-curable isocyanurate derivative and an active energy ray-curable resin other than an isocyanurate derivative are used in combination in the hard coat layer, other than the active energy ray-curable isocyanurate derivative (A) and the isocyanurate derivative
  • the object of the present invention is achieved even after a more severe weather resistance test. The effect is more preferable from the starting point.
  • the hard coat layer preferably contains a photopolymerization initiator to accelerate the curing of the active energy ray-curable resin.
  • photopolymerization initiator examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto. .
  • the hard coat layer according to the present invention is applied on the easy-adhesion layer of the film substrate by the following method as a hard coat layer coating composition by diluting the above-described active energy ray-curable resin with a solvent or the like, and drying. From the viewpoint of productivity, it is preferable to provide a cured product.
  • Solvents include alcohols (methanol, isopropyl alcohol, 1-methoxy-2-propanol, etc.), ketones (methyl ethyl ketone, acetone, methyl isobutyl ketone, etc.) or acetate esters (methyl acetate, ethyl acetate, butyl acetate, etc.) Solvents are preferred.
  • the coating amount is suitably 0.1 to 40 ⁇ m, preferably 0.5 to 30 ⁇ m, as the wet film thickness.
  • the dry film thickness is from 0.1 to 30 ⁇ m, preferably from 1 to 20 ⁇ m, particularly preferably from 6 to 15 ⁇ m.
  • a known coating method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die (extrusion) coater, or an ink jet method can be used. Drying is preferably carried out at a temperature of 40 ° C. or more in the reduced rate drying section because the diluent solvent does not remain in the hard coat layer, and more preferably the temperature in the reduced rate drying zone is 80 ° C. or higher and 130 ° C. It is as follows.
  • the drying process changes from a constant state to a gradually decreasing state when drying starts.
  • the decreasing section is called the decreasing rate drying section.
  • UV curing treatment is generally used from the viewpoint of productivity, and heat treatment is performed after UV curing treatment as necessary.
  • the heat treatment temperature after UV curing is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher.
  • any light source that generates ultraviolet rays can be used without limitation.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 50 to 1000 mJ / cm 2 , preferably 50 to 300 mJ / cm 2 .
  • irradiating active rays it is preferably performed while applying tension in the film transport direction, more preferably while applying tension in the width direction.
  • the tension to be applied is preferably 30 to 300 N / m.
  • the method for applying tension is not particularly limited, and tension may be applied in the transport direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. Thereby, a film having further excellent flatness can be obtained.
  • the hard coat layer may be a single layer or a plurality of layers.
  • the hard coat layer may be divided into two or more layers.
  • a hard-coat layer may be provided in the single side
  • the thickness of the uppermost layer when two or more layers are provided is preferably in the range of 0.05 to 2 ⁇ m.
  • Two or more layers may be formed as a simultaneous multilayer.
  • the simultaneous multi-layer is to form a hard coat layer by applying two or more hard coat layers on a base material by a wet on wet (wet coating method) without passing through a drying step.
  • the layers are stacked one after another with an extrusion coater or simultaneously with a slot die having a plurality of slits. Can be done.
  • the hard coat layer preferably contains an ultraviolet absorber from the viewpoint of the object effect and adhesiveness of the present invention.
  • the ultraviolet absorber is a compound that has an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less and has little absorption of visible light having a wavelength of 400 nm or more. Specific examples include, but are not limited to, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like. Although the following specific examples are given as a benzotriazole type ultraviolet absorber, this invention is not limited to these.
  • UV-1 2- (2'-hydroxy-5'-methylphenyl) benzotriazole
  • UV-2 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole
  • UV-3 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole
  • UV-4 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-chlorobenzotriazole
  • UV-5 2- (2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole
  • UV-6 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
  • UV-7 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-ch
  • UV-10 2,4-dihydroxybenzophenone
  • UV-11 2,2'-dihydroxy-4-methoxybenzophenone
  • UV-12 2-hydroxy-4-methoxy-5-sulfobenzophenone
  • UV-13 bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
  • the above ultraviolet absorber is preferably a benzotriazole ultraviolet absorber or a benzophenone ultraviolet absorber because the transparency of the hard coat layer is excellent.
  • Commercially available products such as PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) can also be used as the polymer ultraviolet absorber.
  • As a constitution containing an ultraviolet absorber it may be contained in a single hard coat layer, but the hard coat layer is composed of two or more layers, and an ultraviolet absorber is added to the hard coat layer in contact with the easily adhesive layer group.
  • the composition to contain is also mentioned. It is preferable that the hard coat layer contains an ultraviolet absorber from the viewpoint that the object and effects of the present invention are satisfactorily exhibited.
  • the thickness of the hard coat layer in contact with the base film is preferably in the range of 0.05 to 2 ⁇ m.
  • Two or more layers may be formed as a simultaneous multilayer.
  • the simultaneous multi-layering is to form a hard coat layer by applying two or more hard coat layers on a base material without going through a drying step.
  • the layers are stacked one after another with an extrusion coater or simultaneously with a slot die having a plurality of slits. Can be done.
  • the hard coat layer may contain a conductive agent in order to impart antistatic properties, and preferred conductive agents include metal oxide particles or ⁇ -conjugated conductive polymers.
  • An ionic liquid is also preferably used as the conductive compound.
  • the hard coat layer has a nonionic surfactant such as a silicone surfactant, a fluorosurfactant or a polyoxyether, an anionic surfactant, from the viewpoint of coating properties and the uniform dispersibility of fine particles. And a fluorine-siloxane graft polymer.
  • the fluorine-siloxane graft polymer refers to a copolymer polymer obtained by grafting polysiloxane containing siloxane and / or organosiloxane alone and / or organopolysiloxane to at least a fluorine resin.
  • Examples of commercially available products include ZX-022H, ZX-007C, ZX-049, ZX-047-D manufactured by Fuji Kasei Kogyo Co., Ltd. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.
  • the hard coat layer may contain inorganic fine particles and organic fine particles as necessary.
  • silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated silicic acid Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate.
  • silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.
  • These inorganic fine particles are preferably coated with an organic component having a reactive functional group on a part of the surface because the scratch resistance is improved while maintaining the transparency of the hard coat film.
  • an organic component having a reactive functional group on a part of the surface for example, a compound containing an organic component such as a silane coupling agent reacts with a hydroxyl group present on the surface of the metal oxide fine particles, and the surface A mode in which an organic component is bonded to a part of the metal particle, a mode in which an organic component is attached to a hydroxyl group present on the surface of a metal oxide fine particle by an interaction such as a hydrogen bond, or one or more inorganic particles in a polymer particle.
  • a compound containing an organic component such as a silane coupling agent reacts with a hydroxyl group present on the surface of the metal oxide fine particles, and the surface A mode in which an organic component is bonded to a part of the metal particle, a mode in which an organic component is attached to a hydroxyl group present on the surface of a metal oxide fine particle by an interaction such as a hydrogen bond, or one or more inorganic particles in a polymer particle.
  • Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, and melamine resin. Powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder, or the like can be added.
  • Preferred fine particles include crosslinked polystyrene particles (for example, SX-130H, SX-200H, SX-350H manufactured by Soken Chemical), polymethyl methacrylate-based particles (for example, MX150 and MX300 manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles. .
  • Examples of the fluorine-containing acrylic resin fine particles include commercially available products such as FS-701 manufactured by Nippon Paint.
  • Examples of the acrylic particles include Nippon Paint: S-4000, and examples of the acrylic-styrene particles include Nippon Paint: S-1200, MG-251.
  • the average particle diameter of these fine particle powders is not particularly limited, but is preferably 0.01 to 5 ⁇ m, and more preferably 0.01 to 1.0 ⁇ m. Moreover, you may contain 2 or more types of microparticles
  • the average particle diameter of the fine particles can be measured by, for example, a laser diffraction particle size distribution measuring device.
  • the ratio of the ultraviolet curable resin composition and the fine particles is desirably 10 to 400 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the resin composition.
  • the hard coat film of the present invention has a pencil hardness, which is an index of hardness, of H or higher, more preferably 3H or higher. If it is 3H or more, it is not only difficult to be damaged when used in a display device, but is also used as a surface protection film for large-sized liquid crystal display devices and digital signage liquid crystal display devices that are often used outdoors. Excellent film strength even when exposed.
  • the pencil hardness is evaluated by the pencil hardness evaluation method specified by JISK5400 using the test pencil specified by JIS S 6006 after the prepared hard coat film is conditioned at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more. It is the value measured according to.
  • the hard coat layer is a method of forming surface irregularities by adding inorganic or organic fine particles as described above, a method of forming surface irregularities using phase separation by pinodal decomposition, or a method of forming protrusions on the surface by pressing a mold.
  • the antiglare property may be imparted.
  • the mold roll those having fine irregularities and coarse ones can be appropriately selected and applied, and patterns, mats, lenticular lenses, and spherical irregularities arranged regularly or randomly can be used.
  • Anti-glare is to reduce the visibility of the reflected image by blurring the outline of the image reflected on the surface so that the reflected image or light reflection is not an issue when using a display device or the like. .
  • the arithmetic average roughness Ra (JIS B0601: 1994) of the surface irregularities of the hard coat layer is preferably 1 to 300 nm.
  • the height of the protrusion shape is preferably 10 nm to 4 ⁇ m.
  • the width of the protrusion shape is 50 nm to 300 ⁇ m, preferably 50 nm to 100 ⁇ m.
  • the 10-point average roughness Rz is 10 times or less the centerline average roughness Ra, and the average mountain valley distance Sm is preferably 5 to 150 ⁇ m, more preferably 20 to 100 ⁇ m.
  • the deviation is 0.5 ⁇ m or less
  • the standard deviation of the average valley distance Sm with respect to the center line is 20 ⁇ m or less
  • the surface having an inclination angle of 0 to 5 degrees is 10% or more.
  • the arithmetic average roughness Ra, Sm, Rz described above is a value measured with an optical interference surface roughness meter (for example, RST / PLUS, manufactured by WYKO) according to JIS B0601: 1994.
  • the kurtosis (Rku) is preferably 3 or less.
  • the kurtosis (Rku) is a parameter that defines the shape of the convex portion of the surface uneven shape.
  • the kurtosis (Rku) of the antiglare layer is more preferably 1.5 to 2.8. Further, the absolute value of the degree of distortion (Rsk) of the surface is preferably 1 or less.
  • the skewness (Rsk) is a parameter indicating the ratio of the convex portion and the concave portion to the average surface of the concavo-convex shape, and the concavo-convex shape becomes a positively large value when there are many convex portions with respect to the average surface, If there are many concave portions with respect to the average surface, the value becomes negatively large.
  • the absolute value of the skewness (Rsk) exceeds 1, white blur tends to occur.
  • the absolute value of the skewness (Rsk) is preferably 0.01 to 0.5.
  • the kurtosis (Rku) and the skewness (Rsk) can be measured using the optical interference type surface roughness meter.
  • the image sharpness (transmission image clarity) according to JIS-K7105 is preferably 5% to 90% when measured with an optical comb width of 0.5 mm.
  • the base film is easy to manufacture and has excellent transparency and adhesion to the easy-adhesion layer, an acrylic resin film, a polycarbonate resin film, a polypropylene resin film, a cycloolefin resin film, and a polyester
  • an acrylic resin film is easy to manufacture and has excellent transparency and adhesion to the easy-adhesion layer
  • a polycarbonate resin film is easy to manufacture and has excellent transparency and adhesion to the easy-adhesion layer
  • a polypropylene resin film a polypropylene resin film
  • a cycloolefin resin film a cycloolefin resin film
  • a polyester is at least one selected from resin-based films.
  • the acrylic resin film is a film containing a resin having a skeleton derived from acrylic acid or methacrylic acid.
  • the acrylic resin include, but are not limited to, poly (meth) acrylic acid ester such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester Copolymer, methyl methacrylate-acrylic acid ester- (meth) acrylic acid copolymer, methyl (meth) acrylate-styrene copolymer, polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate- Cyclohexyl methacrylate copolymer, methyl methacrylate- (meth) acrylate norbornyl copolymer), and the like.
  • poly (meth) acrylic acid ester such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (
  • acrylic resins poly (meth) acrylate C1-6 alkyl such as poly (meth) methyl acrylate is preferable, and methyl methacrylate resin is more preferable.
  • Commercially available acrylic resins include Delpet 60N, 80N (Asahi Kasei Chemicals Corporation), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) ) And the like. Two or more acrylic resins can be used in combination.
  • the polycarbonate resin film will be described.
  • the polycarbonate resin film is a film containing a resin composed of a compound called poly-4,4′-isopropylidene-diphenyl carbonate.
  • This polycarbonate resin can be produced from bisphenol A and carbonyl chloride in the interfacial polycondensation method, and can be produced from bisphenol A and diphenyl carbonate in the transesterification method.
  • a polypropylene resin is a film containing a resin having a skeleton derived from propylene.
  • polypropylene resin is not particularly limited, but is a homopolymer of propylene or a copolymer of propylene and one or more monomers selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 12 carbon atoms. A polymer etc. are mentioned.
  • the cycloolefin resin film is a film containing a resin having a skeleton derived from cycloolefin.
  • cycloolefin resins include, but are not limited to, resins obtained by subjecting a ring-opening (co) polymer of norbornene monomers to polymer modification such as maleic acid addition or cyclopentadiene addition as necessary.
  • examples thereof include resins obtained by addition polymerization of norbornene monomers and resins obtained by addition polymerization of norbornene monomers and olefin monomers such as ethylene and ⁇ -olefin.
  • norbornene monomers used for obtaining a ring-opening (co) polymer of norbornene monomers include, for example, norbornene, 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl Examples include -2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5-methyl-norbornene.
  • a tungsten, molybdenum, or chromium catalyst called a metathesis polymerization catalyst is preferably used.
  • a cycloolefin resin-type film a zeonore film (made by Nippon Zeon Co., Ltd.), an arton film (made by JSR Co., Ltd.), etc. are mentioned.
  • the polyester resin film will be described.
  • the polyester resin film is preferably a biaxially stretched polyester resin film from the viewpoint of thermal and mechanical stability.
  • a biaxially stretched polyester film is a polyester resin film that has been stretched in two directions and heat-treated as necessary.
  • Dicarboxylic acids used in the polyester resin include aromatic dicarboxylic acids such as terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, diphenyl carboxylic acid, diphenyl sulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, 5-sodium sulfone dicarboxylic acid, and phthalic acid.
  • oxalic acid succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, and paraoxybenzoic acid and other oxycarboxylic acids.
  • succinic acid adipic acid
  • sebacic acid dimer acid
  • maleic acid fumaric acid and other aliphatic dicarboxylic acids
  • cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids and paraoxybenzoic acid and other oxycarboxylic acids.
  • paraoxybenzoic acid and other oxycarboxylic acids can be used.
  • the glycols used in the polyester resin include aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and neopentylglycol, and polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, and polypropylene glycol.
  • alicyclic glycols such as cyclohexanedimethanol, aromatic glycols such as bisphenol A and bisphenol S can be used.
  • terephthalic acid or naphthalenedicarboxylic acid it is preferable to use terephthalic acid or naphthalenedicarboxylic acid as the dicarboxylic acid, and ethylene glycol as the glycol.
  • polyester resin film examples include a polyethylene terephthalate film.
  • an alkaline earth metal compound a manganese compound, a cobalt compound, an aluminum compound, an antimony compound, a titanium compound, a germanium compound or the like as a catalyst during polymerization.
  • a catalyst two or more of these dicarboxylic acids, glycols, and catalysts may be used in combination.
  • a polyester resin film is preferable from the viewpoint that heat resistance, mechanical strength, dimensional stability, and the object effect of the present invention are more satisfactorily exhibited.
  • the thickness of the base film is preferably 10 ⁇ m or more and 350 ⁇ m or less, more preferably 20 ⁇ m or more and 200 ⁇ m or less.
  • the thickness of the base film is preferably 10 ⁇ m or more and 350 ⁇ m or less, more preferably 20 ⁇ m or more and 200 ⁇ m or less.
  • the base film having a width of 1 to 4 m is used. If it exceeds 4 m, conveyance becomes difficult.
  • the length of the substrate film is preferably 500 to 10,000 m, more preferably 1000 m to 7000 m. By setting it as the range of the said length, it is excellent in the processability in application
  • the base film usually has an arithmetic average surface roughness (Ra) of 2 nm to 10 nm, more preferably 2 nm to 6 nm.
  • the base film can be subjected to mat treatment as necessary.
  • mat treatment scratch resistance and handling in the treatment after the production of the film base material is improved.
  • the arithmetic average surface roughness (Ra) of the base film subjected to such a mat treatment is preferably 2 nm or more and 2 ⁇ m or less, more preferably 2 nm or more and 1 ⁇ or less.
  • the fine particles added for the mat treatment preferably have an average particle size of 0.005 to 3 ⁇ m.
  • Fine particles include inorganic particles such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and crosslinked polymers. And so on.
  • silicon dioxide is preferably used from the viewpoint that handling properties and haze increase of the base film can be suppressed.
  • the base film preferably has a total light transmittance of 90% or more, more preferably 92% or more. Moreover, as a realistic upper limit, it is about 99%. Further, the haze value is preferably 2% or less, more preferably 1.5% or less. The total light transmittance and haze value can be measured according to JIS K7361 and JIS K7136.
  • the in-plane retardation Ro of the base film is preferably in the range of 0 to 200 nm and the retardation Rth in the thickness direction is in the range of ⁇ 150 to 150 nm.
  • Ro and Rth are values defined by the following formulas (I) and (II).
  • Formula (I) Ro (nx ⁇ ny) ⁇ d
  • Formula (II) Rth ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d (Where nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the direction perpendicular to the slow axis in the substrate film plane, and nz is the refractive index in the thickness direction of the film) And d is the film thickness (nm).)
  • the retardation can be determined at a wavelength of 590 nm in an environment of 23 ° C. and 55% RH using, for example, KOBRA-21ADH (Oji Scientific Instruments).
  • the substrate film When the substrate film has the retardation, when used in a liquid crystal display device, it suppresses the conversion action of the polarization direction of the transmitted light, and optimizes and controls the polarization in the transmission axis direction of the polarizer. Excellent.
  • the method for producing the base film is not particularly limited.
  • the raw material for flakes of synthetic resin and additives such as a plasticizer are mixed by a known mixing method to prepare a thermoplastic resin composition in advance. Can do.
  • thermoplastic resin composition can be obtained by, for example, pre-blending with a mixer such as an omni mixer and then extruding and kneading the obtained mixture.
  • a mixer such as an omni mixer
  • the kneader used for extrusion kneading is not particularly limited, and for example, a known kneader such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader can be used.
  • a known method such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, or a compression molding method can be used.
  • the solution casting method (solution casting method) and the melt extrusion method are preferable from the viewpoint of productivity.
  • thermoplastic resin composition extruded and kneaded in advance may be used, or other additives such as a synthetic resin and a plasticizer are separately dissolved in a solvent to obtain a uniform mixed solution, and then a solution. It may be formed by a casting method (solution casting method) or a melt extrusion method.
  • Solvents used in the solution casting method include, for example, chlorinated solvents such as chloroform and dichloromethane; aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; methanol, ethanol, and isopropanol Alcohol solvents such as n-butanol and 2-butanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), ethyl acetate, diethyl ether, etc. It is done. These solvents may be used alone or in combination of two or more. Examples of the apparatus for performing the solution casting method (solution casting method) include a drum casting machine, a band casting machine, and a spin coater.
  • chlorinated solvents such as chloroform
  • melt extrusion method examples include a T-die method and an inflation method.
  • the molding temperature of the film during melt extrusion is preferably 150 ° C. or higher and 350 ° C. or lower, more preferably 200 ° C. or higher and 300 ° C. or lower.
  • a T-die When forming a film by the T-die method, a T-die is attached to the tip of a known single-screw extruder or twin-screw extruder, the film is extruded and wound up, and the film is obtained in a roll state. it can. Under the present circumstances, it is also possible to set it as a uniaxial stretching process by adjusting the temperature of a winding roll suitably, and adding extending
  • the base film may be an unstretched film or a stretched film.
  • stretching a uniaxially stretched film may be sufficient and a biaxially stretched film may be sufficient.
  • a biaxially stretched film it may be biaxially stretched simultaneously or sequentially biaxially stretched. In the case of biaxial stretching, the mechanical strength is improved and the film performance is improved.
  • the stretching temperature when performing the stretching step is preferably near the glass transition temperature of the thermoplastic resin composition of the film raw material, specifically, (glass transition temperature-30) ° C. to (glass transition temperature + 100) ° C. It is preferably carried out, more preferably (glass transition temperature ⁇ 20) ° C. to (glass transition temperature + 80) ° C. If the stretching temperature is lower than (glass transition temperature ⁇ 30) ° C., a sufficient stretching ratio cannot be obtained, which is not preferable. If the stretching temperature is higher than (glass transition temperature + 100) ° C., resin flow occurs, and stable stretching cannot be performed.
  • the draw ratio defined by the area ratio can be preferably in the range of 1.1 to 25 times, more preferably in the range of 1.3 to 10 times.
  • the stretching speed (one direction) is preferably in the range of 10 to 20000% / min, more preferably in the range of 100 to 10,000% / min. If it is slower than 10% / min, it takes time to obtain a sufficient draw ratio, and the production cost is increased, which is not preferable. If it is faster than 20000% / min, the stretched film may be broken, which is not preferable. Furthermore, in order to stabilize the optical isotropy and mechanical properties of the base film, a heat treatment (annealing) can be performed after the stretching treatment.
  • the amount of heat applied during stretching or heat treatment may be used for drying after applying an easy-adhesion layer described later as a water-based paint.
  • both ends in the width direction of the film may be embossed (knurled) to prevent blocking.
  • the processing portions at both ends of the film cannot be used, and the portions are generally cut and discarded.
  • masking may be performed with a protective film in order to prevent scratching.
  • a plasticizer may be added to the resin composition forming the film base as necessary.
  • the plasticizer is not particularly limited, but has a functional group capable of interacting with a synthetic resin by hydrogen bonding or the like so as not to cause haze of the base film or bleed out or volatilize from the base film.
  • plasticizers include, but are not limited to, phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, polyhydric alcohol plasticizers.
  • Glycolate plasticizers citrate ester plasticizers, fatty acid ester plasticizers, carboxylic ester plasticizers, polyester plasticizers, sugar esterified products (particularly compounds having a furanose structure and / or a pyranose structure are preferred) Etc.
  • These plasticizers may be used in combination.
  • the plasticizer is preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the base film.
  • a base film may contain the ultraviolet absorber described in the hard-coat layer.
  • an ultraviolet absorber having a molecular weight of 400 or more is preferable because it is difficult to volatilize at a high boiling point and hardly scatters during high temperature molding.
  • antioxidants can also be added to the base film in order to improve the thermal decomposability and thermal colorability during molding.
  • An antistatic agent may be added.
  • a phosphorus-based flame retardant may be added to the base film.
  • Phosphorus flame retardants include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, condensed aryl phosphate ester, halogenated alkyl phosphate ester, halogen-containing condensed phosphate ester, halogen-containing phosphorous phosphorus
  • acid esters or a mixture of two or more types can be mentioned.
  • the base film preferably has a defect of 5 ⁇ m or more in diameter in the film plane of 1 piece / 10 cm square or less.
  • the number of defects is greater than 1/10 cm square, for example, when the film is tensioned during processing in a later process, the film may break with the defects as a starting point, and productivity may decrease.
  • the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.
  • the base film preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more, in the measurement based on JIS-K7127-1999.
  • the upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.
  • the easy-adhesion layer according to the present invention represents a layer provided in order to improve interlayer adhesion between the base film and the hard coat layer, and specifically, when the base film and the hard coat layer are directly bonded.
  • polyester resins are preferable from the viewpoint that the objective effect of the present invention is easily exerted, and it is preferable to use 50% by mass or more of polyester resins with respect to the components constituting the easy-adhesion layer.
  • each resin will be described.
  • the polyester resin is produced by esterifying (transesterifying) a dicarboxylic acid and a diol and polycondensing the polyester resin according to a known method.
  • dicarboxylic acid examples include aromatic dicarboxylic acids or esters such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, succinic acid, sebacic acid, and dodecanedioic acid. Hydroxycarboxylic acids such as hydroxybenzoic acid or their esters can be used.
  • diol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, bisphenols, and the like.
  • the component which has a hydrophilic group may be copolymerized and hydrophilicity may be provided.
  • examples of such a component having a hydrophilic group include dicarboxylic acid components such as 5-sodium sulfoisophthalic acid, and diol components such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.
  • dicarboxylic acid components such as 5-sodium sulfoisophthalic acid
  • diol components such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.
  • the polyester resins it is preferable to use in combination two or more resins having different glass transition points from the viewpoint of the object effect of the present invention and prevention of oligomer precipitation by heating.
  • the polyester resin (X) having a glass transition point Tg of 105 ° C. or higher and lower than 135 ° C. those using 2,6-naphthalenedicarboxylic acid and / or sodium sulfonate / isophthalic acid as the acidic component are preferable. More preferably, an acidic component using sodium, sulfonate, or isophthalic acid is preferable.
  • the content molar ratio of sodium sulfonate / isophthalic acid is preferably 15/50 or less, more preferably 10/50 or less, when the total acidic content of the polyester resin (X) is 50.
  • polyester resin (Y) having a glass transition point Tg of 65 ° C. or higher and lower than 95 ° C. those using terephthalic acid and / or trimellitic acid as the acidic component are preferable, and those using trimellitic acid are more preferable. preferable.
  • the molar ratio of trimellitic acid is preferably 20/50 or less, more preferably 15/50 or less, assuming that the total acidic content of the polyester resin (Y) is 50.
  • ethylene glycol is preferred.
  • the acrylic resin can be synthesized by polymerizing a reactive polymer having a skeleton derived from acrylic acid or methacrylic acid.
  • reactive polymers include those having a carboxyl group such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxyphenyl acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxybutyl (meta ) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and other hydroxyl groups, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, Those having an amide group such as N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, those having a glycidyl group such as glycidyl (meth) acrylate, 7-amino-3,7-dimethyloc
  • copolymer components other than the above that constitute the acrylic resin include acrylic ester, methacrylic ester, propylene, vinyl chloride, cellulose, ethylene, ethyleneimine, vinyl alcohol, peptide, and vinyl. Pyridine-based, diene-based, fluorine-based, acrylonitrile-based, and the like can be mentioned. From the viewpoints of versatility and coating properties, it is preferable to include acrylate-based and methacrylic ester-based.
  • the component which comprises these acrylic resins can be used individually or in combination of multiple types.
  • the urethane resin can be synthesized from a polyhydroxyl compound, diisocyanate, and a low molecular weight chain extender containing at least two hydrogen atoms that react with the diisocyanate by a known method. For example, after synthesizing a relatively high molecular weight polyurethane in a solvent, water is added little by little to phase inversion emulsification, and the solvent is removed by decompression, or polyethylene glycol or carboxyl group is introduced as a hydrophilic group in the polymer. There is a method in which the urethane prepolymer dissolved or dispersed in water is added and reacted with a chain extender.
  • polyhydroxyl compounds used in the production of urethane resins include carboxylic acids such as phthalic acid, adipic acid, dimerized linolenic acid and maleic acid; glycols such as ethylene glycol, propylene glycol, butylene glycol and diethylene glycol; Polyester polyols obtained by dehydration condensation reaction from methylolpropane, hexanetriol, glycerin, trimethylolethane, pentaerythritol, etc .; polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, polyoxypropylene triol, polyoxyethylene poly Initiators are inorganic acids such as oxypropylene triol, sorbitol, pentaerythritol, sucrose, starch and phosphoric acid Polyoxypropylene polyols, polyether polyols such as polyoxypropylene polyoxyethylene polyol, acrylic polyol, a derivative of castor
  • diisocyanates used in the production of urethane resins include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tetramethylene Diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4 '-Biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4' Biphenylene diisocyanate,
  • chain extenders used in the production of urethane resins include ethylene glycol, 1,4-butanediol, trimethylolpropane, triisopropanolamine, N, N-bis (2-hydroxypropyl) aniline, hydroquinone-bis Polyols such as ( ⁇ -hydroxyethyl) ether and resorcinol-bis ( ⁇ -hydroxyethyl) ether, ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, tolylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminodiphenylmethane, diaminodicyclohexyl Examples include methane, piperazine, isophoronediamine, polyamines such as diethylenetriamine and dipropylenetriamine, hydrazines, and water. These chain extenders can be used alone
  • the synthetic reaction in the production of the urethane-based resin can be performed in the presence of a catalyst such as an organic tin compound, organic bismuth, or amine, and among these, it is particularly preferable to perform in the presence of an organic tin compound.
  • a catalyst such as an organic tin compound, organic bismuth, or amine, and among these, it is particularly preferable to perform in the presence of an organic tin compound.
  • organic tin compounds include stannous acetate, stannous octoate, stannous laurate, stannous oleate and the like; dibutyltin acetate, dibutyltin dilaurate, dibutyltin maleate Dialkyltin salts of carboxylic acids such as dibutyltin di-2-ethylhexoate, dilauryltin diacetate, dioctyltin diacetate; trialkyl hydroxides such as trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide Tin: Dialkyltin oxide such as dibutyltin oxide, dioctyltin oxide and dilauryltin oxide; Dialkyltin chloride such as dibutyltin dichloride and dioctyltin dichloride, etc., and these may be used alone. More than one species may be used in combination
  • a resin selected from a polyester resin, an acrylic resin, and a urethane resin is applied to a base film as an aqueous emulsion or an aqueous solution (hereinafter referred to as “aqueous emulsion etc.”) and dried. Can be formed. Moreover, after apply
  • the solid content of the water-based emulsion is usually 10% by mass or more and 50% by mass or less.
  • Water is used as the main solvent for the aqueous emulsion and the like, but a small amount of an organic solvent miscible with water may be used. Examples of such organic solvents include lower alcohols, polyhydric alcohols and alkyl ethers or alkyl esters thereof.
  • Water-based emulsions, etc. are known as dip coating methods, air knife coating methods, curtain coating methods, roller coating methods, wire bar coating methods, gravure coating methods, extrusion coating methods (die coating methods), etc. Can be applied. Subsequently, an easily bonding layer can be formed by drying the applied water-based emulsion and the like.
  • crosslinking agent it is preferable to add a crosslinking agent to the aqueous emulsion for forming the easy-adhesion layer, if necessary.
  • the crosslinking agent include melamine, oxazoline, aldehyde, N-methylol compound, dioxane derivative, active vinyl compound, active halogen compound, isoxazole, dialdehyde starch, isocyanate compound, and silane coupling agent. .
  • These crosslinking agents may be used alone or in combination of two or more.
  • the addition amount of the crosslinking agent is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 15% by mass or less with respect to the total amount of the hydrophilic resin.
  • other resin components such as amino group-containing resins, surfactants, slipping agents, dyes, UV absorbers, matting agents (silica) , Colloidal silica, etc., preferably having an average particle size of 0.005 to 3 ⁇ m), preservatives, thickeners, film-forming aids, antistatic agents, antioxidants, and the like.
  • the total light transmittance of the base film provided with the easy adhesion layer is preferably 90% or more, and more preferably 91% or more.
  • the haze of the base film provided with the easy adhesion layer is preferably 2% or less, more preferably 1.5% or less.
  • the total light transmittance is less than 90%, when used in a display device, the luminance is reduced or the original color of the article looks dark.
  • the haze greatly exceeds 2%, the article appears whitish and cloudy when used in a display device, which may undesirably impair the original appearance of the article such as an image of a flat panel display or home appliances.
  • the hard coat film of the present invention can be provided with a functional layer such as an antireflection layer or a transparent conductive thin layer.
  • the hard coat film according to the present invention can be used as an antireflection film having an external light antireflection function by coating an antireflection layer on the hard coat layer.
  • the antireflection layer is preferably laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference.
  • the antireflection layer is composed of a low refractive index layer having a lower refractive index than the protective film as the support, or a combination of a high refractive index layer and a low refractive index layer having a higher refractive index than the protective film as the support.
  • it is.
  • it is an antireflection layer composed of three or more refractive index layers, and three layers having different refractive indexes from the support side are divided into medium refractive index layers (high refractive index layers having a higher refractive index than the support).
  • an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.
  • the layer structure of the antireflection film the following structure is conceivable, but is not limited thereto.
  • the low refractive index layer preferably contains silica-based fine particles, and the refractive index is preferably in the range of 1.30 to 1.45 when measured at 23 ° C. and wavelength of 550 nm.
  • the film thickness of the low refractive index layer is preferably 5 nm to 0.5 ⁇ m, more preferably 10 nm to 0.3 ⁇ m, and most preferably 30 nm to 0.2 ⁇ m.
  • the composition for forming a low refractive index layer preferably contains at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles.
  • the particles having the outer shell layer and having a porous or hollow interior are preferably hollow silica-based fine particles.
  • composition for forming a low refractive index layer may contain an organosilicon compound represented by the following general formula (OSi-1), a hydrolyzate thereof, or a polycondensate thereof.
  • OSi-1 organosilicon compound represented by the following general formula (OSi-1)
  • hydrolyzate thereof a hydrolyzate thereof
  • polycondensate thereof a polycondensate thereof.
  • R represents an alkyl group having 1 to 4 carbon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.
  • a solvent and if necessary, a silane coupling agent, a curing agent, a surfactant and the like may be added. Further, it may contain a thermosetting and / or photocurable compound mainly containing a fluorine-containing compound containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. Specifically, a fluorine-containing polymer or a fluorine-containing sol-gel compound is used.
  • fluorine-containing polymer examples include hydrolysates and dehydration condensates of perfluoroalkyl group-containing silane compounds [eg (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], and fluorine-containing monomers. Examples thereof include fluorine-containing copolymers having units and cross-linking reactive units as constituent units.
  • the refractive index of the high refractive index layer is preferably adjusted to a range of 1.4 to 2.2 by measuring at 23 ° C. and a wavelength of 550 nm.
  • the thickness of the high refractive index layer is preferably 5 nm to 1 ⁇ m, more preferably 10 nm to 0.2 ⁇ m, and most preferably 30 nm to 0.1 ⁇ m.
  • the means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like.
  • Metal oxide The metal oxide fine particles used preferably have a refractive index of 1.80 to 2.60, more preferably 1.85 to 2.50.
  • the kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S
  • a metal oxide having at least one element selected from the group consisting of Al, In, Sn, Sb, Nb, a halogen element, Ta and the like is doped with a minute amount of atoms. May be. A mixture of these may also be used.
  • at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium tin oxide (ITO), antimony doped tin oxide (ATO), and zinc antimonate is used. It is particularly preferable to use it as the main component. In particular, it is preferable to contain zinc antimonate particles.
  • the average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, and is particularly preferably 10 to 150 nm.
  • the average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased.
  • the shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.
  • the metal oxide fine particles may be surface-treated with an organic compound.
  • an organic compound By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . Therefore, the amount of surface modification with a preferable organic compound is 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 3% by mass with respect to the metal oxide particles.
  • the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred. Two or more kinds of surface treatments may be combined.
  • the high refractive index layer may contain a ⁇ -conjugated conductive polymer.
  • the ⁇ -conjugated conductive polymer can be used as long as it is an organic polymer having a main chain composed of a ⁇ -conjugated system. Examples thereof include polythiophenes, polypyrroles, polyanilines, polyphenylenes, polyacetylenes, polyphenylene vinylenes, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of ease of polymerization and stability, polythiophenes, polyanilines, and polyacetylenes are preferable.
  • the ⁇ -conjugated conductive polymer can provide sufficient conductivity and solubility in a binder resin even if it is not substituted, but in order to further improve conductivity and solubility, an alkyl group, a carboxy group, a sulfo group, an alkoxy group.
  • a functional group such as a group, a hydroxy group, or a cyano group may be introduced.
  • the ionic compound include imidazolium-based, pyridium-based, alicyclic amine-based, aliphatic amine-based, aliphatic phosphonium-based cations and inorganic ion-based compounds such as BF 4 ⁇ and PF 6 ⁇ , CF 3 SO 2 ⁇ , and the like. , (CF 3 SO 2 ) 2 N ⁇ , CF 3 CO 2 —, etc.
  • the ratio of the polymer to the binder is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the polymer, and particularly preferably 100 to 200 parts by mass of the binder with respect to 100 parts by mass of the polymer.
  • a transparent conductive thin layer may be formed on the hard coat layer of the hard coat film.
  • a generally widely known transparent conductive material can be used.
  • a transparent conductive material such as indium oxide, tin oxide, indium tin oxide, gold, silver, or palladium can be used. These can be formed as a thin film on the hard coat film by vacuum deposition, sputtering, ion plating, solution coating, or the like.
  • a transparent conductive material that is excellent in transparency and electrical conductivity and is mainly composed of any one of indium oxide, tin oxide, and indium tin oxide, which can be obtained at a relatively low cost, can be suitably used.
  • the thickness of the transparent conductive thin film varies depending on the material to be applied, it cannot be said unconditionally.
  • the surface resistivity is 1000 ⁇ or less, preferably 500 ⁇ or less. A range of 20 nm or more and 80 nm or less, preferably 70 nm or less is preferable. In such a thin film, visible light interference fringes due to uneven thickness of the transparent conductive thin layer are unlikely to occur.
  • the hard coat film of this invention is preferable at the point by which the performance excellent in visibility (clearness) is exhibited by using it for an image display apparatus.
  • an image display device a reflection type, a transmission type, a semi-transmission type liquid crystal display device, a liquid crystal display device of various driving methods such as a TN type, an STN type, an OCB type, a VA type, an IPS type and an ECB type, an organic EL display Examples thereof include a device and a plasma display.
  • the hard coat film of the present invention when used for a touch panel member of a liquid crystal display device including a touch panel, it is preferable in terms of excellent visibility and durability against pen input (such as scratches caused by sliding). .
  • FIG. 1 An example when used for a touch panel is shown in FIG.
  • a transparent conductive thin film 12 is formed on the transparent hard coat film 11 of the present invention, and the glass substrate 13 on which the transparent conductive thin film 15 is formed is spaced apart from the transparent conductive thin film 15 with a certain distance therebetween. By making them face each other, the resistive touch panel 10 can be configured. Electrodes (not shown) are arranged at the ends of the hard coat film 11 and the glass substrate 13. When the user presses down the hard coat film 11 with the transparent conductive thin film 12 with a finger or a pen, the transparent conductive thin film 12 comes into contact with the transparent conductive thin film 15 on the glass substrate 13. The pressed position is detected by electrically detecting this contact through the electrode at the end.
  • a liquid crystal display device with a touch panel can be configured by mounting the touch panel 10 of FIG. 2 on the color liquid crystal display panel 20.
  • Example 1 Preparation of base film 1 with an easy adhesion layer> Polyethylene terephthalate containing no filler was melt-extruded at 280 ° C., and cast on a 20 ° C. cast drum applied with an electrostatic force to produce an unstretched sheet. This sheet was preheated at 100 ° C., and stretched at a temperature of 3 times in the longitudinal direction by roll stretching. Thereafter, the easy-adhesion layer water-based paint 1 adjusted to a concentration of 4.5% was applied to both sides of the sheet. After coating, the film was stretched 3.5 times in the width direction at 120 ° C. and heat-treated at 220 ° C.
  • Polyester resin (X) having a Tg of 120 ° C. and a sodium / sulfonate / isophthalic acid molar ratio of 7/50 19 parts by mass
  • Polyester resin (Y) having a Tg of 80 ° C. and a trimellitic acid molar ratio of 12/50 45 parts by mass
  • ⁇ Preparation of base film 3 with an easy adhesion layer> In the production of the base film 1, the coating amount of the easy-adhesion layer water-based paint 3 was adjusted so that the film thickness of the easy-adhesion layer was 150 nm, and the easy-adhesion layer water-based paint 1 was changed to the easy-adhesion layer water-based paint 3. Except for the above, a base film 3 with an easy adhesion layer was obtained in the same manner.
  • ⁇ Preparation of base film 4 with an easy adhesion layer> In the production of the base film 1, the coating amount of the easy-adhesion layer water-based paint 4 was adjusted so that the film thickness of the easy-adhesion layer was 150 nm, and the easy-adhesion layer water-based paint 1 was changed to the easy-adhesion layer water-based paint 4. Except for the above, a base film 4 with an easily adhesive layer was obtained in the same manner.
  • Aqueous urethane having a solid content of 40% by mass (“Aron Neotan UE-1300” manufactured by Toagosei Co., Ltd.) 25 parts by mass Hydroxyethyl methacrylate 5 parts by mass Potassium persulfate 0.2 parts by mass Colloidal silica having a particle size of 150 nm 2 parts by mass Part
  • ⁇ Preparation of base film 5 with an easy adhesion layer> In the production of the base film 1, the coating amount of the easy-adhesion layer water-based paint 5 was adjusted so that the film thickness of the easy-adhesion layer was 150 nm, and the easy-adhesion layer water-based paint 1 was changed to the easy-adhesion layer water-based paint 5. Except for the above, a base film 5 with an easy adhesion layer was obtained in the same manner.
  • a reaction vessel was charged with 0.12 parts by mass of nium tetrakispentafluorophenylborate (manufactured by Strem) and 0.33 parts by mass of allyltributyltin (manufactured by Aldrich) dissolved in 10 parts by mass of toluene.
  • nium tetrakispentafluorophenylborate manufactured by Strem
  • allyltributyltin manufactured by Aldrich
  • the mass average molecular weight (Mw) was measured, the number average molecular weight (Mn) was 100200, the mass average molecular weight (Mw) was 256300, and the molecular weight distribution (Mw / Mn) was 2.56.
  • Norbornene dope solution Norbornene polymer 1 100 parts by mass Silicon oxide fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) 0.1 parts by mass Methylene chloride 400 parts by mass Ethanol 40 parts by mass Butanol 5 parts by mass
  • the above materials were mixed to prepare a dope solution, and the obtained dope solution was cast from a casting die onto a support having a temperature of 35 ° C. made of a stainless steel endless belt to form a web.
  • the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 100% by mass.
  • the application amount of the water-based paint was adjusted to the peeled web so that the film thickness of the easy-adhesion layer was 150 nm and applied to both sides of the web. After coating, the film was transported while being dried at 120 ° C., and then held at both ends of the web with a tenter, and then stretched at 150 ° C.
  • the film was further dried at 160 ° C.
  • the substrate with an easy-adhesion layer is a cycloolefin film having a norbornene ring having a width of 1.5 m, a film thickness of 80 ⁇ m, and a length of 6000 m, which is subjected to a knurling process of 10 mm width and 5 ⁇ m average height at both ends Film 6 was obtained.
  • ⁇ Preparation of base film 7 with an easy adhesion layer> In the production of the base film 6, a base film 7 with an easy-adhesion layer was produced in the same manner except that the norbornene dope liquid was changed to the following acrylic dope liquid.
  • the following materials are sequentially put into a sealed container, the temperature in the container is raised from 20 ° C. to 80 ° C., and the mixture is stirred for 3 hours while maintaining the temperature at 80 ° C. to obtain methyl methacrylate / methyl acrylate.
  • the copolymer was completely dissolved.
  • the silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester.
  • the dope was filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope solution 2.
  • Methyl methacrylate / methyl acrylate copolymer 9: 1 molar ratio 100 parts by mass [2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole] 1 part by mass Methylene chloride 400 parts by mass Methanol 100 parts by mass Silicon oxide fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) 0.1 parts by mass
  • both ends are subjected to a knurling process with a width of 10 mm and an average height of 5 ⁇ m, wound up, and a 125 ⁇ m thick propylene film in which an easy adhesion layer having a width of 1.5 m, a length of 6000 m, and 150 nm is formed on both sides.
  • a base film 8 with an adhesive layer was obtained.
  • the illuminance of the irradiated part is 100 mW / cm 2 using an ultraviolet lamp and the irradiation amount is 0
  • the coating layer was cured at 3 J / cm 2 , a hard coat layer 1 having a dry film thickness of 8 ⁇ m was formed and wound up, and a roll-shaped hard coat film 1 was produced.
  • Hard coat layer composition 1 The following materials were stirred and mixed to obtain hard coat layer coating composition 1.
  • a hard coat film 2 was produced in the same manner except that the hard coat layer composition 2 was changed to the following on the produced base film 1.
  • Hard coat layer composition 2 The following materials were stirred and mixed to obtain hard coat layer coating composition 2.
  • a hard coat film 3 was produced in the same manner except that the hard coat layer coating composition 3 was changed to the following on the produced base film 1.
  • Hard coat layer composition 3 (Hard coat layer composition 3) The following materials were stirred and mixed to obtain hard coat layer coating composition 3.
  • a hard coat film 4 was produced in the same manner except that the hard coat layer coating composition 4 was changed to the following on the produced base film 1.
  • Hard coat layer composition 4 (Hard coat layer composition 4) The following materials were stirred and mixed to obtain hard coat layer coating composition 4.
  • Hard coat films 5 to 14 were prepared in the same manner as in the preparation of hard coat film 1, except that the hard coat layer coating composition and the base film with an easy-adhesion layer were changed as shown in Table 1.
  • Each hard coat film 1 to 14 after the durability test is conditioned for 14 hours in an atmosphere of 23 ° C. and 55% RH, and is cylindrical using a type 1 test apparatus in accordance with JIS K5600-5-1.
  • the flexibility was evaluated by the mandrel method. It shows that it is excellent in the flexibility, so that the numerical value of the diameter of a mandrel is low.
  • tris (2-acryloyloxyethyl) isocyanurate which is an active energy ray-curable isocyanurate derivative of the hard coat layer resin in Table 1, is described as TAIC, and isocyanuric acid ethoxy-modified diacrylate is described as DAIC.
  • TAIC active energy ray-curable isocyanurate derivative of the hard coat layer resin in Table 1
  • DAIC isocyanuric acid ethoxy-modified diacrylate
  • an easily bonding layer and a base film abbreviation are as follows.
  • PET Polyethylene terephthalate film
  • COF Cycloolefin film
  • ACF Acrylic film
  • PP Propylene film
  • polyester resin, acrylic resin and urethane resin are selected on both sides of at least one base film selected from acrylic resin film, polypropylene resin film, cycloolefin resin film, and polyester resin film.
  • the hard-coating film of the present invention consisting of an easy-adhesion layer containing at least one resin and a hard-coating layer containing an active energy ray-curable isocyanurate derivative is excellent in blocking resistance and flexibility. I know that.
  • the base film is made of a polyester resin film
  • the easy-adhesion layer has a glass transition point Tg of 105 ° C. or more and less than 135 ° C.
  • a hard coat film composed of a resin (X) and a polyester resin (Y) having a glass transition point Tg of 65 ° C. or higher and lower than 95 ° C. and containing trimellitic acid as an acid component is particularly excellent in blocking resistance. Since it has flexibility, it turns out that it is a particularly preferable structure.
  • Example 2 In the production of the hard coat film 1 of Example 1, the active energy ray-curable isocyanurate derivative of the hard coat layer coating composition 1 is not tris (2-acryloyloxyethyl) isocyanurate (A) or an isocyanurate derivative. Except that the mass ratio of the active energy ray-curable resin (pentaerythritol tri / tetraacrylate) (B) was changed to hard coat layer coating compositions 5 to 8 changed as shown in Table 2, Examples In the same manner as in Example 1, hard coat films 15 to 18 were produced.
  • Example 2 For the obtained hard coat films 15 to 18 and the hard coat film 1 produced in Example 1, the storage period of blocking resistance was changed to 15 days, and the storage period of the flexible durability test was set to 750. Evaluation was performed in the same manner as in Example 1 except that the time was changed. The obtained results are shown in Table 2.
  • Example 3 ⁇ Preparation of hard coat film 19>
  • the following hard coat layer coating composition 9 is filtered through a polypropylene filter having a pore diameter of 0.4 ⁇ m to prepare a hard coat layer coating solution, which is applied using an extrusion coater, After drying at 80 ° C., a hard coat layer 1 having a dry film thickness of 1 ⁇ m was formed by curing the coating layer using an ultraviolet lamp at an irradiation part with an illuminance of 80 mW / cm 2 and an irradiation amount of 50 mJ / cm 2 .
  • the hard coat layer coating composition 1 is applied onto the hard coat layer 1 by an extrusion coater, dried at 80 ° C., and purged with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. While using an ultraviolet lamp, the illuminance of the irradiated part is 100 mW / cm 2 , the irradiation amount is 0.3 J / cm 2 , the coating layer is cured, and the hard coat layer 2 having a dry film thickness of 7 ⁇ m is formed and wound up. A hard coat film 19 was produced.
  • Hardcoat layer coating composition 9 The following materials were stirred and mixed to obtain hard coat layer coating composition 9.
  • a hard coat film 20 was produced in the same manner except that the hard coat layer coating composition 9 was changed to the hard coat layer coating composition 10 in the production of the hard coat film 19.
  • Hardcoat layer coating composition 10 (Hardcoat layer coating composition 10) The following materials were stirred and mixed to obtain a hard coat layer coating composition 10.
  • Adhesion evaluation weather resistance test
  • the hard coat films 19 and 20 and the hard coat film 1 produced in Example 1 were cut out for samples each having a size of 10 cm ⁇ 10 cm, and assumed to be used outdoors. Next, after 500 cycles were placed at 85 ° C. for 30 minutes alternately), the sample was irradiated with light for 168 hours with a light resistance tester (eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.).
  • a light resistance tester eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.
  • the method After conditioning the hard coat films 19 and 20 after the weather resistance test and the hard coat film 1 prepared in Example 1 in an atmosphere of 23 ° C. and 55% RH for 12 hours, the method conforms to JISK5400 at intervals of 1 mm. Make 11 cuts vertically and horizontally, make 1 mm square, 100 grids, apply cellophane tape, peel off at 90 degrees, count the number of grids remaining without peeling, Evaluated by criteria.
  • the peeled area ratio was less than 5% ⁇ : The peeled area ratio was less than 10% ⁇ : The peeled area ratio was 10% or more
  • the hard coat film of the present invention exhibits the objective effect of the present invention even in a more severe durability test by including an ultraviolet absorber in the hard coat layer, and is further excellent. It is preferable because it has excellent adhesion.
  • Example 4 ⁇ Preparation of conductive hard coat film 1>
  • a hard coat film was produced in the same manner except that the hard coat layer composition 1 was applied on both sides.
  • a transparent conductive thin film of indium tin oxide (ITO) having a surface resistivity of about 400 ⁇ is provided on one side of the produced hard coat film using a sputtering method, and the conductive hard coat film 1 shown in FIG. 3 is produced. did.
  • ITO indium tin oxide
  • ⁇ Preparation of conductive hard coat film 2> In producing the hard coat film 2, a hard coat film was produced in the same manner except that the hard coat layer composition 2 was applied on both sides. A transparent conductive thin film of indium tin oxide (ITO) having a surface resistivity of about 400 ⁇ was provided on one side of the prepared hard coat film using a sputtering method, and a conductive hard coat film 2 was prepared.
  • ITO indium tin oxide
  • ⁇ Preparation of resistive touch panel liquid crystal display device 1 The conductive hard coat film of a commercially available resistive film type touch panel liquid crystal display device (model name: LCD-USB10XB-T, manufactured by IO DATA) is peeled off, and the produced conductive hard coat film 1 is as shown in FIG.
  • the resistive film type touch panel liquid crystal display device 1 was produced by bonding so that the hard coat layer was on the viewing side.
  • resistive touch panel liquid crystal display device 2 was prepared in the same manner except that the conductive hard coat film 1 was changed to the conductive hard coat film 2 in the production of the resistive touch panel liquid crystal display device 1, and the following items were evaluated. went.
  • ⁇ The fluorescent lamp looks straight.
  • X The fluorescent lamp looks bent.
  • Pen sliding resistance A polyacetal pen with a tip of 0.08 mm ⁇ is used on the surface of the hard coat layer of each conductive hard coat film used in the liquid crystal display device of the resistance film type touch panel. The hard coat layer was scratched and peeled off visually at the sliding portion after reciprocating 150,000 times on a straight line of 40 mm at a moving speed of 100 mm / sec.
  • the liquid crystal display device of the resistive film type touch panel using the conductive hard coat film 1 of the present invention was good in both visibility and pen sliding resistance.
  • Hard coat film of this invention 12 Transparent conductive thin film 13 Glass substrate 14 Spacer 20 Color liquid crystal display panel 30 Base film with an easily bonding layer 31 Hard coat layer 32 ITO layer (transparent conductive thin film) 40 conductive hard coat film

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Abstract

L'invention concerne un film de revêtement dur présentant des propriétés de souplesse et de blocage améliorées après soumission à un test de durabilité ; et un dispositif d'affichage d'images. Le film de revêtement dur comprend une couche hautement adhésive sur les deux surfaces d'un film de substrat qui est au moins un film sélectionné dans le groupe constitué par un film de résine acrylique, un film de résine polypropylène, un film de résine cyclo-oléfinique et un film de résine polyester ; et une couche de revêtement dur déposée sur au moins une surface de la couche hautement adhésive. Le film de revêtement dur est caractérisé en ce que la couche hautement adhésive contient au moins une résine sélectionnée dans le groupe constitué par une résine polyester, une résine acrylique et une résine uréthane, et en ce qu'il contient un dérivé d'isocyanurate durci par un rayonnement d'énergie active.
PCT/JP2011/006200 2010-11-15 2011-11-07 Film de revêtement dur et dispositif d'affichage d'images WO2012066743A1 (fr)

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JP7154681B2 (ja) 2018-01-26 2022-10-18 日本製紙株式会社 ハードコートフィルムの製造方法
JP2019128544A (ja) * 2018-01-26 2019-08-01 日本製紙株式会社 ハードコートフィルム及びその製造方法
JP2019128542A (ja) * 2018-01-26 2019-08-01 日本製紙株式会社 ハードコートフィルム及びその製造方法
JP2019128543A (ja) * 2018-01-26 2019-08-01 日本製紙株式会社 ハードコートフィルム及びその製造方法
WO2019146622A1 (fr) * 2018-01-26 2019-08-01 日本製紙株式会社 Film de revêtement dur et son procédé de production
JP7154680B2 (ja) 2018-01-26 2022-10-18 日本製紙株式会社 ハードコートフィルムの製造方法
JP7166057B2 (ja) 2018-01-26 2022-11-07 日本製紙株式会社 ハードコートフィルムの製造方法
JP7166056B2 (ja) 2018-01-26 2022-11-07 日本製紙株式会社 ハードコートフィルムの製造方法
US11718721B2 (en) 2018-01-26 2023-08-08 Nippon Paper Industries Co., Ltd. Hard coat film and method for producing same
JP2019128545A (ja) * 2018-01-26 2019-08-01 日本製紙株式会社 ハードコートフィルム及びその製造方法
JP2023528501A (ja) * 2020-06-03 2023-07-04 東友ファインケム株式会社 易接着層形成用組成物及びこれを用いたハードコーティングフィルム
JP7497465B2 (ja) 2020-06-03 2024-06-10 東友ファインケム株式会社 易接着層形成用組成物及びこれを用いたハードコーティングフィルム

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