WO2019107950A2 - Film pour appareil d'affichage optique, élément optique comportant ce film, et appareil d'affichage optique comprenant ce film - Google Patents

Film pour appareil d'affichage optique, élément optique comportant ce film, et appareil d'affichage optique comprenant ce film Download PDF

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WO2019107950A2
WO2019107950A2 PCT/KR2018/014907 KR2018014907W WO2019107950A2 WO 2019107950 A2 WO2019107950 A2 WO 2019107950A2 KR 2018014907 W KR2018014907 W KR 2018014907W WO 2019107950 A2 WO2019107950 A2 WO 2019107950A2
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meth
film
acrylate
coating layer
weight
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PCT/KR2018/014907
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Korean (ko)
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WO2019107950A3 (fr
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신동명
김도영
김성한
김태지
김영훈
황오현
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삼성에스디아이 주식회사
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Publication of WO2019107950A3 publication Critical patent/WO2019107950A3/fr

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/02Physical, chemical or physicochemical properties
    • B32B7/023Optical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/02Physical, chemical or physicochemical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/02Physical, chemical or physicochemical properties
    • B32B7/022Mechanical properties
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14Protective coatings, e.g. hard coatings
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/10Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/26Polymeric coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51Elastic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/20Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention relates to a film for an optical display device, an optical member including the same, and an optical display device including the same.
  • the film of the optical display device may include a protective film disposed on the outside of the optical display device and formed on the window film and / or the window film to enable the display image to be viewed and to protect the window film.
  • the protection films for the conventional window films were given preference to the protection from external environment and the rework characteristics, but it was difficult to apply the folding characteristics to the foldable optical display devices.
  • Protection against external environment is generally achieved by improving the hardening density, improving the hardness, and solidifying the resin / organic / inorganic particles with a rigid structure.
  • the folding property it is possible to realize a smooth coating by crosslinking with a resin having a reduced hardening density and good flexibility.
  • the film for an optical display device may be composed of a base layer and a hard coat layer formed on one surface of the base layer.
  • a thermoplastic polyurethane (TPU) film or a substrate layer in which a thin polyethylene terephthalate (PET) film or a polyimide (PI) film is laminated in a multilayer structure or a double layer structure may be used for improving flexibility and impact resistance.
  • PET polyethylene terephthalate
  • PI polyimide
  • the TPU film is not easy to apply because it is thick and has poor appearance characteristics.
  • the thin PET film or PI film has excellent appearance properties, the impact resistance, particularly the impact resistance evaluation result by the pen drop described below, is not good.
  • An object of the present invention is to provide a film for an optical display device having a multilayer structure of a first coating layer, a base layer and a second coating layer and having a low haze and an excellent appearance.
  • Another object of the present invention is to provide a film for an optical display device having a multilayer structure of a first coating layer, a base layer and a second coating layer, and having excellent foldability in both directions of the first coating layer and the second coating layer.
  • Another object of the present invention is to provide a film for an optical display device having a low yellow index, excellent light fastness reliability, low sheet resistance, and excellent adhesion between a substrate layer and a coating layer.
  • a film for an optical display device of the present invention comprises a first coating layer, a base layer, and a second coating layer sequentially formed, wherein the first coating layer comprises urethane (meth) acrylate, N-vinylpyrrolidone and an initiator And the indentation modulus measured on the surface of the first coating layer with respect to the film for an optical display device may be about 10 MPa to about 60 MPa.
  • the film for an optical display device of the present invention is characterized in that a first coating layer, a base layer and a second coating layer are sequentially formed, and the first coating layer is formed of a composition for a first coating layer containing urethane (meth) Wherein the indentation modulus measured on the surface of the first coating layer with respect to the film for an optical display device is about 10 MPa to about 60 MPa and the indentation modulus measured on the surface of the second coating layer with respect to the optical display device film is about 5 GPa to about 12 GPa .
  • the second coating layer comprises urethane (meth) acrylate; (Meth) acrylate monomers; Zirconia particles, and silica particles; Silicone additive; And a second coating layer containing an initiator.
  • the second coating layer comprises urethane (meth) acrylate; (Meth) acrylate monomers; Zirconia particles; Silicone additive; And a second coating layer containing an initiator.
  • the first coating layer may have a thickness of from about 50 ⁇ to about 150 ⁇ .
  • the second coating layer may have a thickness of about 10 mu m or less.
  • the base layer is a urethane-based resin film and may have a thickness of about 50 ⁇ or less.
  • the base layer may be an isotropic film or a retardation film.
  • the urethane (meth) acrylate may have an elongation of from about 2% to about 20%.
  • the second coating layer comprises about 40 parts by weight to about 85 parts by weight of the urethane (meth) acrylate, 100 parts by weight of the urethane (meth) acrylate monomer and zirconia particles, (Meth) acrylate monomer, about 5 to about 50 parts by weight of said (meth) acrylate monomer, about 0.01 to about 10 parts by weight of said zirconia particles, said urethane (meth) About 0.01 part by weight to about 5 parts by weight of the silicone additive, about 0.01 to about 10 parts by weight of the initiator, based on 100 parts by weight of the total amount of the silicone additive.
  • the second coating layer may further comprise a dye and an antistatic agent.
  • the dye of the second coating layer may comprise from about 0.05 wt% to about 0.1 wt%, and the antistatic agent may comprise at least about 11 wt%.
  • Y2 represents the yellow index measured on the film for an optical display device
  • Y1 is the yellow index measured by the same method after the film for an optical display device in which Y2 was measured was allowed to stand for 72 hours with a UV-B lamp).
  • the second coating layer may be formed of a composition for a second coating layer comprising urethane (meth) acrylate, a (meth) acrylate monomer, silica particles, a silicone additive and an initiator.
  • the (meth) acrylate monomer may comprise a (meth) acrylate monomer having an alkylene oxide group.
  • the urethane (meth) acrylate may comprise from 11 to 20 functional urethane (meth) acrylates.
  • the second coating layer comprises about 40 to about 85 parts by weight of the urethane (meth) acrylate, about 85 to about 85 parts by weight of the urethane (meth) acrylate in the total of 100 parts by weight of the urethane (meth) acrylate monomer, (Meth) acrylate monomer, about 100 parts by weight of the (meth) acrylate monomer, about 100 parts by weight of the About 0.01 parts by weight to about 5 parts by weight of the silicone additive to about 0.01 parts by weight to about 10 parts by weight of the initiator.
  • the base layer is a polyimide film, and a buffer layer may be further formed between the base layer and the second coating layer.
  • An adhesive layer may be further formed on one surface of the first coating layer at 1-2.
  • the optical member of the present invention may comprise a film for an optical display device of the present invention.
  • the optical display device of the present invention may include a film for an optical display device of the present invention.
  • the present invention provides a film for an optical display device having a multilayer structure of a first coating layer, a base layer and a second coating layer and having a low haze and an excellent appearance.
  • the present invention provides a film for an optical display device having a multilayer structure of a first coating layer, a base layer and a second coating layer and having excellent foldability with respect to both the direction of the first coating layer and the direction of the second coating layer.
  • the present invention provides a multilayer structure of a first coating layer, a base layer and a second coating layer, and provides a film for an optical display device excellent in impact resistance, scratch resistance, abrasion resistance, and adhesion.
  • the present invention provides a film for an optical display device having a low yellow index, excellent light fastness and flexibility, and excellent adhesion between a substrate layer and a coating layer.
  • FIG. 1 is a cross-sectional view of a film for an optical display device according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of an optical display device according to an embodiment of the present invention.
  • FIG. 3 is a cross-sectional view of an optical display device according to another embodiment of the present invention.
  • (meth) acrylic means acrylic and / or methacrylic.
  • the "elongation" of urethane (meth) acrylate means a specimen having a thickness of 200 ⁇ m and a width of 10 mm manufactured using an Instron apparatus and measuring the elongation at a marking distance of 30 mm (according to JIS K7311).
  • the "average particle diameter" of the organic nanoparticles in the present specification is the particle diameter of the organic nanoparticles expressed by the Z-average value measured by a Zetasizer nano-ZS instrument of Malvern, .
  • in-plane retardation (Re) is an in-plane retardation value at a wavelength of 550 nm and is a value represented by the following formula A:
  • nx and ny are the refractive index in the direction of the slow axis and the refractive index in the fast axis direction of the base layer at a wavelength of 550 nm, respectively, and d is the thickness (unit: nm) of the base layer).
  • film for an optical display device refers to a window film disposed on the outer side of an optical display device to allow an image to be viewed, a protective film formed on the window film to protect the window film, And may refer to a substrate film when it includes a film and a coating layer formed on the substrate film.
  • X to Y means not less than X and not more than Y (X? And? Y) when describing the numerical range.
  • a first coating layer 110, a base layer 130, and a second coating layer 120 may be sequentially formed on the optical display device film 100.
  • the first coating layer 110 and the second coating layer 120 are sequentially formed on the substrate layer 130 or when the second coating layer 120 and the first coating layer 110 are sequentially formed on the substrate layer 130, There may be a problem that the scratch property and the impact resistance property are deteriorated.
  • the base layer 130 supports the first coating layer 110 and the second coating layer 110, respectively, to increase the mechanical strength of the optical display device film 100.
  • the substrate layer 130 may be an optically transparent resin film.
  • the substrate layer 130 may have a light transmittance of about 85% to about 100%, e.g., 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 (PET), polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, Polyvinyl acetate, polyvinyl chloride (PVC), polynorbornene, polyvinyl acetate, polyvinyl acetate, polyvinyl acetate, polyvinyl chloride, polyvinyl chloride, polybutylene terephthalate and the like, cellulose ester including acrylic, cyclic olefin polymer (COP), triacetyl cellulose
  • the substrate layer 130 has a thickness About 100 ⁇ or less, For example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, For example, from about 20 ⁇ to about 50 ⁇ . Within this range, folding resistance, impact resistance and scratch resistance can be good.
  • the substrate layer 130 may have a refractive index of from about 1.40 to about 1.65, such as 1.40, 1.45, 1.50, 1.55, 1.60, 1.65, specifically about 1.45 to about 1.60.
  • the refractive index of the first coating layer and the second coating layer is appropriate, so that the haze of the optical display device film is not increased, and the screen visibility can be improved when the window film is laminated on top of the window film.
  • the substrate layer is an isotropic film and can be a film having a Re of about 5 nm or less, such as about 0 nm to about 1 nm.
  • the isotropic film can exhibit its own function without interfering with the retardation function of various retardation films positioned under the window film or the window film.
  • the substrate layer is a retardation film, and the Re may be greater than about 5 nm, specifically about 50 nm to about 30,000 nm.
  • the retardation film supports the first coating layer and the second coating layer, and has an optical compensation function, thereby providing additional functions to the optical display device.
  • the base layer can have a Re of about 100 nm to about 160 nm, for example, a quarter-wave retardation film. In this case, the polarizing sunglass effect can be exhibited.
  • the base layer can have a Re of about 200 nm to about 300 nm, for example, a? / 2 phase difference film. In this case, it is laminated with the? / 4 retardation film to improve the display form and lower the reflectance by the external light, thereby improving the visibility of the screen.
  • the substrate layer can be an ultra high-refraction film having a Re of at least about 8,000 nm, at least about 15,000 nm, and at most about 30,000 nm. In this case, it is possible to suppress the occurrence of iridescence and stain.
  • Substrate layer 130 may be prepared by conventional methods.
  • the substrate layer may be prepared by film-forming a composition comprising the optically transparent resin by melt extrusion or solvent casting methods.
  • the produced film can be uniaxially or biaxially stretched by a conventional method to have the above-mentioned retardation Re.
  • the substrate layer may not be surface-treated, but may be surface-treated to facilitate lamination of the first coating layer or the second coating layer, to suppress their peeling, and to provide additional functions.
  • the substrate layer may not be surface-treated, but may be surface-treated to facilitate lamination of the first coating layer or the second coating layer, to suppress their peeling, and to provide additional functions.
  • plasma treatment, corona treatment, or the like may be surface-treated to facilitate lamination of the first coating layer or the second coating layer, to suppress their peeling, and to provide additional functions.
  • the first coating layer is the first coating layer
  • the first coating layer 110 may be formed directly on one side of the substrate layer 130 (the lower surface of the substrate layer) to support the substrate layer 130 and the second coating layer 120. This "directly formed” means that no other adhesive layer, adhesive layer, or adhesive layer is interposed between the substrate layer and the first coating layer.
  • the first coating layer 110 can be adhered to the display device in an optical display device via an adhesive layer or the like, and the base layer and the second coating layer are respectively laminated on the light output surface of the first coating layer. Therefore, in the optical display device, the light emitted from the light source or the OLED panel can be transmitted in the order of the first coating layer, the base layer and the second coating layer.
  • the impact resistance of the optical display device film may be sharply lowered.
  • the urethane-based resin film is used as the substrate layer by forming the first coating layer 110 on the base layer which is a urethane-based resin film, the haze can be lowered and the optical characteristics can be improved while securing the contrast folding property and the impact resistance.
  • the first coating layer 110 may have a thickness ranging from about 50 ⁇ m to about 150 ⁇ m such as 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 125, 130, 135, 140, 145, 150 ⁇ ⁇ , preferably about 100 ⁇ ⁇ to about 150 ⁇ ⁇ .
  • a thickness ranging from about 50 ⁇ m to about 150 ⁇ m such as 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 125, 130, 135, 140, 145, 150 ⁇ ⁇ , preferably about 100 ⁇ ⁇ to about 150 ⁇ ⁇ .
  • the first coating layer 110 may have a refractive index of about 1.45 to about 1.7, such as 1.45, 1.5, 1.55, 1.60, 1.65, 1.7, specifically about 1.5 to about 1.65. In the above range, the refractive index of the second coating layer and the substrate layer is appropriate, so that the haze of the film for an optical display device is not increased and the appearance is excellent, and the screen visibility can be improved when stacked on the window film.
  • the first coating layer 110 may be formed as a non-tacky coating layer by applying a composition for the first coating layer to one surface of the base layer 130 and then curing.
  • the application and curing methods are by conventional methods known to those skilled in the art.
  • the composition for the first coating layer may comprise urethane (meth) acrylate, N-vinylpyrrolidone and an initiator.
  • the composition for the first coating layer does not contain conventionally known solid or liquid shockproof reinforcing agents and the like.
  • the composition for the first coating layer may exhibit sufficient impact resistance even with urethane (meth) acrylate, N-vinylpyrrolidone and initiator alone.
  • the urethane (meth) acrylate can form a matrix of the first coating layer and can cause the first coating layer to exhibit the impact function.
  • Urethane (meth) acrylate has an elongation of about 2% to about 20%, such as 2,3,4,5,6,7, 8,9, 10,11, 12,13,14,15,16, 17, 18, 19, 20%.
  • the substrate layer is a non-urethane-based resin film in the elongation percentage range
  • the film for an optical display device can have improved impact resistance, abrasion resistance, and foldability in both the compression direction and the tensile direction.
  • the indentation modulus measured in the first coating layer of the film for an optical display device is in the range of about 10 MPa to about 60 MPa, for example, 10, 15, 20, 25, 30, 35, 40, 45, , And 60 MPa.
  • the indentation modulus of elasticity is in the above range, the impact resistance measured by the second coating layer of the film for an optical display device is excellent, so that it can be used for an optical display device.
  • the film for optical display devices can be improved in wear resistance, foldability in both the compression direction and the tensile direction.
  • the indentation modulus can be from about 10 MPa to about 40 MPa.
  • (Meth) acrylate having a weight average molecular weight of from about 1,000 g / mol to about 40,000 g / mol, such as 1000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, and 4000 g / mol.
  • the impact resistance of the film for an optical display device can be enhanced, and scratch resistance and bendability can be improved.
  • the urethane (meth) acrylate is a bifunctional to trifunctional (meth) acrylate based and has a weight average molecular weight of about 1,000 g / mol to about 30,000 g / mol, preferably about 1,000 g / mol Gt; g / mol. ≪ / RTI > Within the above-mentioned range, the coating layer having a thin thickness can also have the above-described impact resistance, scratch resistance and folding property, and more abrasion resistance.
  • Urethane (meth) acrylate can be produced by polymerization of a (poly) functional polyol, a polyfunctional isocyanate compound and a (meth) acrylate compound having a hydroxyl group, or a commercially available product.
  • the polymerization method is as known to those skilled in the art.
  • the polyfunctional polyol may include at least one of an aromatic polyol, an aliphatic polyol, and an alicyclic polyol.
  • the polyol may include, but is not limited to, one or more of a polyester diol, a polycarbonate diol, a polyolefin diol, a polyether diol, a polythioether diol, a polysiloxane diol, a polyacetal diol, and a polyester amide diol.
  • the multifunctional isocyanate compound may comprise any aliphatic, alicyclic or aromatic isocyanate.
  • the (meth) acrylate compound having a hydroxyl group may be at least one selected from the group consisting of hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, hydroxypropyl (meth) But are not limited to, hydroxybutyl (meth) acrylate, chlorohydroxypropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and the like.
  • the urethane (meth) acrylate may be a monomer, an oligomer or a resin having the elongation and the like described above.
  • the elongation and weight average molecular weight of the urethane (meth) acrylate can be attained by adjusting the dropping rate, content, etc. of each component during the urethane (meth) acrylate production process.
  • the urethane (meth) acrylate may be used in an amount of about 80 parts by weight to about 99 parts by weight, for example, 80, 81, 82, 83, 84 parts by weight per 100 parts by weight of the total amount of urethane (meth) acrylate, N-vinylpyrrolidone, , 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 parts by weight, preferably about 85 parts by weight to about 99 parts by weight, To about 95 parts by weight, from about 90 parts by weight to about 95 parts by weight.
  • the film for an optical display device is excellent in impact resistance and scratch resistance, and the curvature radius can be lowered together with the substrate layer to increase the foldability, and the above-mentioned indentation elastic modulus can be ensured.
  • N-vinylpyrrolidone enhances the adhesion between the first coating layer and the substrate layer, and prevents the first coating layer from peeling off from the substrate layer even in repetitive folding of the film for optical display devices.
  • N-vinylpyrrolidone is used in an amount of from about 0.1 parts by weight to about 10 parts by weight, for example, from 0.1, 0.5, 1, 1.5, 2 (parts by weight) per 100 parts by weight of the total of the urethane (meth) acrylate, N-vinylpyrrolidone, , 2.5, 3.5, 4.5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 parts by weight, preferably about 1 part by weight to about 10 parts by weight, Parts by weight to about 7 parts by weight.
  • adhesion between the first coating layer and the substrate layer can be improved without affecting the other physical properties of the film for an optical display device.
  • the initiator can be used to cure the urethane (meth) acrylate (partial polymerization) or to cure the composition for the first coating layer into a film.
  • the initiator may include at least one of a photopolymerization initiator and a thermal polymerization initiator. Any photopolymerization initiator can be used as long as it can induce polymerization reaction of the radical polymerizable compound in a curing process by light irradiation or the like.
  • a photopolymerization initiator a benzoin-based, hydroxy ketone-based, aminoketone-based or phosphine oxide-based photoinitiator can be used.
  • the thermal polymerization initiator is not particularly limited as long as it has the above physical properties, and for example, a conventional initiator such as an azo compound, a peroxide compound, or a redox compound can be used.
  • the initiator may be used in an amount of from about 0.0001 part by weight to about 10 parts by weight, for example, from 0.0001, 0.1, 0.5, 1, 1.5, 2, 2.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 parts by weight, specifically about 0.1 part by weight to about 10 parts by weight.
  • the curing reaction can be completely proceeded, the remaining amount of the initiator remains, the permeability can be prevented from being lowered, the bubble generation can be lowered, and the reactivity can be improved.
  • the composition for the first coating layer is a solvent-free, solventless formulation. However, by further including a solvent, it is possible to improve the coatability of the composition for the first coating layer and improve the surface smoothness of the first coating layer, thereby improving the light transmittance.
  • the solvent may include, for example, methyl ethyl ketone or the like as a conventional solvent known to those skilled in the art, but is not limited thereto.
  • composition for the first coating layer may further comprise conventional additives.
  • the additive may include, but is not limited to, an antistatic agent, an antioxidant, an ultraviolet absorber, a pigment, a leveling agent and the like.
  • the second coating layer is the second coating layer
  • the second coating layer 120 may be formed directly on the other surface of the base layer 130 to protect the film for the optical display device or to protect the optical display device from various elements such as a polarizer, Can be protected. This "directly formed” means that no adhesive layer, adhesive layer or laminating layer is interposed between the base layer and the second coating layer.
  • the second coating layer 120 is not particularly limited, but may be a hard coating layer.
  • the second coating layer 120 may have a thickness of about 10 ⁇ m or less, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 ⁇ m, specifically about 5 ⁇ m or less. Within the above range, it is possible to increase impact resistance and scratch resistance even with thin film for optical display devices.
  • the second coating layer 120 may have a refractive index of from about 1.40 to about 1.75, for example, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, specifically about 1.45 to about 1.65. In this range, the refractive index of the first coating layer and the substrate layer is appropriate, so that the haze of the film for an optical display device is not increased and the appearance is excellent, and the screen visibility can be improved when the window film is laminated.
  • the second coating layer 120 may be formed of a composition for the second coating layer.
  • composition for the second coating layer will be described.
  • the composition for the second coating layer may comprise a urethane (meth) acrylate, a (meth) acrylate monomer, a zirconia particle, a silicone additive and an initiator.
  • the urethane (meth) acrylate has a weight average molecular weight of about 1,000 g / mol to about 8,000 g / mol, for example, 1000, 2000, 3000, 4000, 5000, 6000 , 7000, 8000 g / mol, and an elongation of about 1% to about 25%, such as 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25%.
  • a weight average molecular weight of about 1,000 g / mol to about 8,000 g mol, for example, 1000, 2000, 3000, 4000, 5000, 6000 , 7000, 8000 g / mol, and an elongation of about 1% to about 25%, such as 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25%.
  • the film for an optical display device of the present invention is prepared by adjusting the elongation of urethane (meth) acrylate and the content of urethane (meth) acrylate contained in the first coating layer and the second coating layer, respectively, ) Acrylate relative to the total elongation of the urethane (meth) acrylate in the second coating layer to improve impact resistance and foldability in outfolding and in folding.
  • the film 100 for an optical display device has a three-layer structure of a film for an optical display device, i.e., a first coating layer, a base layer, and a second coating layer sequentially formed on the first coating layer surface, Lt; / RTI > can be larger than the indentation modulus of elasticity measured by the method of the present invention.
  • the indentation modulus measured on the first coating layer side is in the range of from about 10 MPa to about 60 MPa, such as 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 MPa, preferably about 10 MPa to about 40 MPa
  • the indentation modulus measured on the surface of the second coating layer may be from about 5 GPa to about 12 GPa, for example, 5, 6, 7, 8, 9, 10, 11, 12 GPa, preferably about 6 GPa to about 10 GPa.
  • the film for an optical display device may have both excellent folding resistance and scratch resistance.
  • the urethane (meth) acrylate may be a monomer, an oligomer or a resin having the aforementioned elongation, weight average molecular weight, and number of functional groups.
  • the urethane (meth) acrylate is a urethane (meth) acrylate having two or more, preferably two, kinds of urethanes having different elongation, weight average molecular weight and functional group number in the range of the elongation, weight average molecular weight, ) Acrylate.
  • one urethane (meth) acrylate in the mixture of urethane (meth) acrylates is referred to as a "third urethane (meth) acrylate" and the other urethane (meth) (Meth) acrylate and the fourth urethane (meth) acrylate have the aforementioned elongation, weight average molecular weight, or functional group number range, and they may have one or more of elongation, weight average molecular weight and functional group number Can be different.
  • the third urethane (meth) acrylate is a (functional) acrylate having from 7 to 10 functionalities and has a weight average molecular weight of from about 1,000 g / mol to less than about 4,000 g / mol, such as 1000, 300, 3100, 3200, 3300, 3400, 3500, 2500, 2600, 2700, 2800, 2900, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14%. ≪ / RTI > Within the above range, it is possible to improve the impact resistance, scratch resistance and bendability of the optical display device film.
  • the third urethane (meth) acrylate has a weight average molecular weight of from about 1,500 g / mol to about 2,500 g / mol, an elongation of from about 5% to about 10 %. ≪ / RTI > Within the above-mentioned range, the second coating layer having a thin thickness can also have the above-described impact resistance, scratch resistance, foldability, and wear resistance.
  • the third urethane (meth) acrylate can be, but not limited to, UA11064 (Entis).
  • the fourth urethane (meth) acrylate is a tetrafunctional to hexafunctional (meth) acrylate based and has a weight average molecular weight of from about 4,000 g / mol to about 8,000 g / mol, such as 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 6100, 6200, 6300, 6400, Molar ratio of about 15% to about 25%, for example, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25%.
  • the fourth urethane (meth) acrylate has a weight average molecular weight of about 4,000 g / mol to about 6,000 g / mol and a elongation of about 15% to about 20 %. ≪ / RTI > Within the above-mentioned range, the second coating layer having a thin thickness can improve the impact resistance, scratch resistance and foldability as described above, and can further enhance the stretching effect.
  • the fourth urethane (meth) acrylate can be, but not limited to, CHTF-9696AN (Chemton).
  • the fourth urethane (meth) acrylate may be included in a predetermined amount relative to the third urethane (meth) acrylate. In such a case, when it is included together with the zirconia particles, the impact resistance, the scratch resistance and the bending property can be improved.
  • the fourth urethane (meth) acrylate comprises about 20% to about 200% by weight of the third urethane (meth) acrylate, such as 20,30,40,50,60,70,80,90,100,110 , 120, 130, 140, 150, 160, 170, 180, 190, 200%, preferably from about 20% to about 100% by weight and from about 20% to about 50% by weight.
  • the second coating layer having a thin thickness can improve the impact resistance, scratch resistance and foldability as described above, and can further enhance the stretching effect.
  • the urethane (meth) acrylate can be produced by the polymerization of the above-mentioned polyfunctional polyol, polyfunctional isocyanate compound and (meth) acrylate compound having a hydroxyl group.
  • the polyfunctional polyol may include the above-mentioned polyfunctional polyol
  • the polyfunctional isocyanate compound may include the above-mentioned polyfunctional isocyanate compound.
  • the (meth) acrylate compound having a hydroxyl group may be at least one selected from the group consisting of hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, hydroxypropyl (meth) But are not limited to, hydroxybutyl (meth) acrylate, chlorohydroxypropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and the like.
  • the elongation and weight average molecular weight of the urethane (meth) acrylate can be attained by adjusting the dropping rate, content, etc. of each component during the urethane (meth) acrylate production process.
  • the urethane (meth) acrylate may be used in an amount of about 40 parts by weight to about 85 parts by weight, for example, 40, 41, 42, 43, or 40 parts by weight based on 100 parts by weight of the total of urethane (meth) acrylate, (meth) acrylate monomer, 65, 63, 64, 65, 66, 67, 68, 59, 55, 56, 57, 58, 59, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85 parts by weight.
  • the film for an optical display device is excellent in impact resistance and scratch resistance, and the curvature radius can be lowered together with the substrate layer to increase the foldability.
  • the curvature radius can be lowered together with the substrate layer to increase the foldability.
  • (Meth) acrylate monomers are bifunctional to hexafunctional (meth) acrylate monomers which can be cured with urethane (meth) acrylate to increase hardness.
  • the (meth) acrylate monomer may be a non-urethane based (meth) acrylate monomer that does not contain a urethane group.
  • (Meth) acrylate monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol Acrylate, neopentyl glycol adipate di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, (Meth) acrylate, di (meth) acryloxyethyl isocyanurate, allyl cyclohexyl di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, (Meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modified tri Acrylate such
  • the (meth) acrylate monomer is a trifunctional (meth) acrylate such as ethylene oxide modified trimethylolpropane tri (meth) acrylate including ethoxylated (6) trimethylolpropane tri (meth) ) Acrylate may be used.
  • a trifunctional (meth) acrylate such as ethylene oxide modified trimethylolpropane tri (meth) acrylate including ethoxylated (6) trimethylolpropane tri (meth) ) Acrylate may be used.
  • (Meth) acrylate monomer is used in an amount of about 5 parts by weight to about 50 parts by weight, for example, 5, 6, 7, 8, or 10 parts by weight, based on 100 parts by weight of the total amount of urethane (meth) acrylate, (meth) acrylate monomer, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 45, 46, 47, 48, 49, 50 parts by weight, for example about 5 parts by weight to about 40 parts by weight, 10 parts by weight to about 40 parts by weight, and about 10 parts by weight to about 30 parts by weight.
  • the second coating layer having a thin thickness can improve the impact resistance, scratch resistance and foldability described above.
  • the zirconia particles can increase the scratch resistance of the second coating layer.
  • Zirconia particles have an average particle size (D50) of about 200 nm or less, for example, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 170, 180, 190, 200 nm, specifically about 5 nm or more and about 100 nm or less, More specifically from about 20 nm to about 50 nm. Within this range, the scratch resistance can be improved without increasing the haze of the second coating layer.
  • the "average particle diameter (D50)" means a typical average particle diameter known to a person skilled in the art.
  • the surface treatment with the (meth) acrylate compound has a good dispersibility with the urethane (meth) acrylate and (meth) acrylate monomers, thereby lowering the haze of the film for optical display devices have.
  • the zirconia particles may be used in an amount of about 0.01 to about 10 parts by weight, for example, 0.01, 0.1, 0.5, 1, 1.5, 2, or 3 parts by weight, based on 100 parts by weight of the total of urethane (meth) acrylate, (meth) acrylate monomer, About 1 part by weight to about 10 parts by weight, about 5 parts by weight, about 5 parts by weight, about 2.5 parts by weight, To about 10 parts by weight.
  • the second coating layer having a thin thickness can improve the impact resistance, scratch resistance and foldability described above.
  • the silicone additive may include conventional silicone additives known to those skilled in the art to improve the surface properties of the second coating layer.
  • the silicone additive may include, but is not limited to, polyether-modified acrylic polydimethylsiloxane and the like.
  • the silicone additive may be used in an amount of about 0.01 to about 5 parts by weight, for example, 0.01, 0.5, 1, 1.5, 2 or 2.5 parts by weight based on 100 parts by weight of the total of the urethane (meth) acrylate, (meth) acrylate monomer and zirconia particles. , 3, 3.5, 4, 4.5, 5 parts by weight, specifically about 0.1 part by weight to about 2 parts by weight, about 0.1 part by weight to about 1 part by weight. Within this range, the surface properties of the second coating layer may be good without affecting other components.
  • the initiator may include a radical photoinitiator.
  • the initiator may be an acetophenone-based compound, a benzylketal-based compound, a cyclohexylphenylketone-based compound, or a mixture thereof, but is not limited thereto.
  • (Meth) acrylate, (meth) acrylate monomer, and zirconia particles in an amount of 100 parts by weight based on the total amount of the urethane (meth) About 0.01 part by weight to about 10 parts by weight, specifically about 1 part by weight to about 5 parts by weight.
  • the curing reaction can be completely proceeded, the remaining amount of the initiator remains, the permeability can be prevented from being lowered, bubbling can be reduced, and the reactivity can be improved.
  • the composition for the second coating layer may further include a solvent to facilitate coating of the composition for the second coating layer.
  • the solvent may include, but is not limited to, methyl ethyl ketone, methyl isobutyl ketone, and the like.
  • composition for the second coating layer may further comprise conventional additives known to those skilled in the art for imparting additional functions to the second coating layer.
  • additives may include, but are not limited to, antioxidants, stabilizers, surfactants, pigments, dyes, antistatic agents, leveling agents, surface energy modifiers, defoamers, UV absorbers,
  • composition for the second coating layer of another embodiment will be described.
  • the composition for the second coating layer may comprise urethane (meth) acrylate, (meth) acrylate monomers, zirconia particles, silicone additives, initiators, dyes and antistatic agents. Is substantially the same as the composition for the second coating layer of one embodiment, except that it further comprises a dye and an antistatic agent.
  • the film for an optical display device formed of the composition for the second coating layer of this embodiment has a YI of about 1.0 or less and a YI of about 1.0 or less and can be used with high reliability in an optical display device.
  • DELTA YI can be measured by the following equation (1).
  • Y2 represents the yellow index measured on the film for an optical display device
  • Y1 is the yellow index measured by the same method after leaving for 30 minutes at room temperature after irradiating the film for optical display with Y2 for 72 hours in a UV-B lamp).
  • YI is about 0 or more and 0.6 or less, and? YI is about 0 or more and 0.9 or less.
  • the dye may have a maximum absorption wavelength of from about 300 nm to about 500 nm, for example, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, , 480, 490, 500 nm, preferably from about 300 nm to about 400 nm.
  • the dyes may be PANAX GD-16 (Woo Sung Chemical Co.), FP-1025, PA-905, and the like, but are not limited thereto.
  • the dye may comprise from about 0.05% to about 0.1% by weight of the second coating layer. Within this range, the yellowing can be suppressed without affecting the function of the other components, and the transmittance of the film for an optical display device can be prevented from being lowered.
  • the dye may be included in an amount of about 0.05 part by weight to about 0.15 part by weight, preferably about 0.05 part by weight to about 0.1 part by weight, based on 100 parts by weight of the total of urethane (meth) acrylate, (meth) acrylate monomer and zirconia particles .
  • the yellowing can be suppressed without affecting the function of the other components, and the transmittance of the film for an optical display device can be prevented from being lowered.
  • the antistatic agent suppresses the generation of static electricity by lowering the sheet resistance of the second coating layer when the film for an optical display device is disposed at the outermost side of the optical display device.
  • the sheet resistance measured in the second coating layer of the film for an optical display device can be about 5 x 10 11 ? /? Or less.
  • the antistatic agent may include conventional antistatic agents known to those skilled in the art.
  • an ionic liquid as the antistatic agent, the surface resistance can be sufficiently lowered in the composition of the second coating layer of the present invention, and the ionic liquid may not leak out even after a long period of use.
  • ionic liquids of tetraalkylammonium cations and sulfonate imide anions can be used.
  • the antistatic agent may comprise at least about 11 wt%, preferably from about 11 wt% to about 15 wt%, more preferably from about 11 wt% to about 13 wt%, of the second coating layer. Within this range, antistatic properties can be improved without affecting the function of other components, and adhesion between the base layer and the second coating layer can be good.
  • the antistatic agent is used in an amount of about 7 parts by weight or more and less than about 13 parts by weight, preferably about 11 parts by weight or more and less than about 13 parts by weight based on 100 parts by weight of the total amount of urethane (meth) acrylate, (meth) acrylate monomer, , From about 11 parts by weight to about 12.5 parts by weight. Within this range, antistatic properties can be improved without affecting the function of other components, and adhesion between the base layer and the second coating layer can be good.
  • composition for the second coating layer may comprise a urethane (meth) acrylate, a (meth) acrylate monomer, silica particles, a silicone additive and an initiator.
  • Urethane (meth) acrylate is referred to as "fifth urethane (meth) acrylate" for convenience.
  • the fifth urethane (meth) acrylate may have a (meth) acrylate structure having an 11 to 20 functional groups, preferably 13 to 18 functional groups, and a elongation percentage of 5% to 15%. Within the above range, it is possible to improve the impact resistance, scratch resistance and bendability of the optical display device film.
  • the fifth urethane (meth) acrylate may comprise a cyclopropylene group. In this case, excellent scratch resistance can be obtained by controlling the crosslink density.
  • the urethane (meth) acrylate may be used in an amount of about 40 parts by weight to about 85 parts by weight, for example, 40, 41, 42, 43, or 40 parts by weight based on 100 parts by weight of the total of the urethane (meth) acrylate, (meth) acrylate monomer, 65, 63, 64, 65, 66, 67, 68, 59, 55, 56, 57, 58, 59, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85 parts by weight.
  • the film for an optical display device is excellent in impact resistance and scratch resistance, and the curvature radius can be lowered together with the substrate layer to increase the foldability.
  • the curvature radius can be lowered together with the substrate layer to increase the foldability.
  • (Meth) acrylate monomers may include (meth) acrylate monomers having an alkylene oxide group.
  • the alkylene oxide group may be an alkylene oxide group having from 1 to 5 carbon atoms, preferably from 2 to 5 carbon atoms.
  • the (meth) acrylate monomer may be selected from the group consisting of polyethylene glycol di (meth) acrylate and propylene oxide modified trimethylolpropane tri (meth) acrylate including polyethylene glycol (600) di (meth) (6) trimethylol propane tri (meth) acrylate, and the like, and the like.
  • the (meth) acrylate monomer may be a non-urethane based, bifunctional to hexafunctional (meth) acrylate monomer containing no urethane bond.
  • (Meth) acrylate monomer may be used in an amount of about 5 parts by weight to about 50 parts by weight, for example, 5, 6, 7, 8, or 10 parts by weight per 100 parts by weight of the total of urethane (meth) acrylate, (meth) acrylate monomer, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 45, 46, 47, 48, 49, 50 parts by weight, for example about 5 parts by weight to about 40 parts by weight, 10 parts by weight to about 40 parts by weight, and about 10 parts by weight to about 30 parts by weight.
  • the second coating layer having a thin thickness can improve the impact resistance, scratch resistance and foldability described above.
  • the silica particles can enhance the scratch resistance of the second coating layer.
  • the silica particles may have an average particle size (D50) of about 200 nm or less, specifically about 5 nm to about 100 nm, and about 20 nm to about 50 nm. Within this range, the scratch resistance can be improved without increasing the haze of the second coating layer.
  • the average particle diameter (D50) means a typical average particle diameter known to a person skilled in the art.
  • the silica particles may not be surface-treated, but the surface treatment with the (meth) acrylate compound has good dispersibility with the urethane (meth) acrylate and (meth) acrylate monomers, thereby lowering the haze of the film for optical display devices have.
  • the silica particles may be used in an amount of about 0.01 to about 10 parts by weight, for example, 0.01, 0.1, 0.5, 1, 2, 3, or 4 parts by weight per 100 parts by weight of the total of the urethane (meth) acrylate, (meth) acrylate monomer, 4, 5, 6, 7, 8, 9, 10 parts by weight, for example about 1 part by weight to about 10 parts by weight, and about 5 parts by weight to about 10 parts by weight.
  • the second coating layer having a thin thickness can improve the impact resistance, scratch resistance and foldability described above.
  • the silicon-based additive and the initiator are as described above.
  • composition for the second coating layer may comprise the above-mentioned solvent.
  • the composition for the second coating layer may form a buffer layer by partially dissolving the polyimide film and intermixing the composition for the second coating layer and the polyimide film.
  • the buffer layer can facilitate the flexibility and scratch resistance of the film for an optical display device.
  • a functional layer may be further formed on the second coating layer 120 (the upper surface of the second coating layer) to provide an additional function to the film for an optical display device.
  • the functional layer may be one of anti-finger, low reflection, anti-glare, anti-contamination, anti-reflection, The above functions can be provided.
  • the functional layer may be formed by applying a composition for forming a functional layer on the second coating layer 120, or may be laminated on the second coating layer 120 through an adhesive layer or an adhesive layer. In other embodiments, the functional layer may be formed such that one side of the second coating layer 120 is a functional layer.
  • the tofu layer may be formed of a composition comprising a fluorine solvent, a fluorine monomer or oligomer thereof, and a silane coupling agent.
  • the laminated layer may have a thickness of from about 20 nm to about 200 nm, preferably from about 30 nm to about 100 nm.
  • the optical display device film 100 has a total light transmittance of about 89% or more, about 89% to about 99%, a haze of about 1.5% or less, preferably about 1.1% or less, in a visible light region, for example, a wavelength of about 380 nm to about 780 nm, ≪ / RTI > Within this range, the appearance is good and can be used in an optical display device.
  • the optical display device film 100 may have a radius of curvature of about 5 mm or less, for example, about 1 mm or less. Specifically, the optical display device film 100 may have a curvature radius of about 5 mm or less, for example, 3 mm or less when folded in the direction of the second coating layer 120 (compression direction). The optical display device film 100 may have a radius of curvature of about 5 mm or less, about 3 mm or less, for example, about 1 mm or less when folded in the first coating layer 110 direction (tensile direction). In the above range, excellent foldability can be used for a flexible optical display device.
  • the "radius of curvature” indicates that a 75 ⁇ ⁇ -thick polyethylene terephthalate film is laminated on the lower surface of the first coating layer of the film for optical display device so that the length of the specimen having a length x width of 10 cm x 5 cm is 1/2 This means the minimum value at which no crack occurs at the folded portion when folded.
  • the optical display device film 100 may have a bending stiffness of about 7N or less, preferably about 5N or less. Bending stiffness is a force applied to a film for an optical display device when the film for an optical display device is bent to a radius of curvature of 1 to 3 mm toward the second coating layer (hard coating layer). The greater the bending stiffness is, the greater the force applied to the film for an optical display device when the film for an optical display device is bent to a radius of curvature of 1 mm to 3 mm so that at least one of the first coating layer and the second coating layer Cracks will occur.
  • the film for an optical display device of the present invention can prevent cracks from occurring even when the entire film for an optical display device is bent without separation between the first coating layer, the base layer and the second coating layer.
  • the bending stiffness can be measured according to Fig.
  • the optical display device film 100 may have a thickness of about 250 ⁇ or less, specifically about 220 ⁇ or less. In the above range, it can be used in an optical display device.
  • an adhesive layer may be further formed on the lower surface of the second coating layer, that is, the surface opposite to the surface on which the base layer is laminated in the second coating layer.
  • the adhesive layer can adhere the film for an optical display device to a polarizing plate, a touch panel, a window film or the like of a display element.
  • the pressure sensitive adhesive layer may include a pressure sensitive adhesive (PSA), a transparent pressure sensitive adhesive (OCA), or the like.
  • the adhesive layer may be formed of a pressure sensitive adhesive composition comprising a (meth) acrylic copolymer as the (meth) acrylic adhesive layer.
  • the pressure sensitive adhesive composition may comprise a (meth) acrylic copolymer, a crosslinking agent.
  • (Meth) acryl-based copolymer is a copolymer of a (meth) acrylic monomer having an alkyl group and a (meth) acrylic monomer having a hydroxyl group, a (meth) acrylic monomer having a carboxylic acid group, a (meth) acrylic monomer having a heterocyclic group, ) Acrylic monomer, and (meth) acrylic monomer having an alicyclic group.
  • the crosslinking agent may include one or more of an isocyanate-based, amine-based, epoxy-based, aziridine-based, metal chelate-based crosslinking agent.
  • the pressure sensitive adhesive composition comprises a monomer mixture for a (meth) acrylic copolymer having a hydroxyl group; Initiator; And one or more of macromonomers and organic nanoparticles.
  • the monomer mixture may be contained in the pressure-sensitive adhesive composition in the state of a monomer mixture in which polymerization is not carried out at all, but the monomer mixture may be contained as a partially polymerized partial polymer.
  • the pressure-sensitive adhesive composition comprises a monomer mixture for a (meth) acrylic copolymer having a hydroxyl group; Initiator; And organic nanoparticles.
  • the monomer mixture may be composed of a hydroxyl group-containing (meth) acrylate and an alkyl group-containing (meth) acrylate.
  • the hydroxyl group-containing (meth) acrylate can provide the adhesion of the adhesive layer.
  • the hydroxyl group-containing (meth) acrylate may be a (meth) acrylate containing at least one hydroxyl group.
  • the hydroxyl group-containing (meth) acrylate may be at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (Meth) acrylate, diethylene glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, trimethylolethane di (meth) acrylate
  • the hydroxyl group-containing (meth) acrylate is used in an amount of about 5% by weight to about 40% by weight, for example, about 8% by weight to about 30% by weight, in the total amount of the hydroxyl group-containing (meth) 10 wt% to about 30 wt%.
  • the adhesive strength and endurance reliability of the adhesive layer in the above range can be further improved.
  • the alkyl group-containing (meth) acrylate may become a copolymer to form a matrix of an adhesive layer.
  • the alkyl group-containing (meth) acrylate may include an unsubstituted linear or branched alkyl (meth) acrylate having 1 to 20 carbon atoms.
  • the alkyl group-containing (meth) acrylate is used in an amount of about 60% by weight to about 95% by weight, such as about 65% by weight to about 92% by weight of the total of the hydroxyl group-containing (meth) acrylate and alkyl group- 68 wt% to about 90 wt%, and about 70 wt% to about 90 wt%.
  • the adhesive strength and endurance reliability of the adhesive layer in the above range can be further improved.
  • the monomer mixture may further comprise copolymerizable monomers.
  • the copolymerizable monomer may be contained in the (meth) acrylic copolymer to provide additional effects to the (meth) acrylic copolymer, the pressure sensitive adhesive composition or the pressure sensitive adhesive layer.
  • the copolymerizable monomer is a monomer having an ethylene oxide, a monomer having propylene oxide, a monomer having an amine group, a monomer having an alkoxy group, a monomer having a phosphoric acid group, or a monomer having an alkyl group (meth) , A monomer having a sulfonic acid group, a monomer having a phenyl group, a monomer having a silane group, a monomer having a carboxylic acid group, and an amide group-containing (meth) acrylate.
  • the copolymerizable monomer is used in an amount of about 15 parts by weight or less, specifically about 10 parts by weight or less, more specifically about 0.05 part by weight to about 8 parts by weight, based on 100 parts by weight of the sum of the hydroxyl group-containing (meth) acrylate and alkyl group- By weight.
  • the pressure-sensitive adhesive composition can further improve the adhesive force and the recoverability of the pressure-sensitive adhesive film.
  • Initiators can be used to cure (partially polymerize) the monomer mixture into a (meth) acrylic copolymer or to cure a viscous liquid into a film.
  • the initiator may include at least one of a photopolymerization initiator and a thermal polymerization initiator.
  • any photopolymerization initiator can be used as long as it can induce the polymerization reaction of the radical polymerizable compound described below in a curing process by light irradiation or the like.
  • benzoin, hydroxy ketone, amino ketone or phosphine oxide photoinitiators can be used.
  • the thermal polymerization initiator is not particularly limited as long as it has the above-mentioned physical properties, and for example, ordinary initiators such as an azo-based compound, a peroxide-based compound or a redox-based compound can be used.
  • the initiator is used in an amount of from about 0.0001 part by weight to about 5 parts by weight, specifically from about 0.001 part by weight to about 5 parts by weight, based on 100 parts by weight of the sum of the hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) acrylate constituting the (meth) About 3 parts by weight.
  • the curing reaction can be completely carried out, and the remaining amount of the initiator remains, the permeability can be prevented from being lowered, the bubble generation can be lowered, and the reactivity can be improved.
  • the macromonomer may have a functional group curable by an active energy ray and may be polymerized with a hydroxyl group-containing (meth) acrylate and an alkyl group-containing (meth) acrylate.
  • R 1 is hydrogen or a methyl group
  • X represents a single bond or a divalent coupler
  • Y is methyl (meth) acrylate, ethyl (meth) acrylate, n- butyl (meth) acrylate, iso- butyl (Meth) acrylate, t-butyl (meth) acrylate, styrene, and (meth) acrylonitrile.
  • the macromonomer may have a number average molecular weight of from about 2,000 to about 20,000, specifically from about 2,000 to about 10,000, more specifically from about 4,000 to about 8,000. Within the above range, sufficient adhesive strength can be obtained, heat resistance is excellent, and deterioration of workability due to an increase in viscosity of the pressure-sensitive adhesive composition can be suppressed.
  • the macromonomer may have a glass transition temperature of from about 40 ⁇ to about 150 ⁇ , specifically from about 60 ⁇ to about 140 ⁇ , more specifically from about 80 ⁇ to about 130 ⁇ . In this range, the pressure-sensitive adhesive layer can exhibit a sufficient cohesive force, and can suppress the degree of stickiness and deterioration of the adhesive force.
  • the coupler is an arylene group, -NR a C1 to C10 alkyl groups, C7 to C13 aryl alkyl group, C6 to C12 2 - (wherein, R 2 is an alkyl group of hydrogen, or a C1 to C5), COO-, - O-, -S-, -SO 2 NH-, -NHSO 2 -, may be a group derived from -NHCOO-, -OCONH, or heterocyclic.
  • the divalent linking group may be represented by the following formulas (1a) to (1d):
  • a macromonomer wherein the terminal is methacryloyl group and the segment corresponding to Y is methyl methacrylate, the segment corresponding to Y is styrene, the segment corresponding to Y is a styrene / acryl Macromonomers in which the segment corresponding to Y is butyl acrylate, and the like can be used.
  • the macromonomer may be used in an amount of about 20 parts by weight or less, specifically about 0.1 part by weight to about 20 parts by weight, about 0.1 part by weight to about 10 parts by weight, based on 100 parts by weight of the sum of the hydroxyl group-containing (meth) acrylate and alkyl group- About 0.5 parts by weight to about 5 parts by weight.
  • the viscoelasticity of the adhesive layer can be balanced with the modulus and the restoring force, and the increase in haze of the adhesive layer can be prevented.
  • the organic nanoparticles may have an average particle size of from about 10 nm to about 400 nm, specifically from about 10 nm to about 300 nm, more specifically from about 30 nm to about 280 nm, and more specifically from about 50 nm to about 280 nm.
  • the transparency of the adhesive layer may be good, with the total light transmittance in the visible light region not exceeding 90%, without affecting the folding of the adhesive layer.
  • the difference in refractive index between the organic nanoparticles and the (meth) acrylic copolymer having a hydroxyl group may be about 0.1 or less, specifically about 0 or more and about 0.05 or less, specifically about 0 or more and about 0.02 or less. In the above range, the transparency of the adhesive layer can be excellent.
  • the organic nanoparticles may have a refractive index of from about 1.35 to about 1.70, specifically from about 1.40 to about 1.60. Within this range, the transparency of the adhesive layer may be excellent.
  • the organic nanoparticles may include, but are not limited to, core-shell type and simple nanoparticles such as a bead type.
  • core-shell type the core and the shell can satisfy the following formula 2: that is, both the core and the shell can be nanoparticles that are organic materials.
  • Tg (s) is the glass transition temperature (unit: ⁇ ⁇ ) of the shell.
  • the term "shell” means the outermost layer of the organic nanoparticles.
  • the core may be a single spherical particle. However, the core may further comprise additional layers surrounding the spherical particles if they have the above glass transition temperature.
  • the glass transition temperature of the core can be from about -150 ⁇ to about 10 ⁇ , specifically about -150 ⁇ to about -5 ⁇ , more specifically about -150 ⁇ to about -20 ⁇ . Within this range, there may be a low temperature and / or room temperature viscoelastic effect of the adhesive layer.
  • the core may contain at least one of polyalkyl (meth) acrylate, polysiloxane or polybutadiene having the above glass transition temperature.
  • the polyalkyl (meth) acrylate may be at least one selected from the group consisting of polymethyl acrylate, polyethylacrylate, polypropyl acrylate, polybutyl acrylate, polyisopropyl acrylate, polyhexyl acrylate, polyhexyl methacrylate, polyethylhexyl acrylate And polyethylhexyl methacrylate, polysiloxane, and is not necessarily limited thereto.
  • the polysiloxane can be, for example, an organosiloxane (co) polymer.
  • the organosiloxane (co) polymer may be one which is not cross-linked, or a cross-linked (co) polymer may be used.
  • an organosiloxane (co) polymer in a crosslinked state can be used. It is a crosslinked form of organosiloxane, specifically crosslinked dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane or a mixture of two or more thereof.
  • a refractive index of from about 1.41 to about 1.50 can be controlled by using a copolymerized form of two or more organosiloxanes.
  • the crosslinking state of the organosiloxane (co) polymer can be determined by the degree of dissolution by various organic solvents. As the crosslinking state deepens, the degree of dissolution by the solvent becomes smaller. As the solvent for determining the crosslinking state, acetone, toluene and the like can be used. Specifically, the organosiloxane (co) polymer may have a portion which is not dissolved by acetone or toluene. The insoluble fraction of the organosiloxane copolymer to toluene can be about 30% or more.
  • the organosiloxane (co) polymer may further comprise an alkyl acrylate crosspolymer.
  • the alkyl acrylate crosslinked polymer may be selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate.
  • n-butyl acrylate or 2-ethylhexyl acrylate having a low glass transition temperature may be used.
  • the glass transition temperature of the shell can be from about 15 ⁇ to about 150 ⁇ , specifically from about 35 ⁇ to about 150 ⁇ , more specifically from about 50 ⁇ to about 140 ⁇ . In the above range, the dispersibility of the organic nanoparticles in the (meth) acrylic copolymer may be excellent.
  • the shell may comprise a polyalkyl methacrylate having said glass transition temperature.
  • PMMA polymethylmethacrylate
  • PMMA polyethylmethacrylate
  • polypropylmethacrylate polypropylmethacrylate
  • polybutylmethacrylate polyisopropylmethacrylate
  • polyisobutylmethacrylate polycyclohexylmethacrylate Rate, < / RTI > but is not necessarily limited thereto.
  • the core may comprise from about 30 wt% to about 99 wt%, specifically from about 40 wt% to about 95 wt%, and more specifically from about 50 wt% to about 90 wt%, of the organic nanoparticles.
  • the folding property of the adhesive layer may be good in a wide temperature range.
  • the shell may comprise from about 1% to about 70%, specifically from about 5% to about 60%, more specifically from about 10% to about 50%, by weight of the organic nanoparticles.
  • the folding property of the adhesive layer may be good in a wide temperature range.
  • the organic nanoparticles may be used in an amount of about 0.1 to about 20 parts by weight, specifically about 0.5 to about 10 parts by weight per 100 parts by weight of the sum of the hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) About 0.5 parts by weight to about 8 parts by weight.
  • the modulus of the pressure-sensitive adhesive layer at high temperature can be increased, the folding property of the pressure-sensitive adhesive layer at room temperature and high temperature can be improved, and the low temperature and / or room temperature viscoelasticity of the pressure-
  • the organic nanoparticles can be prepared by conventional emulsion polymerization, suspension polymerization, or solution polymerization.
  • the pressure-sensitive adhesive composition may further include a silane coupling agent.
  • silane coupling agent those conventionally known to those skilled in the art can be used. For example, there can be mentioned 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl tri
  • a silicon compound having an epoxy structure such as methoxysilane
  • a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane and (meth) acryloxypropyltrimethoxysilane
  • Containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-a
  • the silane coupling agent may be included in an amount of about 0.01 to about 3 parts by weight, specifically about 0.01 to about 1 part by weight, based on 100 parts by weight of the total (meth) . In the above range, reliability can be secured in the bending state at the high temperature and high humidity described above, and the difference in peeling force between low temperature, normal temperature and high temperature can be low.
  • the pressure-sensitive adhesive composition may further include a crosslinking agent.
  • the crosslinking agent can increase the degree of crosslinking of the pressure-sensitive adhesive composition and increase the mechanical strength of the pressure-sensitive adhesive layer.
  • the crosslinking agent may be a bifunctional (meth) acrylate such as a polyfunctional (meth) acrylate capable of being cured with an active energy ray, such as hexanediol diacrylate, or a trifunctional to hexafunctional (meth) acrylate .
  • the crosslinking agent is used in an amount of about 0.001 part by weight to about 5 parts by weight, specifically about 0.003 part by weight to about 3 parts by weight, specifically about 0.005 part by weight, and more preferably, about 0.005 part by weight, based on 100 parts by weight of the total (meth) acrylate containing hydroxyl group and Parts by weight to about 1 part by weight. There is an effect of excellent adhesion and reliability in the above range.
  • the adhesive layer may have a thickness of from about 10 ⁇ ⁇ to about 50 ⁇ ⁇ , preferably from about 20 ⁇ ⁇ to about 30 ⁇ ⁇ . Within this range, impact and bending properties may be simultaneously excellent.
  • a release film may be further formed on the lower surface of the adhesive layer.
  • the release film is a conventional film known to those skilled in the art and can prevent the adhesive layer from being contaminated by external foreign matter.
  • FIG. 2 is a cross-sectional view of an optical display device according to an embodiment of the present invention.
  • the flexible optical display 300 includes a display portion 310, a polarizing plate 320, a touch screen panel 330, a window film 340, and a film 350 for an optical display device
  • the optical display device film 350 may include a film for an optical display device according to an embodiment of the present invention.
  • the display unit 310 for driving the flexible optical display 300 may include an optical element including an OLED, an LED, a quantum dot light emitting diode (QLED) formed on a substrate and a substrate, or an LCD device .
  • the display unit 310 may include a lower substrate, a thin film transistor, an organic light emitting diode, a planarization layer, a protection layer, and an insulation layer.
  • the polarizing plate 320 may implement polarizing of the inner light or prevent reflection of external light to realize a display or increase the contrast ratio of the display.
  • the polarizing plate may be composed of a polarizer alone.
  • the polarizing plate may include a polarizing film and a protective film formed on one or both sides of the polarizing film.
  • the polarizing plate may include a polarizer and a protective coating layer formed on one or both sides of the polarizer.
  • the polarizer, the protective film, and the protective coating layer may be conventional ones known to those skilled in the art.
  • the touch screen panel 330 senses a change in capacitance generated when a conductor such as a human body or a stylus touches the touch panel, and generates an electrical signal.
  • the display unit 310 can be driven by this signal.
  • the touch screen panel 330 may include a first sensor electrode and a second sensor electrode formed between the first sensor electrode and the first sensor electrode, the second sensor electrode being formed by patterning a flexible and conductive conductor. have.
  • the conductor for the touch screen panel 330 may include, but is not limited to, metal nanowires, conductive polymers, carbon nanotubes, and the like.
  • the window film 340 may be formed at the outer periphery of the flexible optical display device 300 to protect the optical display device.
  • the window film 340 may be a window coating layer alone or a film having a window coating layer formed on a substrate layer.
  • the base layer may be formed of a polyester resin including polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate and the like, polycarbonate resin, poly (meth) acrylate resin including polymethylmethacrylate and the like, A polystyrene resin, a polyamide resin, a polyimide resin, and a cycloolefin polymer.
  • the base layer may be a single layer or may be a multilayer in which a plurality of films are laminated by an adhesive layer.
  • the substrate layer may be a film laminate in which a first film, an adhesive layer, and a second film are sequentially laminated.
  • the pressure-sensitive adhesive layer may be formed of the above-described OCA pressure-sensitive adhesive composition.
  • the window coating layer may be formed of a composition for a window coating layer comprising a silicone resin, a cross-linking agent, and an initiator.
  • an adhesive film is further formed between the polarizer 320 and the touch screen panel 330 and / or between the touch screen panel 330 and the window film 340 to form a polarizing plate, a touch screen panel, Can be strengthened.
  • FIG. 3 is a cross-sectional view of an optical display device according to another embodiment of the present invention.
  • the flexible optical display 400 includes a display unit 310, a polarizing plate 320, a touch screen panel 330, a window film 340 ', and a protective film 350'
  • the film 340 ' may include a film for an optical display device according to an embodiment of the present invention.
  • the optical display device film 350 ' may include a commonly used protective film for a window film.
  • the protective film 350 ' includes a film for an optical display according to an embodiment of the present invention may also be included in the scope of the present invention.
  • the optical display device of the present invention can also include a non-flexible optical display device.
  • the optical member of the present invention may comprise a film for an optical display device of the present invention.
  • the optical member comprises a window film and a protective film formed on the window film
  • the protective film may comprise a film for an optical display according to embodiments of the present invention.
  • the window film and the protective film can be directly formed in contact with each other.
  • the window film is not particularly limited, but may include a base coat layer formed of a silicone resin and a base coat layer for foldability.
  • the optical member is a film for an optical display device of the present invention. And a window coating layer formed on one surface of the optical display device film.
  • composition for the first coating layer impact resistant layer
  • impact resistant layer impact resistant layer
  • composition for the second coating layer used in the following examples and comparative examples are as follows.
  • A 46 parts by weight of a first urethane (meth) acrylate, (A2) 46 parts by weight of a second urethane (meth) acrylate, (B) 5 parts by weight of N-vinylpyrrolidone, And 3 parts by weight of an initiator were mixed to prepare a composition for a first coating layer in a solventless form.
  • (A1) 30.1 parts by weight of a third urethane (meth) acrylate, (A2) 16.5 parts by weight of a fourth urethane (meth) acrylate, 7.5 parts by weight of a (B1) (meth) acrylate monomer, 4 parts by weight of zirconia particles, 0.05 parts by weight of silicone additive (D), and 1.5 parts by weight of (E1) initiator were mixed and mixed with 40.7 parts by weight of methyl ethyl ketone as a solvent to prepare a composition for the second coating layer.
  • Shell structure composed of polybutyl acrylate (PBA) as the core and polymethylmethacrylate (PMMA) as the shell, the shell being 40 wt% of the organic nanoparticles, the average particle diameter being 230 nm, the refractive index being 1.48
  • Organic nanoparticles were prepared. 4 parts by weight of the organic nanoparticles prepared above and 100 parts by weight of a photopolymerization initiator (Irgacure 651) were added to 100 parts by weight of a monomer mixture containing 70% by weight of 2-ethylhexyl acrylate and 30% by weight of 4-hydroxybutyl acrylate Were mixed well in a glass container.
  • PBA polybutyl acrylate
  • PMMA polymethylmethacrylate
  • the mixture was polymerized by replacing the dissolved oxygen in the glass vessel with nitrogen gas and irradiating with ultraviolet rays using a low-pressure lamp (BL Lamp manufactured by Sankyo) for several minutes to obtain a partially polymerized product having a hydroxyl group having a viscosity of about 1000 CPS Meth) acrylic copolymer was obtained. 0.35 parts by weight of an additional photopolymerization initiator (c2) (Irgacure 184) was added to the resulting (meth) acrylic copolymer having a hydroxyl group to prepare a pressure-sensitive adhesive composition.
  • c2 additional photopolymerization initiator
  • the resultant pressure-sensitive adhesive composition was coated on a release-treated PET (polyethylene terephthalate film, thickness: 50 mu m) to form a pressure-sensitive adhesive film having a predetermined thickness.
  • a 75 mu m thick release film was covered on the upper side, and then the both sides were irradiated with a low-pressure lamp (BL Lamp manufactured by Sankyo Company) for 6 minutes to obtain a transparent pressure-sensitive adhesive sheet.
  • the PET film was removed from the transparent pressure-sensitive adhesive sheet to obtain a pressure-sensitive adhesive layer having a predetermined thickness.
  • (A1), 27 parts by weight of a third urethane (meth) acrylate, (A2) 13.5 parts by weight of a fourth urethane (meth) acrylate, 4.5 parts by weight of a (B1) (meth) acrylate monomer, 4 parts by weight of zirconia particles, 0.05 parts by weight of a silicone additive (D), and 1.5 parts by weight of an initiator (E1) were mixed and diluted to a solid concentration of 50% by weight by adding a solvent methyl ethyl ketone.
  • 0.1 part by weight of the (G) dye, and (H) 11 parts by weight of the antistatic agent were added so as to prepare a composition for the second coating layer.
  • composition for a coating layer 51 parts by weight of a second urethane (meth) acrylate, and 3 parts by weight of an initiator (C), based on the solids content, to obtain a composition for a coating layer .
  • a polyethylene terephthalate (PET) film (thickness: 23 mu m, manufacturer: Toray, product name: U403) was used as the substrate layer.
  • the composition for the first coating layer of Production Example 1 was applied to a predetermined thickness on one side of the base layer and the composition for the second coating layer of Production Example 2 was applied to the other side of the base layer to a predetermined thickness and dried at 80 ⁇ for 2 minutes And irradiated with light of 300 mJ / cm 2 under a nitrogen purge condition under a light source (metal halide lamp) to form a first coating layer and a second coating layer.
  • a light source metal halide lamp
  • the adhesive layer (thickness: 30 mu m) of Production Example 3 was adhered to the other surface of the first coating layer to prepare an optical display device film in which an adhesive layer, a first coating layer, a base layer and a second coating layer were sequentially formed .
  • An optical display device film was produced in the same manner as in Example 1, except that the thickness of the first coating layer was changed as shown in Table 1 below.
  • a polyethylene terephthalate (PET) film (thickness: 23 mu m, manufacturer: Toray, product name: U403) was used as the substrate layer.
  • the composition for the first coating layer of Production Example 1 was applied to a predetermined thickness on one surface of the base layer and the composition for the second coating layer of Production Example 4 was applied to the other surface of the base layer to a predetermined thickness and dried at 80 DEG C for 2 minutes And irradiated with light of 300 mJ / cm 2 under a nitrogen purge condition under a light source (metal halide lamp) to form a first coating layer and a second coating layer.
  • An adhesive layer (thickness: 30 mu m) of Production Example 3 was adhered to the other surface of the first coating layer to produce an optical display device film.
  • thermoplastic polyurethane (TPU) film (thickness: 50 mu m, manufacturer: Okura) was used as the substrate layer.
  • the composition for the second coating layer of Production Example 2 was coated on one side of the substrate layer, dried at 80 DEG C for 2 minutes, and irradiated with light of 300 mJ / cm < 2 > under a light source (metal halide lamp) A second coating layer having the same thickness was formed.
  • An optical display device film was produced in the same manner as in Comparative Example 1, except that the thickness of the TPU film was changed as shown in Table 1 below.
  • thermoplastic polyurethane (TPU) film (thickness: 150 mu m, manufacturer: Sheedom, XUS2093) was used as the first coating layer.
  • the composition for the second coating layer of Production Example 2 was coated on one surface of the first coating layer, dried at 80 DEG C for 2 minutes, irradiated with light of 300 mJ / cm < 2 > under a light source (metal halide lamp)
  • a second coating layer having the same thickness as the first coating layer was formed.
  • a polyethylene terephthalate film (thickness: 23 mu m, manufacturer: Toray, product name: U403) was used as the substrate layer.
  • the composition for the second coating layer of Production Example 2 was applied to the surface of the substrate layer to a predetermined thickness, dried at 80 DEG C for 2 minutes, irradiated with light of 300 mJ / cm < 2 > A second coating layer having the same thickness as in Example 1 was formed.
  • a thermoplastic polyurethane (TPU) film (thickness: 50 ⁇ ⁇ , manufactured by Okura)
  • an adhesive layer of Production Example 3 were sequentially formed on the other surface of the substrate layer
  • a film for optical display devices was produced in the same manner.
  • a polyethylene terephthalate film (thickness: 23 mu m, manufacturer: Toray, product name: U403) was used as the substrate layer.
  • the composition for the first coating layer of Production Example 1 was applied to a surface of the substrate layer to a predetermined thickness, dried at 80 DEG C for 2 minutes, irradiated with light of 300 mJ / cm < 2 > under a nitrogen purge condition under a light source A first coating layer having the same thickness as in Example 1 was formed.
  • the composition for the second coating layer of Production Example 2 was applied and cured in the same manner to form a second coating layer having the same thickness as in Example 1.
  • the pressure-sensitive adhesive layer of Production Example 3 was laminated on the other surface of the base layer to produce a film for an optical display device in which a second coating layer, a first coating layer, a base layer and an adhesive layer were successively formed.
  • An optical display device film was produced in the same manner as in Example 1, except that the composition for the coating layer of Production Example 5 was used in place of the composition for the first coating layer of Production Example 1.
  • the second coating layer The substrate layer Adhesive layer
  • the thickness unit is ⁇ m.
  • Comparative Example 7 is different from Example 1 in the stacking order of the layers.
  • Scuff test A glass plate (thickness: 75 ⁇ ⁇ ) was laminated on the lower surface of the adhesive layer of the optical display device films of Examples and Comparative Examples to prepare specimens.
  • the prepared specimens were fixed on a surface physical property measuring instrument (Heidon), steel wool # 0000 was mounted, a weight of 1.5 kg was raised, and the number of scratches after 10 reciprocations on the surface of the second coating layer Respectively. The lower the number, the higher the scratch resistance. When scratch resistance is evaluated, the number of scratch resistance is 5 or less so that scratch resistance is high.
  • Pen Drop Test A specimen was prepared by laminating a polyethylene terephthalate film (thickness: 125 ⁇ ) on the lower surface of the adhesive layer of the films for optical display devices of Examples and Comparative Examples. A ballpoint pen (manufactured by Bic Co.) was freely dropped from the second coating layer of the prepared specimen at a predetermined height to evaluate the initial height at which cracks occurred on the surface of the second coating layer. The cracks were confirmed by optical microscope. The higher the height, the better the impact resistance of Pen Drop.
  • a sample (length x width: 10 cm x 5 cm) was prepared by laminating a polyethylene terephthalate film (thickness: 75 m) on the lower surface of the adhesive layer of the optical display device films of Examples and Comparative Examples.
  • the number of cracks generated at the folded portion was evaluated at room temperature (25 ⁇ ) when the specimen was folded to have a radius of curvature of 1 mm and a length of 1/2 of the specimen. It was evaluated as 'good' when no crack occurred, 'crack when crack occurred,' and 'crackling when each layer was lifted'.
  • folding toward the polyethylene terephthalate film was made in the outfolding direction (tensile direction) and folding toward the second coating layer was made in the folding direction (compression direction).
  • Bending Stiffness The bending stiffness was measured with TA-XT plus (Texture Technologies). The films for optical display devices of Examples and Comparative Examples were cut into rectangular pieces of length x width (18 cm x 10 cm) to prepare test pieces. Bending stiffness was measured at 25 ⁇ ⁇ .
  • the specimen is bent in half in the transverse direction of the specimen and in the direction of the first coating layer of the specimen, and then the upper jig of the TA-XT plus is opposed to the lower jig of the TA- Respectively.
  • the portion of the specimen other than the portion folded at the end of the TA-XT plus was fixed with an acrylic adhesive tape.
  • the bent portion of the specimen and the center of the upper jig and the lower jig of the TA-XT plus coincided with each other.
  • the distance between the upper jig and the lower jig was 20 mm before the upper jig was pressed.
  • the lower jig is fixed and the upper jig is pressed at a speed of 10.2 mm / sec. While the interval between the upper jig and the lower jig is 2 mm (corresponding to a radius of curvature of 1 mm) And the force applied to the specimen was measured.
  • Haze was measured by placing films for optical display devices of Examples and Comparative Examples in NDH-9600 (manufactured by Nippon Denshoku) and directing the second coating layer to the light source.
  • Light transmittance The film for optical display devices of Examples and Comparative Examples was placed in CM-3600A (Konica Minolta), and the total coating light transmittance was measured with the second coating layer facing the light source.
  • CM-3600A Konica Minolta
  • Indentation modulus of elasticity In the films for optical display devices of Examples and Comparative Examples, the first coating layer or the adhesive layer formed on the lower surface of the film was removed. A nano indentor was prepared by using a nano indentation equipment (TI750 Ubi, hysitron) at a first coating layer or a middle portion (unit area: 1 mm 2 ) at 25 ° C and 55% (Vicker indenter) for 5 seconds with a force of 10 mN, creep for 2 seconds, and relaxation for 5 seconds to measure the indentation elastic modulus. The indentation elastic modulus was measured for the second coating layer or one portion thereof in the same manner.
  • Yellowness index (YI) and? YI: CM-3600A (Konica Minolta Co.) The films for optical display devices of Examples and Comparative Examples were placed and the yellow color index was measured with the second coating layer facing the light source.
  • the film for an optical display was left in a UV-B lamp for 72 hours, and the yellow index was measured in the same manner. The difference was calculated as? YI.
  • Adhesion force In a film for optical display devices of Examples and Comparative Examples, 10 pieces of 10 lines in width and 10 pieces in length were cut from the surface of the second coating layer to obtain a total of 100 pieces, and 3M adhesive tape was attached to the second coating layer and then peeled off The number of peeled specimens was confirmed. Good when the number of peeled specimens was 5 or less, and bad when the number of peeled specimens exceeded 5.
  • the film for an optical display according to the embodiment of the present invention satisfies the indentation elastic modulus of 10 MPa to 60 MPa measured on the surface of the first coating layer, even when the film does not include a thermoplastic polyurethane film, And excellent in folding property, scratch resistance, and low haze, thereby exhibiting excellent optical characteristics.
  • Example 4 including a dye and an antistatic agent showed little yellowing due to UV irradiation, and thus it was excellent in reliability and low in sheet resistance so that it could be used as a film for an optical display device.
  • the comparative example including the thermoplastic polyurethane film as the base layer instead of the first coating layer of the present invention and containing the polyurethane film as the base layer has a high indentation elastic modulus and is poor in at least one of foldability and scratch resistance Hayes was also high.
  • (A3) 54 parts by weight of the fifth urethane (meth) acrylate, 36 parts by weight of the (B2) (meth) acrylate monomer, 10 parts by weight of the silica particles (I), 0.2 parts by weight of the silicone additive (D) (E2) initiator in an amount of 3 parts by weight, and mixed with 55 parts by weight of methyl ethyl ketone as a solvent to prepare a composition for a second coating layer.
  • a polyethylene terephthalate (PET) film (thickness: 40 mu m, manufacturer: SKC, product name: TU94-40) was used.
  • the composition for the first coating layer of Production Example 1 was applied to a predetermined thickness on one side of the substrate layer and the composition for the second coating layer was applied to the other side of the substrate layer to a predetermined thickness and dried at 80 DEG C for 2 minutes , And irradiated with light of 300 mJ / cm 2 under a nitrogen halide lamp under a light source (metal halide lamp) to form a first coating layer (thickness: 100 ⁇ m) and a second coating layer.
  • PTT polyethylene terephthalate
  • the adhesive layer (thickness: 30 mu m) of Production Example 3 was adhered to the other surface of the first coating layer to prepare an optical display device film in which an adhesive layer, a first coating layer, a base layer and a second coating layer were sequentially formed .
  • compositions for the second coating layer were prepared by changing each component in the composition for the second coating layer as shown in Table 4 below.
  • the base layer shown in Table 4 was used as the base layer.
  • the composition for the first coating layer of Production Example 1 was used as the composition for the first coating layer.
  • the thickness of the second coating layer was changed as shown in Table 4 below.
  • An optical display device film was produced in the same manner as in Example 5.
  • the substrate layer The second coating layer (parts by weight) Solid content (% by weight) The thickness of the second coating layer (mu m) Kinds Thickness ( ⁇ m) (A3) (B2) (I) (E2) (D)
  • PET 40 54 36 10 3 0.2 - 1.5
  • PET 40 70 20 10 3 0.2 - 1.5
  • PET 40 70 20 10 3 0.2 - 1.5
  • PET 40 PET 40 63 27 10 3 0.2 - 3
  • Example 7 PET 40 70 20 10 3 0.2 - 1.5
  • Example 10 PI 30 63 27 10 3 0.2 - 1.5
  • Example 11 PC 50 63 27 10 3 0.2 - 1.5
  • Example 12 PI 50 54 36 10 3 0.2 45 5
  • Example 13 PI 50 54 36 10 3 0.2 33 5
  • PET film polyethylene terephthalate film, thickness: 40 mu m, manufacturer: SKC, product name: TU94-40
  • PC film polycarbonate film, thickness: 50 mu m, manufacturer: Teijin, product name: WRS148
  • PI film polyimide film, thickness: 50 ⁇ ⁇ , manufacturer: Kolon, product name: K-PI50
  • the thickness of the buffer layer was measured by SEM or TEM (microscope). When the cross-sectional thickness of the buffer layer was less than 2 mu m, it was evaluated as X that no buffer layer was formed. When the cross-sectional thickness of the buffer layer was 2 mu m or more,
  • Example 5 Indentation elastic modulus @ First coating layer (MPa) (GPa) < SEP > Haze (%) Light transmittance (%) YI Scratch resistance Folding ability Crack Strain (%) Whether the buffer layer is formed
  • Example 5 18 8.9 0.98 90.78 0.72 2 Good 13.0 X
  • Example 6 20 9.0 0.85 90.42 0.82 3 Good 11.5 X
  • Example 7 19 8.9 0.94 90.54 0.88 0 Good 9.50 X
  • Example 8 19 9.3 0.97 90.64 0.86 0 Good 7.70 X
  • Example 9 21 9.4 0.89 90.21 0.84 0 Good 6.50 X
  • Example 10 18 8.8 1.01 89.98 0.91 2 Good - O
  • Example 11 19 9.1 0.78 90.14 0.76 0 Good - X
  • Example 12 19 9.3 0.79 89.77 0.92 0 Good 4.5 O
  • Example 13 19 9.2 0.81 89.83 0.93 0 Good 10 O
  • Example 14 19
  • the optical display device film of the present invention satisfies the indentation modulus of 10 MPa to 60 MPa measured on the surface of the first coating layer, even though it does not include the thermoplastic polyurethane film, And the haze was also low, so that the optical characteristics were excellent. It was also confirmed that when the polyimide film was used as the substrate layer, a buffer layer was formed.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

La présente invention a trait à un film pour un appareil d'affichage optique, et à un appareil d'affichage optique comprenant ce film. Le film pour un appareil d'affichage optique possède une première couche de revêtement, une couche de substrat et une seconde couche de revêtement formées de manière séquentielle à l'intérieur de celui-ci. La première couche de revêtement est constituée d'une composition de première couche de revêtement incluant du (méth)acrylate d'uréthane, de la N-vinylpyrrolidone et un initiateur, et le module d'élasticité de pression mesuré dans cette première couche de revêtement par rapport au film pour un appareil d'affichage optique est d'environ 10 MPa à environ 60 MPa.
PCT/KR2018/014907 2017-11-29 2018-11-29 Film pour appareil d'affichage optique, élément optique comportant ce film, et appareil d'affichage optique comprenant ce film WO2019107950A2 (fr)

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KR1020170162283A KR20190063306A (ko) 2017-11-29 2017-11-29 광학표시장치의 보호 필름, 이를 포함하는 광학 부재 및 이를 포함하는 광학표시장치

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KR102147278B1 (ko) 2019-07-05 2020-08-24 에스케이이노베이션 주식회사 폴리이미드계 필름, 커버윈도우용 필름 및 이를 포함하는 디스플레이 장치
KR102147349B1 (ko) 2019-09-30 2020-08-25 에스케이이노베이션 주식회사 윈도우 커버 필름 및 이를 이용한 플렉서블 디스플레이 패널
KR102147299B1 (ko) 2019-09-30 2020-08-24 에스케이이노베이션 주식회사 윈도우 커버 필름 및 이를 포함하는 플렉서블 디스플레이 패널
JPWO2021182443A1 (fr) * 2020-03-09 2021-09-16
US20230301046A1 (en) * 2020-03-09 2023-09-21 Dai Nippon Printing Co., Ltd. Stacked body for flexible display device, stacked body for display device and flexible display device
KR102458462B1 (ko) * 2020-06-23 2022-10-24 코오롱인더스트리 주식회사 간섭 무늬가 개선된 다층 구조의 필름 및 이를 포함하는 표시장치
KR102447338B1 (ko) * 2022-02-15 2022-09-26 이왕기 광학 투명 점착필름용 이형필름, 이를 포함하는 광학 투명 점착필름 및 이의 제조방법

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JP5309677B2 (ja) * 2007-09-21 2013-10-09 コニカミノルタ株式会社 ハードコートフィルムの製造方法
JP5324316B2 (ja) * 2008-05-27 2013-10-23 日東電工株式会社 粘着型偏光板、画像表示装置およびそれらの製造方法
JP4640535B1 (ja) * 2009-10-19 2011-03-02 東洋紡績株式会社 透明導電性フィルム及びこれを用いたタッチパネル
JP6495635B2 (ja) * 2014-12-05 2019-04-03 日東電工株式会社 透明導電性フィルム積層体及びそれを用いて得られるタッチパネル、並びに透明導電性フィルムの製造方法

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