WO2019107950A2 - Film for optical display apparatus, optical member comprising same, and optical display apparatus comprising same - Google Patents

Film for optical display apparatus, optical member comprising same, and optical display apparatus comprising same Download PDF

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Publication number
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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French (fr)
Korean (ko)
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WO2019107950A3 (en
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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/en

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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.

Abstract

Provided are a film for an optical display apparatus and an optical display apparatus comprising the same, the film for an optical display apparatus having a first coating layer, a substrate layer, and a second coating layer sequentially formed therein, wherein the first coating layer is formed of a first coating layer composition comprising urethane (meth)acrylate, N-vinylpyrrolidone, and an initiator, and the modulus of pressing elasticity measured in the first coating layer with respect to the film for an optical display apparatus is about 10MPa to about 60MPa.

Description

광학표시장치용 필름, 이를 포함하는 광학 부재 및 이를 포함하는 광학표시장치 Film for optical display device, optical member including the same, and optical display device including the same
본 발명은 광학표시장치용 필름, 이를 포함하는 광학 부재 및 이를 포함하는 광학표시장치에 관한 것이다.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.
현재 폴더블 광학표시장치의 개발이 가시화되면서, 외부 환경으로부터 폴더블 광학표시장치의 필름이 개발되고 있다. 광학표시장치의 필름은 광학표시장치의 외곽에 배치되어 디스플레이 영상을 볼 수 있게 하는 윈도우 필름 및/또는 윈도우 필름 상에 형성되어 윈도우 필름을 보호하기 위한 보호 필름을 포함할 수 있다. 종전 윈도우 필름용 보호 필름은 외부 환경으로부터의 보호와 리워크 특성이 우선시 되었으나, 폴딩 특성을 구현하지 못하여 폴더블 광학표시장치에 적용이 힘들었다.Currently, the development of a foldable optical display device has become visible, and a film of a foldable optical display device has been developed from an external environment. 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.
외부 환경에의 보호 특성은 일반적으로 경화 밀도 향상이나 경화도 향상 및 Rigid한 구조를 가진 resin들과 유기/무기 입자들을 조합하여, 단단하게 만드는 것으로 구현이 가능하다. 반면에 폴딩 특성의 경우, 경화 밀도의 감소 및 Flexibility가 좋은 resin과의 가교를 통해 말랑한 도막을 만드는 것으로 구현이 가능하다.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. On the other hand, in the case of the folding property, it is possible to realize a smooth coating by crosslinking with a resin having a reduced hardening density and good flexibility.
광학표시장치용 필름은 기재층 및 기재층 일면에 형성된 하드코팅층으로 구성될 수 있다. 굴곡성과 내충격성을 높이기 위해 열가소성 폴리우레탄(TPU) 필름 또는 박형의 폴리에틸렌테레프탈레이트(PET) 필름 또는 폴리이미드(PI) 필름을 복층 또는 이중층 구조로 적층시킨 기재층을 사용할 수 있다. 그러나, TPU 필름은 두께가 두껍고 외관 특성이 좋지 않아서 적용하는데 쉽지 않다. 박형의 PET 필름 또는 PI 필름은 외관 특성은 좋지만 내충격성 특히 하기 상술되는 pen drop에 의한 내충격성 평가 결과가 좋지 않았다.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. However, the TPU film is not easy to apply because it is thick and has poor appearance characteristics. Though 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.
본 발명의 배경기술은 한국공개특허 제2010-0055160호 등에 기술되어 있다.The background art of the present invention is disclosed in Korean Patent Publication No. 2010-0055160.
본 발명의 목적은 제1코팅층, 기재층 및 제2코팅층의 복층 구조이고 헤이즈가 낮아서 외관이 우수한 광학표시장치용 필름을 제공하는 것이다.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.
본 발명의 다른 목적은 제1코팅층, 기재층 및 제2코팅층의 복층 구조이고 제1코팅층 방향, 제2코팅층 방향 양자에 대해 폴딩성이 우수한 광학표시장치용 필름을 제공하는 것이다.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.
본 발명의 또 다른 목적은 제1코팅층, 기재층 및 제2코팅층의 복층 구조이고 내충격성, 내스크래치성, 내마모성, 부착력이 우수한 광학표시장치용 필름을 제공하는 것이다.It is still another object of the present invention 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 excellent in impact resistance, scratch resistance, abrasion resistance and adhesion.
본 발명의 또 다른 목적은 황색 지수가 낮고 내광 신뢰성이 우수하며 면저항이 낮고 기재층과 코팅층 간의 부착력이 우수한 광학표시장치용 필름을 제공하는 것이다.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.
1. 본 발명의 광학표시장치용 필름은 제1코팅층, 기재층, 제2코팅층이 순차적으로 형성되고, 상기 제1코팅층은 우레탄 (메트)아크릴레이트, N-비닐피롤리돈 및 개시제를 포함하는 제1코팅층용 조성물로 형성되고, 상기 광학표시장치용 필름에 대하여 상기 제1코팅층 면에서 측정된 압입 탄성율(indentation modulus)이 약 10MPa 내지 약 60MPa이 될 수 있다.1. 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.
2. 본 발명의 광학표시장치용 필름은 제1코팅층, 기재층, 제2코팅층이 순차적으로 형성되고, 상기 제1코팅층은 우레탄 (메트)아크릴레이트를 포함하는 제1코팅층용 조성물로 형성되고, 상기 광학표시장치용 필름에 대하여 상기 제1코팅층 면에서 측정된 압입 탄성율이 약 10MPa 내지 약 60MPa이고, 상기 광학표시장치용 필름에 대하여 상기 제2코팅층 면에서 측정된 압입 탄성율이 약 5GPa 내지 약 12GPa이 될 수 있다. 2. 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 .
3. 2에서, 상기 제2코팅층은 우레탄 (메트)아크릴레이트; (메트)아크릴레이트 모노머; 지르코니아 입자, 실리카 입자 중 하나 이상; 실리콘계 첨가제; 및 개시제를 포함하는 제2코팅층용 조성물로 형성될 수 있다.3. 2, 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.
4. 1 내지 3에서, 상기 제2코팅층은 우레탄 (메트)아크릴레이트; (메트)아크릴레이트 모노머; 지르코니아 입자; 실리콘계 첨가제; 및 개시제를 포함하는 제2코팅층용 조성물로 형성될 수 있다.4. In 1 to 3, the second coating layer comprises urethane (meth) acrylate; (Meth) acrylate monomers; Zirconia particles; Silicone additive; And a second coating layer containing an initiator.
5. 1 내지 4에서, 상기 제1코팅층은 두께가 약 50㎛ 내지 약 150㎛가 될 수 있다.5. In 1 to 4, the first coating layer may have a thickness of from about 50 탆 to about 150 탆.
6. 1 내지 5에서, 상기 제2코팅층은 두께가 약 10㎛ 이하일 수 있다.6. In 1 to 5, the second coating layer may have a thickness of about 10 mu m or less.
7. 1 내지 6에서, 상기 기재층은 비 우레탄계 수지 필름이고, 두께가 약 50㎛ 이하일 수 있다.7. In 1 to 6, the base layer is a urethane-based resin film and may have a thickness of about 50 탆 or less.
8. 1 내지 7에서, 상기 기재층은 등방성 필름 또는 위상차 필름일 수 있다.8. In 1 to 7, the base layer may be an isotropic film or a retardation film.
9. 1 내지 8에서, 상기 우레탄 (메트)아크릴레이트, N-비닐피롤리돈, 개시제의 총합 100중량부 중 상기 우레탄 (메트)아크릴레이트 약 80중량부 내지 약 99중량부, 상기 N-비닐피롤리돈 약 0.1중량부 내지 약 10중량부, 상기 개시제 약 0.0001 중량부 내지 약 10중량부를 포함할 수 있다.9. The composition according to any one of 1 to 8, wherein from about 80 parts by weight to about 99 parts by weight of the urethane (meth) acrylate in the total of 100 parts by weight of the urethane (meth) acrylate, N-vinylpyrrolidone, About 0.1 parts by weight to about 10 parts by weight of pyrrolidone, and about 0.0001 to about 10 parts by weight of the initiator.
10. 1 내지 9에서, 상기 우레탄 (메트)아크릴레이트는 신율이 약 2% 내지 약 20%일 수 있다.10. In 1 to 9, the urethane (meth) acrylate may have an elongation of from about 2% to about 20%.
11. 1 내지 10에서, 상기 제2코팅층은 상기 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부 중, 상기 우레탄 (메트)아크릴레이트 약 40중량부 내지 약 85중량부, 상기 (메트)아크릴레이트 모노머 약 5중량부 내지 약 50중량부, 상기 지르코니아 입자 약 0.01중량부 내지 약 10중량부, 상기 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부에 대해, 상기 실리콘계 첨가제 약 0.01중량부 내지 약 5중량부, 상기 개시제 약 0.01중량부 내지 약 10중량부를 포함할 수 있다.11. The method according to any one of claims 1 to 10, wherein 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.
12. 1 내지 11에서, 상기 제2코팅층은 염료 및 대전 방지제를 더 포함할 수 있다.12. In 1 to 11, the second coating layer may further comprise a dye and an antistatic agent.
13. 12에서, 상기 제2코팅층 중 상기 염료는 약 0.05중량% 내지 약 0.1중량%, 상기 대전 방지제는 약 11중량% 이상 포함될 수 있다.13. In 12, 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%.
14. 1 내지 13에서, 상기 광학표시장치용 필름은 YI가 약 1.0 이하, 하기 식 1의 △YI가 약 1.0 이하일 수 있다.14. The optical display device according to any one of claims 1 to 13, wherein the YI is about 1.0 or less and the YYI of the formula (1) is about 1.0 or less.
<식 1><Formula 1>
△YI = Y1 - Y2YI = Y1 - Y2
(상기 식 1에서, Y2는 상기 광학표시장치용 필름에 대해 측정한 황색 지수,(In the above formula (1), Y2 represents the yellow index measured on the film for an optical display device,
Y1는 Y2를 측정한 상기 광학표시장치용 필름을 UV-B 램프 72시간 방치한 후 동일한 방법으로 측정한 황색 지수). And 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).
15. 1 내지 14에서, 상기 제2코팅층은 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 실리카 입자, 실리콘계 첨가제 및 개시제를 포함하는 제2코팅층용 조성물로 형성될 수 있다.15. In 1 to 14, 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.
16. 15에서, 상기 (메트)아크릴레이트 모노머는 알킬렌옥사이드기를 갖는 (메트)아크릴레이트 모노머를 포함할 수 있다.At 16. 15, the (meth) acrylate monomer may comprise a (meth) acrylate monomer having an alkylene oxide group.
17. 15에서, 상기 우레탄 (메트)아크릴레이트는 11관능 내지 20관능의 우레탄(메트)아크릴레이트를 포함할 수 있다.At 17. 17. 15, the urethane (meth) acrylate may comprise from 11 to 20 functional urethane (meth) acrylates.
18. 16에서 상기 제2코팅층은 상기 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 실리카 입자의 총합 100중량부 중, 상기 우레탄 (메트)아크릴레이트 약 40중량부 내지 약 85중량부, 상기 (메트)아크릴레이트 모노머 약 5중량부 내지 약 50중량부, 상기 실리카 입자 약 0.01중량부 내지 약 10중량부, 상기 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 실리카 입자의 총합 100중량부에 대해 상기 실리콘계 첨가제 약 0.01중량부 내지 약 5중량부 상기 개시제 약 0.01중량부 내지 약 10중량부를 포함할 수 있다.18. The method according to claim 16, wherein 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.
19. 15에서, 상기 기재층은 폴리이미드 필름이고, 상기 기재층과 상기 제2코팅층 사이에 버퍼층이 더 형성될 수 있다.19. In 15, the base layer is a polyimide film, and a buffer layer may be further formed between the base layer and the second coating layer.
20. 1 내지 2에서, 상기 제1코팅층 일면에 점착층이 더 형성될 수 있다.20. An adhesive layer may be further formed on one surface of the first coating layer at 1-2.
본 발명의 광학부재는 본 발명의 광학표시장치용 필름을 포함할 수 있다.The optical member of the present invention may comprise a film for an optical display device of the present invention.
본 발명의 광학표시장치는 본 발명의 광학표시장치용 필름을 포함할 수 있다. The optical display device of the present invention may include a film for an optical display device of the present invention.
본 발명은 제1코팅층, 기재층 및 제2코팅층의 복층 구조이고 헤이즈가 낮아서 외관이 우수한 광학표시장치용 필름을 제공하였다.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.
본 발명은 제1코팅층, 기재층 및 제2코팅층의 복층 구조이고 제1코팅층 방향, 제2코팅층 방향 양자에 대해 폴딩성이 우수한 광학표시장치용 필름을 제공하였다.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.
본 발명은 제1코팅층, 기재층 및 제2코팅층의 복층 구조이고 내충격성, 내스크래치성, 내마모성, 부착력이 우수한 광학표시장치용 필름을 제공하였다.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.
본 발명은 황색 지수가 낮고 내광 신뢰성 및 굴곡성이 우수하고 기재층과 코팅층 간의 부착력이 우수한 광학표시장치용 필름을 제공하였다.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.
도 1은 본 발명의 일 실시예에 따른 광학표시장치용 필름의 단면도이다.1 is a cross-sectional view of a film for an optical display device according to an embodiment of the present invention.
도 2는 본 발명의 일 실시예에 따른 광학표시장치의 단면도이다.2 is a cross-sectional view of an optical display device according to an embodiment of the present invention.
도 3은 본 발명의 다른 실시예에 따른 광학표시장치의 단면도이다.3 is a cross-sectional view of an optical display device according to another embodiment of the present invention.
도 4는 본 명세서에서 벤딩 스티프니스 측정 평가 도면이다.4 is a bending stiffness measurement evaluation drawing in this specification.
첨부한 도면을 참고하여 실시예에 대하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 동일 또는 유사한 구성 요소에 대해서는 동일한 도면 부호를 붙였다.The present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.
본 명세서에서 "상부"와 "하부"는 도면을 기준으로 정의한 것으로서, 시 관점에 따라 "상부"가 "하부"로 "하부"가 "상부"로 변경될 수 있고, "위(on)" 또는 "상(on)"으로 지칭되는 것은 바로 위뿐만 아니라 중간에 다른 구조를 개재한 경우도 포함할 수 있다. 반면, "직접 위(directly on)", "바로 위" 또는 "직접적으로 형성"으로 지칭되는 것은 중간에 다른 구조를 개재하지 않은 것을 의미한다.The terms "upper" and "lower" in this specification are defined with reference to the drawings, wherein "upper" may be changed to "lower", "lower" What is referred to as "on" may include not only superposition, but also intervening other structures in the middle. On the other hand, what is referred to as "directly on," " directly above, "or" directly formed, "
본 명세서에서 "(메트)아크릴"은 아크릴 및/또는 메타아크릴을 의미한다. As used herein, "(meth) acrylic" means acrylic and / or methacrylic.
본 명세서에서 우레탄 (메트)아크릴레이트의 "신율(elongation)"은 Instron 기기를 이용하여 두께 200㎛, 폭 10mm의 시편을 제작하여 표선 거리 30mm로 측정된 것(JIS K7311 기준)을 의미한다.In the present specification, the "elongation" of urethane (meth) acrylate means a specimen having a thickness of 200 μm 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).
본 명세서에서 유기 나노입자의 "평균 입경"은 Malvern社의 Zetasizer nano-ZS 장비로 수계 또는 유기계 용매에서 측정하여 Z-average 값으로 표현되는 유기 나노입자의 입경 및 SEM/TEM 관찰시 확인되는 입경이다.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, .
본 명세서에서 "면내 위상차(Re)"는 파장 550nm에서의 면내 위상차 값이며, 하기 식 A로 표시되는 값이다:In the present specification, "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:
<식 A><Formula A>
Re = (nx - ny) x dRe = (nx - ny) xd
(상기 식 A에서, nx, ny는 각각 파장 550nm에서 기재층의 지상축 방향의 굴절률, 진상축 방향의 굴절률이고, d는 기재층의 두께(단위:nm)).(In the above 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).
본 명세서에서 "광학표시장치용 필름"은 광학표시장치의 외곽에 배치되어 영상을 볼 수 있게 하는 윈도우 필름, 상기 윈도우 필름 상에 형성되어 윈도우 필름을 보호하기 위한 보호 필름, 또는 상기 윈도우 필름이 기재 필름 및 기재 필름 상에 형성된 코팅층을 포함할 때의 기재 필름을 의미할 수 있다.The term "film for an optical display device" in this specification 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.
본 명세서에서 수치 범위 기재시 X 내지 Y는 X 이상 Y 이하(X≤ 그리고 ≤Y)를 의미한다.In the specification, X to Y means not less than X and not more than Y (X? And? Y) when describing the numerical range.
이하, 본 발명의 일 실시예에 따른 광학표시장치용 필름을 도 1을 참조하여 설명한다. Hereinafter, a film for an optical display device according to an embodiment of the present invention will be described with reference to FIG.
도 1을 참조하면, 광학표시장치용 필름(100)은 제1코팅층(110), 기재층(130), 제2코팅층(120)이 순차적으로 형성될 수 있다. 기재층(130)에 제1코팅층(110), 제2코팅층(120)이 순차적으로 형성되거나 기재층(130)에 제2코팅층(120), 제1코팅층(110)이 순차적으로 형성될 경우 내스크래치성과 내충격 특성이 나빠지는 문제점이 있을 수 있다.Referring to FIG. 1, 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. When 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.
기재층The substrate layer
기재층(130)은 제1코팅층(110), 제2코팅층(110)을 각각 지지하여, 광학표시장치용 필름(100)의 기계적 강도를 높일 수 있다.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.
기재층(130)은 광학적으로 투명한 수지 필름일 수 있다. 예를 들면, 기재층(130)은 파장 550nm에서 광 투과율이 약 85% 내지 약 100%, 예를 들면 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 또는 100% 구체적으로 약 90% 내지 약 99%이고, 우레탄 결합을 함유하지 않는 비-우레탄계 수지 필름으로서, 폴리에틸렌테레프탈레이트(PET), 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리부틸렌나프탈레이트 등을 포함하는 폴리에스테르, 아크릴, 시클릭올레핀폴리머(COP), 트리아세틸셀룰로스(TAC) 등을 포함하는 셀룰로스 에스테르, 폴리비닐아세테이트, 폴리비닐클로라이드(PVC), 폴리노르보르넨, 폴리카보네이트(PC), 폴리아미드, 폴리아세탈, 폴리페닐렌에테르, 폴리페닐렌술피드, 폴리술폰, 폴리에테르술폰, 폴리아릴레이트, 폴리이미드(PI) 중 하나 이상으로 형성된 필름일 수 있다. 기재층(130)은 두께가 약 100㎛ 이하, 예를 들면 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100㎛, 바람직하게는 약 50㎛ 이하, 예를 들면 약 20㎛ 내지 약 50㎛가 될 수 있다. 상기 범위에서, 폴딩성, 내충격성, 내스크래치성이 좋을 수 있다.The substrate layer 130 may be an optically transparent resin film. For example, 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, 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 film may be formed of at least one of polycarbonate (PC), polyamide, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyarylate, polyimide (PI). The substrate layer 130 has a thickness About 100 탆 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 탆 to about 50 탆. Within this range, folding resistance, impact resistance and scratch resistance can be good.
기재층(130)은 굴절률이 약 1.40 내지 약 1.65, 예를 들면 1.40, 1.45, 1.50, 1.55, 1.60, 1.65, 구체적으로 약 1.45 내지 약 1.60이 될 수 있다. 상기 범위에서, 제1코팅층과 제2코팅층 대비 굴절률이 적절하여 광학표시장치용 필름의 헤이즈가 높아지지 않고, 윈도우 필름 상부에 적층시 화면 시인성을 좋게 할 수 있다.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. In the above range, 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.
일 구체예에서, 기재층은 등방성 필름으로서, Re가 약 5nm 이하, 예를 들면 약 0nm 내지 약 1nm인 필름이 될 수 있다. 등방성 필름은 윈도우 필름 또는 윈도우 필름 하에 위치되는 각종 위상차 필름의 위상차 기능을 방해하지 않고 자체 기능을 나타내도록 할 수 있다. 다른 구체예에서, 기재층은 위상차 필름으로서, Re가 약 5nm 초과, 구체적으로 약 50nm 내지 약 30,000nm가 될 수 있다. 위상차 필름은 제1코팅층, 제2코팅층을 지지하면서도 광학보상기능을 가져 광학표시장치에 추가적인 기능을 제공할 수 있다.In one embodiment, 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. In another embodiment, 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.
예를 들면, 기재층은 Re가 약 100nm 내지 약 160nm, 예를 들면 λ/4 위상차 필름이 될 수 있다. 이 경우 편광 선글래스 효과를 나타낼 수 있다. 예를 들면, 기재층은 Re가 약 200nm 내지 약 300nm, 예를 들면 λ/2 위상차 필름이 될 수 있다. 이 경우 λ/4 위상차 필름과 함께 적층되어 디스플레이 형상을 좋게 하고 외광에 의한 반사율을 낮추어 화면 시인성을 좋게 할 수 있다. 예를 들면, 기재층은 Re가 약 8,000nm 이상, 약 15,000nm 이상, 약 30,000nm 이하인 초 고위상차 필름이 될 수 있다. 이 경우 무지개 무라나 얼룩 발생을 억제할 수 있다.For example, 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. For example, 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. For example, 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.
기재층(130)은 통상의 방법으로 제조될 수 있다. 예를 들면, 기재층은 상기 광학적으로 투명한 수지를 포함하는 조성물을 용융 압출 또는 용매 캐스팅 방법으로 필름화하여 제조될 수 있다. 제조된 필름은 통상의 방법으로 1축 또는 2축 연신시켜 상술한 위상차 Re를 갖도록 할 수 있다. Substrate layer 130 may be prepared by conventional methods. For example, 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.
도 1에서 도시되지 않았지만, 기재층은 표면 처리되지 않을 수도 있지만, 제1코팅층 또는 제2코팅층의 적층을 용이하게 하고 이들의 박리를 억제하며 추가적인 기능을 제공하기 위해 표면 처리될 수도 있다. 예를 들면, 플라즈마 처리, 코로나 처리 등으로 처리될 수 있다.Although not shown in Fig. 1, 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. For example, plasma treatment, corona treatment, or the like.
제1코팅층The first coating layer
제1코팅층(110)은 기재층(130)의 일면(기재층의 하부면)에 직접적으로 형성되어 기재층(130)과 제2코팅층(120)을 지지할 수 있다. 상기 "직접적으로 형성"은 기재층과 제1코팅층 사이에 임의의 다른 점착층, 접착층, 또는 점접착층이 개재되지 않음을 의미한다.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.
제1코팅층(110)은 점착층 등을 매개로 광학표시장치에서 디스플레이 소자에 점착될 수 있으며, 기재층과 제2코팅층은 각각 제1코팅층의 광출사면에 적층되어 있다. 따라서, 광학표시장치에 있어서 광원 또는 OLED 패널로부터 나온 발광은 제1코팅층, 기재층 및 제2코팅층의 순서로 투과될 수 있다. 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.
제1코팅층(110)은 내충격 코팅층으로서 기재층(130)이 비-우레탄계 수지 필름인 경우에는 광학표시장치용 필름의 내충격성이 급격하게 저하될 수 있다. 그러나, 비우레탄계 수지 필름인 기재층에 제1코팅층(110)을 형성함으로써 기재층으로 우레탄계 수지 필름을 사용한 경우 대비 폴딩성, 내충격성을 확보하면서, 헤이즈를 낮추어 광 특성을 좋게 할 수 있다. When the first coating layer 110 is an impact resistant coating layer and the base layer 130 is a non-urethane based resin film, the impact resistance of the optical display device film may be sharply lowered. However, when 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.
제1코팅층(110)은 두께가 약 50㎛ 내지 약 150㎛, 예를 들면 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150㎛, 바람직하게는 약 100㎛ 내지 약 150㎛가 될 수 있다. 상기 범위에서, 광학표시장치용 필름의 내충격성을 높이고 박형화 효과도 얻을 수 있으며 인장 방향과 압축 방향 모두에서 폴딩성을 좋게 할 수 있다.The first coating layer 110 may have a thickness ranging from about 50 μm to about 150 μm such as 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 125, 130, 135, 140, 145, 150 占 퐉, preferably about 100 占 퐉 to about 150 占 퐉. Within the above range, it is possible to increase the impact resistance of the film for an optical display device, obtain a thinning effect, and improve the foldability in both the stretching direction and the compressing direction.
제1코팅층(110)은 굴절률이 약 1.45 내지 약 1.7, 예를 들면 1.45, 1.5, 1.55, 1.60, 1.65, 1.7, 구체적으로 약 1.5 내지 약 1.65가 될 수 있다. 상기 범위에서, 제2코팅층, 기재층 대비 굴절률이 적절하여 광학표시장치용 필름의 헤이즈가 높아지지 않아서 외관이 우수하고, 윈도우 필름 상부에 적층시 화면 시인성을 좋게 할 수 있다.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.
제1코팅층(110)은 비 점착성의 코팅층으로서, 제1코팅층용 조성물을 기재층(130)의 일면에 도포한 후 경화시켜 형성될 수 있다. 도포 및 경화 방법은 당업자에게 알려진 통상의 방법에 의한다. 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.
제1코팅층용 조성물은 우레탄 (메트)아크릴레이트, N-비닐피롤리돈 및 개시제를 포함할 수 있다. 제1코팅층용 조성물은 통상적으로 알려진 고상 또는 액상의 내충격 보강제 등을 포함하지 않는다. 제1코팅층용 조성물은 우레탄 (메트)아크릴레이트, N-비닐피롤리돈, 개시제만으로도 충분한 내충격성을 나타낼 수 있다.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.
우레탄 (메트)아크릴레이트는 제1코팅층의 매트릭스를 형성하고 제1코팅층의 내충격 기능을 발현하게 할 수 있다. 우레탄 (메트)아크릴레이트는 신율이 약 2% 내지 약 20%, 예를 들면 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20%가 될 수 있다. 상기 신율 범위에서, 기재층이 비-우레탄계 수지 필름인 경우 광학표시장치용 필름의 내충격성, 내마모성, 압축 방향과 인장 방향 모두에서 폴딩성을 높일 수 있다. 또한, 상기 신율 범위에서 광학표시장치용 필름에 대해 제1코팅층에서 측정한 압입 탄성율이 약 10MPa 내지 약 60MPa, 예를 들면 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60MPa가 될 수 있다. 압입 탄성율이 상기 범위가 됨으로써 광학표시장치용 필름의 제2코팅층에서 측정한 내충격성이 우수하여 광학표시장치 용도로 사용할 수 있게 한다. 또한, 광학표시장치용 필름의 내마모성, 압축 방향과 인장 방향 모두에서 폴딩성을 높일 수 있다. 바람직하게는, 압입 탄성율은 약 10MPa 내지 약 40MPa가 될 수 있다. 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%. When 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. In addition, it is preferable that 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. When 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. In addition, the film for optical display devices can be improved in wear resistance, foldability in both the compression direction and the tensile direction. Preferably, the indentation modulus can be from about 10 MPa to about 40 MPa.
우레탄 (메트)아크릴레이트는 2관능 내지 6관능의 (메트)아크릴레이트로서 중량평균분자량이 약 1,000g/mol 내지 약 40,000g/mol, 예를 들면 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 4000g/mol가 될 수 있다. 상기 범위에서, 광학표시장치용 필름의 내충격성을 높이고, 내스크래치성, 굴곡성을 좋게 할 수 있다. 바람직하게는, 우레탄 (메트)아크릴레이트는 2관능 내지 3관능의 (메트)아크릴레이트계이고, 중량평균분자량이 약 1,000g/mol 내지 약 30,000g/mol, 바람직하게는 약 1,000g/mol 내지 약 5,000g/mol가 될 수 있다. 상기 범위에서, 박형 두께의 코팅층에도 상술한 내충격성, 내스크래치성, 폴딩성을 좋게 할 수 있고, 내마모성이 더 있도록 할 수 있다.(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. Within the above-mentioned range, the impact resistance of the film for an optical display device can be enhanced, and scratch resistance and bendability can be improved. Preferably, 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. &Lt; / RTI &gt; 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.
우레탄 (메트)아크릴레이트는 다관능의 폴리올, 다관능의 이소시아네이트 화합물 및 수산기를 갖는 (메트)아크릴레이트 화합물의 중합에 의해 제조되거나 상업적으로 판매되는 상품을 사용할 수 있다. 중합 방법은 당업자에게 알려진 바와 같다. 다관능의 폴리올은 방향족계 폴리올, 지방족계 폴리올, 지환족계 폴리올 중 하나 이상을 포함할 수 있다. 상기 폴리올은 폴리에스테르 디올, 폴리카보네이트 디올, 폴리올레핀 디올, 폴리에테르 디올, 폴리티오에테르 디올, 폴리실록산 디올, 폴리아세탈디올, 폴리에스테르아미드 디올 중 하나 이상을 포함할 수 있지만 이에 제한되지 않는다. 다관능의 이소시아네이트 화합물은 임의의 지방족, 지환족 또는 방향족 이소시아네이트를 포함할 수 있다. 수산기를 갖는 (메트)아크릴레이트 화합물은 히드록시에틸(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 히드록시프로필(메트)아크릴레이트, 히드록시부틸(메트)아크릴레이트, 클로로히드록시프로필(메트)아크릴레이트, 히드록시헥실(메트)아크릴레이트 등을 포함할 수 있지만, 이에 제한되지 않는다.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.
우레탄 (메트)아크릴레이트는 상술한 신율 등을 갖는, 모노머, 올리고머 또는 수지가 될 수 있다. 우레탄 (메트)아크릴레이트의 신율, 중량평균분자량은 우레탄 (메트)아크릴레이트 제조 과정시 각 성분 등의 적가 속도, 함량 등을 조절하여 달성할 수 있다.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.
우레탄 (메트)아크릴레이트는 우레탄 (메트)아크릴레이트, N-비닐피롤리돈, 개시제의 총합 100중량부 중 약 80중량부 내지 약 99중량부, 예를 들면 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99중량부, 바람직하게는 약 85중량부 내지 약 99중량부, 약 85중량부 내지 약 95중량부, 약 90중량부 내지 약 95중량부로 포함될 수 있다. 상기 범위에서, 광학표시장치용 필름의 내충격성과 내스크래치성이 우수하고 기재층과 함께 곡률반경을 낮추어 폴딩성을 높게 할 수 있으며 상술한 압입 탄성율을 확보할 수 있다.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. Within the above-mentioned range, 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-비닐피롤리돈은 제1코팅층과 기재층 간의 밀착력을 높이고, 광학표시장치용 필름의 반복적인 폴딩에서도 제1코팅층이 기재층으로부터 박리되는 것을 막을 수 있다.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-비닐피롤리돈은 우레탄 (메트)아크릴레이트, N-비닐피롤리돈, 개시제의 총합 100중량부 중 약 0.1중량부 내지 약 10중량부, 예를 들면 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10중량부, 바람직하게는 약 1중량부 내지 약 10중량부, 약 1중량부 내지 약 7중량부로 포함될 수 있다. 상기 범위에서, 광학표시장치용 필름의 다른 물성에 영향을 주지 않으면서 제1코팅층과 기재층 간의 밀착력을 좋게 할 수 있다.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. Within the above range, 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.
개시제는 우레탄 (메트)아크릴레이트를 경화(부분 중합)하거나, 제1코팅층용 조성물을 필름으로 경화시키기 위해서 사용할 수 있다. 개시제는 광중합 개시제, 열중합 개시제 중 하나 이상을 포함할 수 있다. 광중합 개시제는 광조사 등에 의한 경화 과정에서 라디칼 중합성 화합물의 중합 반응을 유도할 수 있는 것이라면, 어느 것이나 사용할 수 있다. 예를 들면, 광중합 개시제는 벤조인계, 히드록시 케톤계, 아미노케톤계 또는 포스핀 옥시드계 광개시제 등을 사용할 수 있다. 열중합 개시제는 전술한 물성을 갖는 것이라면 특별히 한정되지 않고, 예를 들면, 아조계 화합물, 과산화물계 화합물 또는 레독스(redox)계 화합물과 같은 통상의 개시제를 사용할 수 있다.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. For example, as the 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.
개시제는 우레탄 (메트)아크릴레이트, N-비닐피롤리돈, 개시제의 총합 100중량부 중 약 0.0001중량부 내지 약 10중량부, 예를 들면 0.0001, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10중량부, 구체적으로 약 0.1중량부 내지 약 10중량부로 포함될 수 있다. 상기 범위에서, 경화 반응이 완전히 진행될 수 있고, 잔량의 개시제가 남아 투과율이 저하되는 것을 막을 수 있고, 기포 발생을 낮출 수 있고 우수한 반응성을 가질 수 있다.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. In the above range, 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.
제1코팅층용 조성물은 용제를 포함하지 않는 무용제형이다. 그러나, 용제를 더 포함함으로써 제1코팅층용 조성물의 도포성을 높이고 제1코팅층의 표면 평활성을 높여 광 투과성을 좋게 할 수 있다. 용제는 당업자에게 알려진 통상의 용제로서 예를 들면 메틸에틸케톤 등을 포함할 수 있지만 이에 제한되지 않는다.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.
제1코팅층용 조성물은 통상의 첨가제를 더 포함할 수 있다. 예를 들면, 첨가제는 대전방지제, 산화방지제, 자외선 흡수제, 안료, 레벨링제 등을 포함할 수 있지만, 이에 제한되지 않는다.The composition for the first coating layer may further comprise conventional additives. For example, 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.
제2코팅층The second coating layer
제2코팅층(120)은 기재층(130)의 다른 일면에 직접적으로 형성되어 광학표시장치용 필름을 보호하거나 광학표시장치에서 광학표시장치용 필름 하부에 장착되는 각종 소자들 예를 들면 편광판 등을 보호할 수 있다. 상기 "직접적으로 형성"은 기재층과 제2코팅층 사이에 임의의 점착층, 접착층 또는 점접착층이 개재되지 않음을 의미한다.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.
제2코팅층(120)은 특별히 제한되지 않지만 하드코팅층이 될 수 있다.The second coating layer 120 is not particularly limited, but may be a hard coating layer.
제2코팅층(120)은 두께가 약 10㎛ 이하, 예를 들면 1, 2, 3, 4, 5, 6, 7, 8, 9, 10㎛, 구체적으로 약 5㎛ 이하가 될 수 있다. 상기 범위에서, 박형의 광학표시장치용 필름으로도 내충격성과 내스크래치성을 높일 수 있다.The second coating layer 120 may have a thickness of about 10 μm or less, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 μm, specifically about 5 μm or less. Within the above range, it is possible to increase impact resistance and scratch resistance even with thin film for optical display devices.
제2코팅층(120)은 굴절률이 약 1.40 내지 약 1.75, 예를 들면, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 구체적으로 약 1.45 내지 약 1.65가 될 수 있다. 상기 범위에서, 제1코팅층, 기재층 대비 굴절률이 적절하여 광학표시장치용 필름의 헤이즈가 높아지지 않고 외관이 우수하고, 윈도우 필름 상부에 적층시 화면 시인성을 좋게 할 수 있다.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.
제2코팅층(120)은 제2코팅층용 조성물로 형성될 수 있다.The second coating layer 120 may be formed of a composition for the second coating layer.
이하, 제2코팅층용 조성물의 일 실시 형태에 대해 설명한다.Hereinafter, one embodiment of the composition for the second coating layer will be described.
일 실시 형태로, 제2코팅층용 조성물은 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자, 실리콘계 첨가제 및 개시제를 포함할 수 있다.In one embodiment, 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.
우레탄 (메트)아크릴레이트는 4관능 내지 10관능의 (메트)아크릴레이트계로서 중량평균분자량이 약 1,000g/mol 내지 약 8,000g/mol, 예를 들면 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000g/mol, 신율이 약 1% 내지 약 25%, 예를 들면 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%가 될 수 있다. 상기 범위에서, 광학표시장치용 필름의 내충격성, 내스크래치성, 굴곡성을 좋게 할 수 있다.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%. Within the above range, it is possible to improve the impact resistance, scratch resistance and bendability of the optical display device film.
본 발명의 광학표시장치용 필름은 제1코팅층과 제2코팅층에 각각 포함된 우레탄 (메트)아크릴레이트의 신율 및 우레탄 (메트)아크릴레이트의 함량을 조절함으로써 최종적으로는 제1코팅층 중 우레탄 (메트)아크릴레이트의 총 신율을 제2코팅층 중 우레탄 (메트)아크릴레이트의 총 신율 대비 높여 내충격성과 아웃폴딩 및 인폴딩에서의 폴딩성을 좋게 할 수 있다.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.
광학표시장치용 필름(100)은 광학표시장치용 필름 즉 제1코팅층, 기재층, 제2코팅층이 순차적으로 형성된 3층 구조의 시편에 대하여 제2코팅층 면에서 측정한 압입 탄성율은 제1코팅층 면에서 측정한 압입 탄성율에 비하여 클 수 있다. 제1 코팅층 면에서 측정한 압입 탄성율은 약 10MPa 내지 약 60MPa, 예를 들면 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60MPa, 바람직하게는 약 10MPa 내지 약 40MPa, 제 2 코팅층 면에서 측정한 압입 탄성율은 약 5GPa 내지 약 12GPa, 예를 들면 5, 6, 7, 8, 9, 10, 11, 12GPa, 바람직하게는 약 6GPa 내지 약 10GPa가 될 수 있다. 상기 범위에서, 광학표시장치용 필름의 폴딩성과 내스크래치성이 모두 우수할 수 있다.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 &gt; 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. Within the above range, the film for an optical display device may have both excellent folding resistance and scratch resistance.
우레탄 (메트)아크릴레이트는 상술한 신율, 중량평균분자량, 관능기 개수를 갖는, 모노머, 올리고머 또는 수지가 될 수 있다.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.
일 구체예에서, 우레탄 (메트)아크릴레이트는 상술 신율, 중량평균분자량, 관능기 수 범위 내에서 신율, 중량평균분자량, 관능기 수 중 하나 이상이 서로 다른 2종 이상 바람직하게는 2종의 우레탄 (메트)아크릴레이트의 혼합물을 포함할 수 있다. 편의상, 상기 우레탄 (메트)아크릴레이트의 혼합물 중 하나의 우레탄 (메트)아크릴레이트를 "제3우레탄 (메트)아크릴레이트", 다른 하나의 우레탄 (메트)아크릴레이트를 "제4우레탄 (메트)아크릴레이트"라고 할 때, 제3우레탄 (메트)아크릴레이트, 제4우레탄 (메트)아크릴레이트는 상술한 신율, 중량평균분자량 또는 관능기 수 범위를 가지며, 이들은 신율, 중량평균분자량, 관능기수 중 하나 이상이 다를 수 있다.In one embodiment, 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. &Lt; / RTI &gt; For convenience, 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.
일 구체예에서, 제3우레탄 (메트)아크릴레이트는 7관능 내지 10관능의 (메트)아크릴레이트계이고, 중량평균분자량이 약 1,000g/mol 이상 약 4,000g/mol 미만, 예를 들면 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900g/mol, 신율이 약 1% 이상 약 15% 미만, 예를 들면 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14%이 될 수 있다. 상기 범위에서, 광학표시장치용 필름의 내충격성, 내스크래치성, 굴곡성을 좋게 할 수 있다. 바람직하게는, 제3우레탄 (메트)아크릴레이트는 9 관능 내지 10관능의 (메트)아크릴레이트계로서 중량평균분자량이 약 1,500g/mol 내지 약 2,500g/mol, 신율이 약 5% 내지 약 10%가 될 수 있다. 상기 범위에서, 박형 두께의 제2코팅층에도 상술한 내충격성, 내스크래치성, 폴딩성을 좋게 할 수 있고, 내마모성이 더 있도록 할 수 있다. 제3우레탄 (메트)아크릴레이트는 UA11064(Entis社) 등을 사용할 수 있지만, 이에 제한되지 않는다.In one embodiment, 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%. &Lt; / RTI &gt; Within the above range, it is possible to improve the impact resistance, scratch resistance and bendability of the optical display device film. Preferably, 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 %. &Lt; / RTI &gt; 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).
일 구체예에서, 제4우레탄 (메트)아크릴레이트는 4 관능 내지 6관능의 (메트)아크릴레이트계이고, 중량평균분자량이 약 4,000g/mol 내지 약 8,000g/mol 예를 들면 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, 6500, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7600, 7700, 7800, 7900, 8000g/mol, 신율이 약 15% 내지 약 25% 예를 들면 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25%가 될 수 있다. 상기 범위에서, 광학표시장치용 필름의 내충격성, 내스크래치성, 굴곡성을 좋게 할 수 있다. 바람직하게는, 제4우레탄 (메트)아크릴레이트는 5 관능 내지 6관능의 (메트)아크릴레이트계로서 중량평균분자량이 약 4,000g/mol 내지 약 6,000g/mol, 신율이 약 15% 내지 약 20%가 될 수 있다. 상기 범위에서, 박형 두께의 제2코팅층에도 상술한 내충격성, 내스크래치성, 폴딩성을 좋게 할 수 있고, 스트레칭 효과가 더 있도록 할 수 있다. 제4우레탄 (메트)아크릴레이트는 CHTF-9696AN(켐톤社) 등을 사용할 수 있지만, 이에 제한되지 않는다.In one embodiment, 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%. Within the above range, it is possible to improve the impact resistance, scratch resistance and bendability of the optical display device film. Preferably, 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 %. &Lt; / RTI &gt; 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).
제4우레탄 (메트)아크릴레이트는 제3우레탄 (메트)아크릴레이트 대비 소정의 함량으로 포함될 수 있다. 그러한 경우 지르코니아 입자와 함께 포함시 내충격성, 내스크래치성을 높이고 굴곡성도 좋게 할 수 있다. 제4우레탄 (메트)아크릴레이트는 제3우레탄 (메트)아크릴레이트의 약 20중량% 내지 약 200중량%, 예를 들면 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200%, 바람직하게는 약 20중량% 내지 약 100중량%, 약 20중량% 내지 약 50중량%의 함량으로 포함될 수 있다. 상기 범위에서, 박형 두께의 제2코팅층에도 상술한 내충격성, 내스크래치성, 폴딩성을 좋게 할 수 있고, 스트레칭 효과가 더 있도록 할 수 있다.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. 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.
우레탄 (메트)아크릴레이트는 상술한 다관능의 폴리올, 다관능의 이소시아네이트 화합물 및 수산기를 갖는 (메트)아크릴레이트 화합물의 중합에 의해 제조될 수 있다. 다관능의 폴리올은 상술한 다관능의 폴리올을 포함할 수 있고, 다관능의 이소시아네이트 화합물은 상술한 다관능의 이소시아네이트 화합물을 포함할 수 있다. 수산기를 갖는 (메트)아크릴레이트 화합물은 히드록시에틸(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 히드록시프로필(메트)아크릴레이트, 히드록시부틸(메트)아크릴레이트, 클로로히드록시프로필(메트)아크릴레이트, 히드록시헥실(메트)아크릴레이트 등을 포함할 수 있지만, 이에 제한되지 않는다.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, and 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.
우레탄 (메트)아크릴레이트의 신율, 중량평균분자량은 우레탄 (메트)아크릴레이트 제조 과정시 각 성분 등의 적가 속도, 함량 등을 조절하여 달성할 수 있다.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.
우레탄 (메트)아크릴레이트는 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부 중 약 40중량부 내지 약 85중량부, 예를 들면 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85중량부로 포함될 수 있다. 상기 범위에서, 광학표시장치용 필름의 내충격성과 내스크래치성이 우수하고 기재층과 함께 곡률반경을 낮추어 폴딩성을 높게 할 수 있다. 바람직하게는, 약 40중량부 내지 약 80중량부, 약 50중량부 내지 약 80중량부로 포함될 수 있다.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. Within the above range, 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. Preferably from about 40 parts by weight to about 80 parts by weight, from about 50 parts by weight to about 80 parts by weight.
(메트)아크릴레이트 모노머는 2관능 내지 6관능의 (메트)아크릴레이트 모노머로서, 우레탄 (메트)아크릴레이트와 함께 경화되어 경도를 높일 수 있다. 바람직하게는, (메트)아크릴레이트 모노머는 우레탄기를 함유하지 않는 비-우레탄계 (메트)아크릴레이트 모노머일 수 있다.(Meth) acrylate monomers are bifunctional to hexafunctional (meth) acrylate monomers which can be cured with urethane (meth) acrylate to increase hardness. Preferably, the (meth) acrylate monomer may be a non-urethane based (meth) acrylate monomer that does not contain a urethane group.
(메트)아크릴레이트 모노머는 1,4-부탄디올 디(메트)아크릴레이트, 1,6-헥산디올 디(메트)아크릴레이트, 네오펜틸글리콜 디(메트)아크릴레이트, 폴리에틸렌글리콜 (600) 디(메트)아크릴레이트 등을 포함하는 폴리에틸렌글리콜 디(메트)아크릴레이트, 네오펜틸글리콜아디페이트 디(메트)아크릴레이트, 디시클로펜타닐 디(메트)아크릴레이트, 카프로락톤 변성 디시클로펜테닐 디(메트)아크릴레이트, 에틸렌옥시드 변성 디(메트)아크릴레이트, 디(메트)아크릴록시 에틸 이소시아누레이트, 알릴화 시클로헥실 디(메트)아크릴레이트, 트리시클로데칸디메탄올(메트)아크릴레이트, 디메틸롤 디시클로펜탄디(메트)아크릴레이트, 에틸렌옥시드 변성 헥사히드로프탈산 디(메트)아크릴레이트, 트리시클로데칸 디메탄올(메트)아크릴레이트, 네오펜틸글리콜 변성 트리메틸프로판 디(메트)아크릴레이트, 아다만탄 디(메트)아크릴레이트 또는 9,9-비스[4-(2-아크릴로일옥시에톡시)페닐]플루오렌 등과 같은 2관능 (메트)아크릴레이트; 트리메틸롤프로판 트리(메트)아크릴레이트, 디펜타에리쓰리톨 트리(메트)아크릴레이트, 프로피온산 변성 디펜타에리쓰리톨 트리(메트)아크릴레이트, 펜타에리쓰리톨 트리(메트)아크릴레이트, 프로필렌옥시드 변성 트리메틸롤프로판 트리(메트)아크릴레이트, 에톡시레이티드 (6) 트리메틸올프로판 트리(메트)아크릴레이트 등을 포함하는 에틸렌옥시드 변성 트리메틸올프로판 트리(메트)아크릴레이트, 또는 트리스(메트)아크릴록시에틸이소시아누레이트 등의 3관능 (메트)아크릴레이트; 디글리세린 테트라(메트)아크릴레이트 또는 펜타에리쓰리톨테트라(메트)아크릴레이트 등의 4관능 (메트)아크릴레이트; 디펜타에리쓰리톨 펜타(메트)아크릴레이트 등의 5관능 (메트)아크릴레이트; 및 디펜타에리쓰리톨 헥사(메트)아크릴레이트, 카프로락톤 변성 디펜타에리쓰리톨 헥사(메트)아크릴레이트 등의 6관능형 아크릴레이트 등을 들 수 있으나, 이에 제한되는 것은 아니다. 바람직하게는, (메트)아크릴레이트 모노머는 에톡시레이티드 (6) 트리메틸올프로판 트리(메트)아크릴레이트 등을 포함하는 에틸렌옥시드 변성 트리메틸올프로판 트리(메트)아크릴레이트 등의 3관능 (메트)아크릴레이트를 사용할 수 있다.(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 as bifunctional (meth) acrylate such as acrylate (meth) acrylate, acrylonitrile (meth) acrylate, ; (Meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Ethylene oxide modified trimethylolpropane tri (meth) acrylate including trimethylolpropane tri (meth) acrylate, ethoxylated (6) trimethylolpropane tri (meth) acrylate, Trifunctional (meth) acrylates such as acryloxyethyl isocyanurate; Tetrafunctional (meth) acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; Pentafunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; And 6-functional acrylates such as dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, but the present invention is not limited thereto. Preferably, 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.
(메트)아크릴레이트 모노머는 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부 중 약 5중량부 내지 약 50중량부, 예를 들면 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50중량부, 예를 들면 약 5중량부 내지 약 40중량부, 약 10중량부 내지 약 40중량부, 약 10중량부 내지 약 30중량부로 포함될 수 있다. 상기 범위에서, 박형 두께의 제2코팅층에도 상술한 내충격성, 내스크래치성, 폴딩성을 좋게 할 수 있다.(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. Within the above range, the second coating layer having a thin thickness can improve the impact resistance, scratch resistance and foldability described above.
지르코니아 입자는 제2코팅층의 내스크래치성을 높일 수 있다. 지르코니아 입자는 평균 입경(D50)이 약 200nm 이하, 예를 들면 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200nm, 구체적으로 약 5nm 이상 약 100nm 이하, 더 구체적으로 약 20nm 내지 약 50nm가 될 수 있다. 상기 범위에서, 제2코팅층의 헤이즈를 높이지 않고, 내스크래치성을 좋게 할 수 있다. 상기 "평균 입경(D50)"은 당업자에게 알려진 통상의 평균 입경을 의미한다. 지르코니아 입자는 표면 처리되지 않을 수도 있지만, (메트)아크릴레이트 화합물로 표면 처리됨으로써 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머와의 분산성이 좋아서 광학표시장치용 필름의 헤이즈를 더 낮출 수 있다.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. Although the zirconia particles may not be surface-treated, 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.
지르코니아 입자는 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부 중 약 0.01중량부 내지 약 10중량부, 예를 들면 0.01, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10중량부, 예를 들면 약 1중량부 내지 약 10중량부, 약 5중량부 내지 약 10중량부로 포함될 수 있다. 상기 범위에서, 박형 두께의 제2코팅층에도 상술한 내충격성, 내스크래치성, 폴딩성을 좋게 할 수 있다.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. Within the above range, the second coating layer having a thin thickness can improve the impact resistance, scratch resistance and foldability described above.
실리콘계 첨가제는 제2코팅층의 표면 특성을 좋게 하는 것으로 당업자에게 알려진 통상의 실리콘계 첨가제를 포함할 수 있다. 예를 들면, 실리콘계 첨가제는 폴리에테르 변성 아크릴계 폴리디메틸실록산 등을 포함할 수 있지만, 이에 제한되지 않는다. 실리콘계 첨가제는 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부에 대해 약 0.01중량부 내지 약 5중량부, 예를 들면 0.01, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5중량부, 구체적으로 약 0.1중량부 내지 약 2중량부, 약 0.1중량부 내지 약 1중량부로 포함될 수 있다. 상기 범위에서, 다른 성분에 영향을 주지 않고, 제2코팅층의 표면 특성이 좋을 수 있다.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. For example, 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.
개시제는 라디칼형 광개시제를 포함할 수 있다. 개시제는 아세토페논계 화합물, 벤질케탈계 화합물, 시클로헥실페닐케톤계 화합물이나 이들의 혼합물이 사용될 수 있으나, 이에 한정되는 것은 아니다. 바람직하게는 1-히드록시시클로헥실-1-페닐메타논, 2,2-디메톡시-2-페닐아세토페논, 2,2'-디에톡시 아세토페논, 2,2'-디부톡시 아세토페논, 2-히드록시-2-메틸 프로피오페논, p-t-부틸 트리클로로 아세토페논, p-t-부틸 디클로로 아세토페논, 4-클로로 아세토페논, 2,2'-디클로로-4-페녹시 아세토페논, 2-메틸-1-(4-(메틸티오)페닐)-2-모폴리노 프로판-1-온, 2-벤질-2-디메틸 아미노-1-(4-모폴리노 페닐)-부탄-1-온, 또는 이들의 혼합물이 될 수 있다.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. Preferred are 1-hydroxycyclohexyl-1-phenylmethanone, 2,2-dimethoxy-2-phenylacetophenone, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2 2-methylpropiophenone, pt-butyl trichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4- phenoxyacetophenone, 2- 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, or And mixtures thereof.
개시제는 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부에 대해 약 0.01중량부 내지 약 10중량부, 구체적으로 약 1중량부 내지 약 5중량부로 포함될 수 있다. 상기 범위에서, 경화 반응이 완전히 진행될 수 있고, 잔량의 개시제가 남아 투과율이 저하되는 것을 막을 수 있고, 또한 기포 발생을 낮출 수 있고 우수한 반응성을 가질 수 있다.(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. Within the above range, 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.
제2코팅층용 조성물은 용매를 더 포함함으로써 제2코팅층용 조성물의 코팅성을 용이하게 할 수 있다. 용매는 메틸에틸케톤, 메틸이소부틸케톤 등을 포함할 수 있지만, 이에 제한되지 않는다.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.
제2코팅층용 조성물은 제2코팅층에 추가적인 기능을 부여하기 위해 당업자에게 알려진 통상의 첨가제를 더 포함할 수 있다. 첨가제는 산화방지제, 안정화제, 계면활성제, 안료, 염료, 대전방지제, 레벨링제, 표면 에너지 조절제, 소포제, UV 흡수제, 저굴절화제 등을 포함할 수 있지만 이에 제한되지 않는다.The 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. The additives may include, but are not limited to, antioxidants, stabilizers, surfactants, pigments, dyes, antistatic agents, leveling agents, surface energy modifiers, defoamers, UV absorbers,
이하, 다른 실시 형태의 제2코팅층용 조성물을 설명한다.Hereinafter, the composition for the second coating layer of another embodiment will be described.
다른 실시 형태로, 제2코팅층용 조성물은 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자, 실리콘계 첨가제, 개시제, 염료 및 대전 방지제를 포함할 수 있다. 염료 및 대전 방지제를 더 포함하는 점을 제외하고는 일 실시 형태의 제2코팅층용 조성물과 실질적으로 동일하다.In another embodiment, 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.
염료는 기재층에 제1코팅층용 조성물과 제2코팅층용 조성물을 각각 도포한 후 UV 경화시켜 광학표시장치용 필름을 제조할 때, UV를 많이 조사할 경우 광학표시장치용 필름이 노란색으로 변하여 황색 지수 YI 값이 높아지는 것을 막으며, 광학표시장치용 필름의 내광 신뢰성을 높일 수 있다. 본 실시예의 제2코팅층용 조성물로 형성된 광학표시장치용 필름은 YI가 약 1.0 이하, △YI가 약 1.0 이하가 되어, 광학표시장치에서 고 신뢰성으로 사용될 수 있다. △YI는 하기 식 1에 의해 측정될 수 있다.When the composition for a first coating layer and the composition for a second coating layer are respectively coated on a substrate layer and UV cured to produce a film for an optical display device, when a large amount of UV is irradiated, the film for an optical display device turns yellow, The index YI value is prevented from being increased, and the light reliability of the optical display device film can be increased. 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).
<식 1><Formula 1>
△YI = Y1 - Y2YI = Y1 - Y2
(상기 식 1에서, Y2는 광학표시장치용 필름에 대해 측정한 황색 지수,(In the above formula (1), Y2 represents the yellow index measured on the film for an optical display device,
Y1는 Y2를 측정한 광학표시장치용 필름을 UV-B 램프에서 72시간 조사 후 상온 30분 방치한 후 동일한 방법으로 측정한 황색 지수).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).
바람직하게는, YI는 약 0 이상 0.6 이하, △YI는 약 0 이상 0.9 이하가 될 수 있다.Preferably, YI is about 0 or more and 0.6 or less, and? YI is about 0 or more and 0.9 or less.
염료는 최대 흡수 파장이 약 300nm 내지 약 500nm, 예를 들면 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500nm, 바람직하게는 약 300nm 내지 약 400nm 가 되는 염료를 포함할 수 있다. 상기 흡수 파장 범위에서, 광학표시장치용 필름 제조시 황변을 막고, 내광 신뢰성을 높일 수 있다. 염료는 PANAX GD-16(욱성 화학社), FP-1025, PA-905 등을 사용할 수 있지만, 이에 제한되지 않는다. 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. In the above absorption wavelength range, it is possible to prevent the yellowing in the production of a film for an optical display device, and to improve the light reliability. The dyes may be PANAX GD-16 (Woo Sung Chemical Co.), FP-1025, PA-905, and the like, but are not limited thereto.
염료는 제2코팅층 중 약 0.05중량% 내지 약 0.1중량%로 포함될 수 있다. 상기 범위에서, 다른 성분의 기능에 영향을 주지 않고 황변을 억제할 수 있으며 광학표시장치용 필름의 투과율이 낮아지는 것을 막을 수 있다. 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.
염료는 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부에 대해 약 0.05중량부 내지 약 0.15중량부, 바람직하게는 약 0.05중량부 내지 약 0.1중량부로 포함될 수 있다. 상기 범위에서, 다른 성분의 기능에 영향을 주지 않고 황변을 억제할 수 있으며 광학표시장치용 필름의 투과율이 낮아지는 것을 막을 수 있다. 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 . 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.
대전 방지제는 광학표시장치용 필름이 광학표시장치의 최 외곽에 배치되는 경우 제2코팅층의 면저항을 낮추어 정전기 발생을 억제한다. 이를 통해, 광학표시장치용 필름의 제2코팅층에서 측정한 면저항은 약 5 x 1011 Ω/□ 이하가 될 수 있다.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. As a result, 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.
대전 방지제는 당업자에게 알려진 통상의 대전 방지제를 포함할 수 있다. 예를 들면 대전 방지제는 이온성 액체를 사용함으로써, 본 발명의 제2코팅층 조성에서 면 저항을 충분히 낮출 수 있고, 장시간 사용에도 새어나오지 않을 수 있다. 이온성 액체로 테트라알킬암모늄계 양이온과 술포네이트 이미드계 음이온의 이온성 액체를 사용할 수 있다.The antistatic agent may include conventional antistatic agents known to those skilled in the art. For example, by using 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. As the ionic liquid, ionic liquids of tetraalkylammonium cations and sulfonate imide anions can be used.
대전 방지제는 제2코팅층 중 약 11중량% 이상, 바람직하게는 약 11중량% 내지 약 15중량%, 더 바람직하게는 약 11중량% 내지 약 13중량%로 포함될 수 있다. 상기 범위에서, 다른 성분의 기능에 영향을 주지 않고 대전 방지성을 좋게 할 수 있고, 기재층과 제2코팅층 간의 부착력이 좋을 수 있다.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.
대전 방지제는 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부에 대해 약 7중량부 이상 약 13중량부 미만, 바람직하게는 약 11중량부 이상 약 13중량부 미만, 약 11중량부 내지 약 12.5중량부로 포함될 수 있다. 상기 범위에서, 다른 성분의 기능에 영향을 주지 않고 대전 방지성을 좋게 할 수 있고, 기재층과 제2코팅층 간의 부착력이 좋을 수 있다.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.
이하, 또 다른 실시 형태의 제2코팅층용 조성물을 설명한다.Hereinafter, the composition for the second coating layer of still another embodiment will be described.
제2코팅층용 조성물은 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 실리카 입자, 실리콘계 첨가제 및 개시제를 포함할 수 있다.The composition for the second coating layer may comprise a urethane (meth) acrylate, a (meth) acrylate monomer, silica particles, a silicone additive and an initiator.
우레탄 (메트)아크릴레이트는 편의상 "제5우레탄(메트)아크릴레이트"라고 한다. 제5우레탄(메트)아크릴레이트는 11관능 내지 20관능, 바람직하게는 13관능 내지 18관능의 (메트)아크릴레이트계이고, 신율이 5% 내지 15%가 될 수 있다. 상기 범위에서, 광학표시장치용 필름의 내충격성, 내스크래치성, 굴곡성을 좋게 할 수 있다. 일 구체예에서, 제5우레탄(메트)아크릴레이트는 사이클로프로필렌기를 포함할 수 있다. 이러한 경우 가교 밀도 조절을 통한 우수한 내스크래치성의 효과가 있을 수 있다. 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. In one embodiment, the fifth urethane (meth) acrylate may comprise a cyclopropylene group. In this case, excellent scratch resistance can be obtained by controlling the crosslink density.
우레탄 (메트)아크릴레이트는 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 실리카 입자의 총합 100중량부 중 약 40중량부 내지 약 85중량부, 예를 들면 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85중량부로 포함될 수 있다. 상기 범위에서, 광학표시장치용 필름의 내충격성과 내스크래치성이 우수하고 기재층과 함께 곡률반경을 낮추어 폴딩성을 높게 할 수 있다. 바람직하게는, 약 40중량부 내지 약 80중량부, 약 40중량부 내지 약 80중량부, 약 50중량부 내지 약 80중량부로 포함될 수 있다.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. Within the above range, 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. Preferably from about 40 parts by weight to about 80 parts by weight, from about 40 parts by weight to about 80 parts by weight, from about 50 parts by weight to about 80 parts by weight.
(메트)아크릴레이트 모노머는 알킬렌옥사이드기를 갖는 (메트)아크릴레이트 모노머를 포함할 수 있다. 이를 통해 제2코팅층의 굴곡성을 좋게 할 수 있다. 상기 알킬렌옥사이드기는 탄소수 1 내지 탄소수 5, 바람직하게는 탄소수 2 내지 탄소수 5의 알킬렌옥사이드기가 될 수 있다. 예를 들면, (메트)아크릴레이트 모노머는 폴리에틸렌글리콜 (600) 디(메트)아크릴레이트 등을 포함하는 폴리에틸렌글리콜 디(메트)아크릴레이트, 프로필렌옥시드 변성 트리메틸롤프로판 트리(메트)아크릴레이트, 에톡시레이티드 (6) 트리메틸올프로판 트리(메트)아크릴레이트 등을 포함하는 에틸렌옥시드 변성 트리메틸올프로판 트리(메트)아크릴레이트 등을 포함할 수 있다. (메트)아크릴레이트 모노머는 우레탄 결합을 포함하지 않는 비-우레탄계로 2관능 내지 6관능의 (메트)아크릴레이트 모노머일 수 있다.(Meth) acrylate monomers may include (meth) acrylate monomers having an alkylene oxide group. Thus, the flexibility of the second coating layer can be improved. The alkylene oxide group may be an alkylene oxide group having from 1 to 5 carbon atoms, preferably from 2 to 5 carbon atoms. For example, 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.
(메트)아크릴레이트 모노머는 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 실리카 입자의 총합 100중량부 중 약 5중량부 내지 약 50중량부, 예를 들면 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50중량부, 예를 들면 약 5중량부 내지 약 40중량부, 약 10중량부 내지 약 40중량부, 약 10중량부 내지 약 30중량부로 포함될 수 있다. 상기 범위에서, 박형 두께의 제2코팅층에도 상술한 내충격성, 내스크래치성, 폴딩성을 좋게 할 수 있다.(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. Within the above range, the second coating layer having a thin thickness can improve the impact resistance, scratch resistance and foldability described above.
실리카 입자는 제2코팅층의 내스크래치성을 높일 수 있다. 실리카 입자는 평균 입경(D50)이 약 200nm 이하, 구체적으로 약 5nm 내지 약 100nm, 약 20nm 내지 약 50nm가 될 수 있다. 상기 범위에서, 제2코팅층의 헤이즈를 높이지 않고, 내스크래치성을 좋게 할 수 있다. 상기 평균 입경(D50)은 당업자에게 알려진 통상의 평균 입경을 의미한다. 실리카 입자는 표면 처리되지 않을 수도 있지만, (메트)아크릴레이트 화합물로 표면 처리됨으로써 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머와의 분산성이 좋아서 광학표시장치용 필름의 헤이즈를 더 낮출 수 있다.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.
실리카 입자는 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 실리카 입자의 총합 100중량부 중 약 0.01중량부 내지 약 10중량부, 예를 들면 0.01, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10중량부, 예를 들면 약 1중량부 내지 약 10중량부, 약 5중량부 내지 약 10중량부로 포함될 수 있다. 상기 범위에서, 박형 두께의 제2코팅층에도 상술한 내충격성, 내스크래치성, 폴딩성을 좋게 할 수 있다.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. Within the above range, the second coating layer having a thin thickness can improve the impact resistance, scratch resistance and foldability described above.
실리콘계 첨가제, 개시제는 상기에서 상술한 바와 같다.The silicon-based additive and the initiator are as described above.
제2코팅층용 조성물은 상술한 용제를 포함할 수 있다. The composition for the second coating layer may comprise the above-mentioned solvent.
상기 제2코팅층용 조성물은 기재층이 폴리이미드 필름일 경우 폴리이미드 필름을 일부 용해시키고 제2코팅층용 조성물과 폴리이미드 필름이 intermixing됨으로써 버퍼층을 형성할 수 있다. 버퍼층은 광학표시장치용 필름의 굴곡성, 내스크래치성 조절을 용이하게 할 수 있다.When the substrate layer is a polyimide film, 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.
기능성층Functional layer
도 1에서 도시되지 않았지만, 제2코팅층(120) 상(제2코팅층의 상부면)에는 기능성층이 더 형성되어 광학표시장치용 필름에 추가적인 기능을 제공할 수 있다. 예를 들면 기능성층은 내지문성(anti-finger), 저반사(low reflection), 눈부심 방지(anti-glare), 방오(anti-contamination), 반사방지(anti-reflection), 확산, 굴절 기능 중 하나 이상의 기능을 제공할 수 있다. 기능성층은 제2코팅층(120) 상에 기능층 형성용 조성물을 도포하여 형성하거나 접착층 또는 점착층을 통해 제2코팅층(120) 상에 적층될 수 있다. 다른 구체예에서, 기능성층은 제2코팅층(120)의 일면이 기능성층이 되도록 형성될 수도 있다. Although not shown in FIG. 1, 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. For example, 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.
일 구체예에서, 내지문성층은 불소 용제, 불소 모노머 또는 그의 올리고머, 실란 커플링제를 포함하는 조성물로 형성될 수 있다. 내지문성층은 두께가 약 20nm 내지 약 200nm, 바람직하게는 약 30nm 내지 약 100nm가 될 수 있다.In one embodiment, 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.
광학표시장치용 필름(100)은 가시광 영역 예를 들면 파장 약 380nm 내지 약 780nm에서 전광선 투과율이 약 89% 이상, 약 89% 내지 약 99%, 헤이즈가 약 1.5% 이하, 바람직하게는 약 1.1% 이하가 될 수 있다. 상기 범위에서, 외관이 좋아서 광학표시장치에 사용될 수 있다.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, &Lt; / RTI &gt; Within this range, the appearance is good and can be used in an optical display device.
광학표시장치용 필름(100)은 곡률반경이 약 5mm 이하 예를 들면 약 1mm 이하가 될 수 있다. 구체적으로, 광학표시장치용 필름(100)은 제2코팅층(120) 방향(압축 방향, compression direction)으로 폴딩시 곡률반경이 약 5mm 이하 예를 들면 3mm 이하가 될 수 있다. 광학표시장치용 필름(100)은 제1코팅층(110) 방향(인장 방향, tensile direction)으로 폴딩시 곡률반경이 약 5mm 이하, 약 3mm 이하 예를 들면 약 1mm 이하가 될 수 있다. 상기 범위에서, 폴딩성이 우수하여 플렉시블 광학표시장치에 사용될 수 있다. 상기 "곡률반경"은 광학표시장치용 필름 중 제1코팅층의 하부면에 두께 75㎛의 폴리에틸렌테레프탈레이트 필름이 적층되고 길이 x 폭 10cm x 5cm의 시편에 대하여 25℃에서 길이 방향의 1/2 되도록 접었을 때 접히는 부분에서 크랙이 발생하지 않게 될 때의 최소값을 의미한다.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 占 퐉 -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.
광학표시장치용 필름(100)은 벤딩 스티프니스(bending stiffness)가 약 7N 이하, 바람직하게는 약 5N 이하가 될 수 있다. 벤딩 스티프니스는 광학표시장치용 필름을 제2코팅층(하드코팅층) 방향으로 곡률반경 1 내지 3mm로 구부렸을 때 광학표시장치용 필름에 걸리는 힘이다. 벤딩 스티프니스가 클수록 광학표시장치용 필름을 곡률반경 1mm 내지 3mm로 구부렸을 때 광학표시장치용 필름에 걸리는 힘이 커져서 광학표시장치용 필름을 구부렸을 때 제1코팅층 및/또는 제2코팅층 중 하나 이상에 크랙이 발생하게 된다. 본 발명의 광학표시장치용 필름은 제1코팅층, 기재층, 및 제2코팅층 간의 분리 없이 광학표시장치용 필름 전체가 구부린 상태에서도 크랙 발생이 없도록 할 수 있다. 벤딩 스티프니스는 도 4에 따라 측정할 수 있다.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.
광학표시장치용 필름(100)은 두께가 약 250㎛ 이하, 구체적으로 약 220㎛ 이하가 될 수 있다. 상기 범위에서, 광학표시장치에 사용될 수 있다. The optical display device film 100 may have a thickness of about 250 탆 or less, specifically about 220 탆 or less. In the above range, it can be used in an optical display device.
이하, 본 발명의 다른 실시예의 광학표시장치용 필름을 설명한다.Hereinafter, a film for an optical display device according to another embodiment of the present invention will be described.
본 발명의 다른 실시예의 광학표시장치용 필름은 제2코팅층 하부면 즉 제2코팅층에서 기재층이 적층되는 면과 대향하는 면에 점착층이 더 형성될 수 있다. 점착층은 광학표시장치용 필름을 디스플레이 소자 예를 들면 편광판, 터치 패널, 윈도우 필름 등에 점착시킬 수 있다.In the film for an optical display device according to another embodiment of the present invention, 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.
점착층은 감압 점착제(PSA), 투명 점착제(OCA) 등을 포함할 수 있다. 일 구체예에서, 점착층은 (메트)아크릴계 점착층으로서, (메트)아크릴계 공중합체를 포함하는 점착제 조성물로 형성될 수 있다.The pressure sensitive adhesive layer may include a pressure sensitive adhesive (PSA), a transparent pressure sensitive adhesive (OCA), or the like. In one embodiment, the adhesive layer may be formed of a pressure sensitive adhesive composition comprising a (meth) acrylic copolymer as the (meth) acrylic adhesive layer.
일 구체예에서, 점착제 조성물은 (메트)아크릴계 공중합체, 가교제를 포함할 수 있다. (메트)아크릴계 공중합체는 알킬기를 갖는 (메트)아크릴계 단량체 및 수산기를 갖는 (메트)아크릴계 단량체, 카르복시산기를 갖는 (메트)아크릴계 단량체, 헤테로 지환족기를 갖는 (메트)아크릴계 단량체, 방향족기를 갖는 (메트)아크릴계 단량체, 지환족기를 갖는 (메트)아크릴계 단량체 중 하나 이상을 포함하는 단량체 혼합물의 공중합체일 수 있다. 가교제는 이소시아네이트계, 아민계, 에폭시계, 아지리딘계, 금속 킬레이트계 가교제 중 하나 이상을 포함할 수 있다.In one embodiment, 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.
다른 구체예에서, 점착제 조성물은 수산기를 갖는 (메트)아크릴계 공중합체를 위한 단량체 혼합물; 개시제; 및 매크로모노머와 유기 나노입자 중 하나 이상을 포함할 수 있다. 단량체 혼합물은 중합이 전혀 되지 않은 단량체 혼합물 상태로 점착제 조성물에 포함될 수도 있으나 단량체 혼합물이 일부 부분 중합된 부분 중합체로 포함될 수도 있다. 바람직하게는, 점착제 조성물은 수산기를 갖는 (메트)아크릴계 공중합체를 위한 단량체 혼합물; 개시제; 및 유기 나노입자를 포함할 수 있다. 상기 단량체 혼합물은 수산기 함유 (메트)아크릴레이트 및 알킬기 함유 (메트)아크릴레이트로 구성될 수 있다.In another embodiment, 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. Preferably, 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.
수산기 함유 (메트)아크릴레이트는 점착층의 점착력을 제공할 수 있다. 수산기 함유 (메트)아크릴레이트는 1개 이상의 수산기를 함유하는 (메트)아크릴레이트일 수 있다. 예를 들면, 수산기 함유 (메트)아크릴레이트는 2-히드록시에틸 (메트)아크릴레이트, 2-히드록시프로필 (메트)아크릴레이트, 3-히드록시프로필(메트)아크릴레이트, 2-히드록시부틸 (메트)아크릴레이트, 4-히드록시부틸 (메트)아크릴레이트, 6-히드록시헥실 (메트)아크릴레이트, 1,4-시클로헥산디메탄올 모노 (메트)아크릴레이트, 1-클로로-2-히드록시프로필 (메트)아크릴레이트, 디에틸렌글리콜 모노(메트)아크릴레이트, 1,6-헥산디올 모노(메트)아크릴레이트, 펜타에리스리톨 트리(메트)아크릴레이트, 디펜타에리스리톨 펜타(메트)아크릴레이트, 네오펜틸글라이콜 모노(메트)아크릴레이트, 트리메틸올프로판 디(메트)아크릴레이트, 트리메틸올에탄 디(메트)아크릴레이트, 2-히드록시-3-페닐옥시프로필(메트)아크릴레이트, 4-히드록시사이클로펜틸(메트)아크릴레이트, 4-히드록시사이클로헥실 (메트)아크릴레이트 및 사이클로헥산디메탄올 모노(메트)아크릴레이트 중 1종 이상일 수 있다. 수산기 함유 (메트)아크릴레이트는 상기 수산기 함유 (메트)아크릴레이트 및 알킬기 함유 (메트)아크릴레이트 총합 중 약 5중량% 내지 약 40중량%, 예를 들면 약 8중량% 내지 약 30중량%, 약 10중량% 내지 약 30중량%로 포함될 수 있다. 상기 범위에서 점착층의 접착력 및 내구 신뢰성이 더욱 향상될 수 있다.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. For example, 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, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4- Hydroxycyclopentyl (meth) acrylate (Meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and the like. 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.
알킬기 함유 (메트)아크릴레이트는 공중합체가 되어 점착층의 매트릭스를 형성할 수 있다. 알킬기 함유 (메트)아크릴레이트는 비치환된 탄소수 1 내지 20의 선형 또는 분지형의 알킬 (메트)아크릴산 에스테르를 포함할 수 있다. 예를 들면, 메틸 (메트)아크릴레이트, 에틸 (메트)아크릴레이트, 프로필 (메트)아크릴레이트, n-부틸 (메트)아크릴레이트, t-부틸 (메트)아크릴레이트, iso-부틸 (메트)아크릴레이트, 펜틸 (메트)아크릴레이트, 헥실 (메트)아크릴레이트, 헵틸 (메트)아크릴레이트, 에틸헥실 (메트)아크릴레이트, 옥틸 (메트)아크릴레이트, 이소옥틸 (메트)아크릴레이트, 노닐 (메트)아크릴레이트, 데실 (메트)아크릴레이트, 라우릴 (메트)아크릴레이트 및 이소보닐 (메트)아크릴레이트 중 하나 이상을 포함할 수 있다. 알킬기 함유 (메트)아크릴레이트는 상기 수산기 함유 (메트)아크릴레이트 및 알킬기 함유 (메트)아크릴레이트 총합 중 약 60중량% 내지 약 95중량%, 예를 들면 약 65중량% 내지 약 92중량%, 약 68중량% 내지 약 90중량%, 약 70중량% 내지 약 90중량%로 포함될 수 있다. 상기 범위에서 점착층의 접착력 및 내구 신뢰성이 더욱 향상될 수 있다.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. (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (Meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and isobonyl (meth) acrylate. 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.
상기 단량체 혼합물은 공중합성 단량체를 더 포함할 수 있다. 공중합성 단량체는 (메트)아크릴계 공중합체에 포함되어, (메트)아크릴계 공중합체, 점착제 조성물 또는 점착층에 추가적인 효과를 제공할 수 있다. 공중합성 단량체는 수산기 함유 (메트)아크릴레이트와 알킬기 함유 (메트)아크릴레이트와 다른 단량체로서, 에틸렌 옥사이드를 갖는 단량체, 프로필렌 옥사이드를 갖는 단량체, 아민기를 갖는 단량체, 알콕시기를 갖는 단량체, 인산기를 갖는 단량체, 설폰산기를 갖는 단량체, 페닐기를 갖는 단량체, 실란기를 갖는 단량체, 카르복시산기를 갖는 단량체, 및 아미드기 함유 (메트)아크릴레이트 중 하나 이상을 포함할 수 있다.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.
공중합성 단량체는 상기 수산기 함유 (메트)아크릴레이트 및 알킬기 함유 (메트)아크릴레이트 총합 100중량부에 대해 약 15 중량부 이하, 구체적으로 10 중량부 이하, 더욱 구체적으로는 약 0.05중량부 내지 약 8중량부로 포함될 수 있다. 상기 범위에서 점착제 조성물은 점착 필름의 접착력 및 리커버리성을 더욱 향상시킬 수 있다.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. In the above range, the pressure-sensitive adhesive composition can further improve the adhesive force and the recoverability of the pressure-sensitive adhesive film.
개시제는 상기 단량체 혼합물을 (메트)아크릴계 공중합체로 경화(부분 중합)하거나, 점성 액체를 필름으로 경화시키기 위해서 사용할 수 있다. 개시제는 광중합 개시제, 열중합 개시제 중 하나 이상을 포함할 수 있다. 광중합 개시제로서는, 광조사 등에 의한 경화 과정에서 하기 전술한 라디칼 중합성 화합물의 중합 반응을 유도할 수 있는 것이라면, 어느 것이나 사용할 수 있다. 예를 들면, 벤조인계, 히드록시 케톤계, 아미노케톤계 또는 포스핀 옥시드계 광개시제 등을 사용할 수 있다. 열중합 개시제는, 전술한 물성을 갖는 것이라면 특별히 한정되지 않고, 예를 들면, 아조계 화합물, 과산화물계 화합물 또는 레독스(redox)계 화합물과 같은 통상의 개시제를 사용할 수 있다.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. As the photopolymerization 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. For example, 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.
개시제는 (메트)아크릴계 공중합체를 구성하는 상기 수산기 함유 (메트)아크릴레이트 및 알킬기 함유 (메트)아크릴레이트 총합 100중량부에 대해 약 0.0001 중량부 내지 약 5중량부, 구체적으로 약 0.001 중량부 내지 약 3 중량부로 포함될 수 있다. 상기 범위에서 경화 반응이 완전히 진행될 수 있고, 잔량의 개시제가 남아 투과율이 저하되는 것을 막을 수 있고, 또한 기포 발생을 낮출 수 있고 우수한 반응성을 가질 수 있다.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. In the above range, 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.
매크로모노머는 활성 에너지선에 의해 경화 가능한 작용기를 가져, 수산기 함유 (메트)아크릴레이트 및 알킬기 함유 (메트)아크릴레이트와 중합될 수 있다. 구체적으로, 매크로모노머는 하기 화학식 1로 표시될 수 있다: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. Specifically, the macromonomer may be represented by the following formula (1): &lt; EMI ID =
<화학식 1>&Lt; Formula 1 >
Figure PCTKR2018014907-appb-I000001
Figure PCTKR2018014907-appb-I000001
(상기 화학식 1에서, R1은 수소 또는 메틸기, X는 단일 결합 또는 2가 결합기, Y는 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, n-부틸(메트)아크릴레이트, iso-부틸(메트)아크릴레이트, t-부틸(메트)아크릴레이트, 스티렌, (메트)아크릴로니트릴로부터 선택되는 1개 또는 2개 이상을 중합시켜 얻어지는 폴리머 쇄).(In Formula 1, 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.
매크로모노머는 수평균분자량이 약 2,000 내지 약 20,000, 구체적으로 약 2,000 내지 약 10,000, 더 구체적으로 약 4,000 내지 약 8,000이 될 수 있다. 상기 범위에서, 충분한 점착 강도를 얻을 수 있고, 내열성이 우수하고, 점착제 조성물의 점도 상승에 의한 작업성의 저하를 억제할 수 있다. 매크로모노머는 유리전이온도가 약 40℃ 내지 약 150℃, 구체적으로 약 60℃ 내지 약 140℃, 더 구체적으로 약 80℃ 내지 약 130℃가 될 수 있다. 상기 범위에서, 점착층은 충분한 응집력을 나타낼 수 있고, 끈끈한 정도나 점착력의 저하를 억제할 수 있다.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 캜 to about 150 캜, specifically from about 60 캜 to about 140 캜, more specifically from about 80 캜 to about 130 캜. 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.
2가 결합기는 C1 내지 C10의 알킬렌기, C7 내지 C13의 아릴알킬렌기, C6 내지 C12의 아릴렌기, -NR2-(이때, R2는 수소, 또는 C1 내지 C5의 알킬기), COO-, -O-, -S-, -SO2NH-, -NHSO2-, -NHCOO-, -OCONH, 또는 복소환으로부터 유도되는 기 등이 될 수 있다.2 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.
또한, 2가 결합기는 하기 화학식 1a 내지 화학식 1d로 표시될 수 있다:The divalent linking group may be represented by the following formulas (1a) to (1d):
<화학식 1a><Formula 1a>
Figure PCTKR2018014907-appb-I000002
Figure PCTKR2018014907-appb-I000002
<화학식 1b>&Lt; EMI ID =
Figure PCTKR2018014907-appb-I000003
Figure PCTKR2018014907-appb-I000003
<화학식 1c>&Lt; Formula 1c >
Figure PCTKR2018014907-appb-I000004
Figure PCTKR2018014907-appb-I000004
<화학식 1d><Formula 1d>
Figure PCTKR2018014907-appb-I000005
Figure PCTKR2018014907-appb-I000005
(상기 화학식 1a 내지 화학식 1d에서, *는 원소의 연결 부위)(In the above Chemical Formulas (1a) to (1d), * denotes the connecting site of the element)
매크로모노머는 시판품을 사용할 수 있다. 예를 들어, 말단이 메타크릴로일기이면서, Y에 해당되는 세그먼트가 메틸메타크릴레이트인 매크로모노머, Y에 해당되는 세그먼트가 세그먼트가 스티렌인 매크로모노머, Y에 해당되는 세그먼트가 세그먼트가 스티렌/아크릴로니트릴인 매크로모노머, Y에 해당되는 세그먼트가 세그먼트가 부틸아크릴레이트인 매크로모노머 등을 이용할 수 있다.Commercial macromonomers may be used. For example, 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.
매크로모노머는 상기 수산기 함유 (메트)아크릴레이트 및 알킬기 함유 (메트)아크릴레이트 총합 100중량부에 대해 약 20중량부 이하, 구체적으로 약 0.1중량부 내지 약 20중량부, 약 0.1중량부 내지 약 10중량부, 약 0.5중량부 내지 약 5중량부로 포함될 수 있다. 상기 범위에서, 점착층의 점탄성과 모듈러스 및 복원력의 균형을 이룰 수 있고, 점착층의 헤이즈 상승을 막을 수 있다. 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. Within the above range, 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.
유기 나노입자는 평균 입경이 약 10nm 내지 약 400nm, 구체적으로 약 10nm 내지 약 300nm, 더욱 구체적으로 약 30nm 내지 약 280nm, 더욱 구체적으로 약 50nm 내지 약 280nm가 될 수 있다. 상기 범위에서, 점착층의 폴딩에 영향을 주지 않으며, 가시광 영역에서 전광선 투과율이 약 90% 이상으로 점착층의 투명도가 좋을 수 있다.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. In the above range, 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.
유기 나노입자는 수산기를 갖는 (메트)아크릴계 공중합체와의 굴절률 차이가 약 0.1 이하, 구체적으로 약 0 이상 약 0.05 이하, 구체적으로 약 0 이상 약 0.02 이하가 될 수 있다. 상기의 범위에서, 점착층의 투명도가 우수할 수 있다. 유기 나노입자는 굴절률이 약 1.35 내지 약 1.70, 구체적으로 약 1.40 내지 약 1.60이 될 수 있다. 상기 범위에서, 점착층의 투명도가 우수할 수 있다.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.
유기 나노입자는 코어-쉘 형을 비롯하여 비드(bead)형 등의 단순 나노입자 등도 포함될 수 있으나, 이에 한정하지 않는다. 코어-쉘 형일 경우에, 상기 코어와 쉘은 하기 식 2를 만족할 수 있다: 즉, 코어와 쉘 모두 유기 물질인 나노입자일 수 있다. 상기와 같은 입자 형태를 가질 경우, 점착층의 폴딩성이 좋고, 탄성과 유연성의 발란스 물성에 효과가 있을 수 있다.The organic nanoparticles may include, but are not limited to, core-shell type and simple nanoparticles such as a bead type. In the case of a 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. When the above-mentioned particle form is used, the adhesive property of the adhesive layer is good, and the balance property of elasticity and flexibility can be effective.
<식 2><Formula 2>
Tg(c) < Tg(s)Tg (c) &lt; Tg (s)
(상기 식 2에서 Tg(c)는 코어의 유리전이온도(단위:℃)이고, Tg(s)는 쉘의 유리전이온도(단위:℃)이다).(Unit: 占 폚), and Tg (s) is the glass transition temperature (unit: 占 폚) of the shell.
본 명세서에서 "쉘"은 유기 나노입자 중 최외곽층을 의미한다. 코어는 하나의 구형 입자일 수 있다. 그러나, 코어는 상기의 유리전이온도를 갖는다면 구형 입자를 감싸는 추가적인 층을 더 포함할 수도 있다.As used herein, 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.
구체적으로, 코어의 유리전이온도는 약 -150℃ 내지 약 10℃, 구체적으로 약 -150℃ 내지 약 -5℃, 더욱 구체적으로 약 -150℃ 내지 약 -20℃가 될 수 있다. 상기 범위에서 점착층의 저온 및/또는 상온 점탄성 효과가 있을 수 있다. 코어는 상기의 유리전이온도를 갖는 폴리알킬(메트)아크릴레이트, 폴리실록산 또는 폴리부타디엔 중 1 종 이상 포함할 수 있다. Specifically, the glass transition temperature of the core can be from about -150 캜 to about 10 캜, specifically about -150 캜 to about -5 캜, more specifically about -150 캜 to about -20 캜. 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.
폴리알킬(메트)아크릴레이트는 폴리메틸아크릴레이트, 폴리에틸아크릴레이트, 폴리프로필아크릴레이트, 폴리부틸아크릴레이트, 폴리이소프로필아크릴레이트, 폴리헥실아크릴레이트, 폴리헥실메타크릴레이트, 폴리에틸헥실아크릴레이트 및 폴리에틸헥실메타크릴레이트, 폴리실록산 중 하나 이상을 포함할 수 있고, 반드시 이에 제한되는 것은 아니다. 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.
폴리실록산은 예를 들어, 오가노실록산 (공)중합체가 될 수 있다. 오가노실록산 (공)중합체는 가교가 되지 않은 것을 사용할 수도 있고, 가교된 (공)중합체를 사용할 수도 있다. 내충격성, 착색성을 위해 가교상태의 오가노 실록산 (공)중합체를 사용할 수 있다. 이는 가교된 형태의 오가노실록산으로써, 구체적으로 가교된 디메틸실록산, 메틸페닐실록산, 디페닐실록산 또는 그 2 이상의 혼합물 등을 사용할 수 있다. 2 이상의 오가노실록산이 공중합된 형태를 사용함으로써 굴절률 약 1.41 내지 약 1.50을 조절할 수 있다. 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. In order to impart impact resistance and colorability, 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.
오가노실록산 (공)중합체의 가교상태는 각종 유기용매에 의해 용해되는 정도를 가지고 판단할 수 있다. 가교 상태가 심화될수록 용매에 의해 용해되는 정도가 작아진다. 가교 상태를 판단하기 위한 용매로는 아세톤이나 톨루엔 등을 사용할 수 있으며, 구체적으로 오가노실록산 (공)중합체는 아세톤이나 톨루엔에 의해 용해되지 않는 부분을 가질 수 있다. 오가노실록산 공중합체의 톨루엔에 대한 불용성분이 약 30% 이상이 될 수 있다.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.
추가적으로 상기 오가노실록산 (공)중합체에는 알킬아크릴레이트 가교중합체를 더 포함할 수 있다. 상기 알킬아크릴레이트 가교중합체는 메틸아크릴레이트, 에틸아크릴레이트, n-부틸아크릴레이트, 2-에틸헥실 아크릴레이트 등을 사용할 수 있다. 예를 들어 유리전이온도가 낮은 n-부틸아크릴레이트 또는 2-에틸헥실 아크릴레이트를 사용할 수 있다.Additionally, 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. For example, n-butyl acrylate or 2-ethylhexyl acrylate having a low glass transition temperature may be used.
구체적으로, 쉘의 유리전이온도는 약 15℃ 내지 약 150℃, 구체적으로 약 35℃ 내지 약 150℃, 더욱 구체적으로 약 50℃ 내지 약 140℃가 될 수 있다. 상기의 범위에서 (메트)아크릴계 공중합체 중 유기 나노입자의 분산성이 우수할 수 있다. 쉘은 상기 유리전이온도를 갖는 폴리알킬메타아크릴레이트를 포함할 수 있다. 예를 들어, 폴리메틸메타크릴레이트(PMMA), 폴리에틸메타크릴레이트, 폴리프로필 메타크릴레이트, 폴리부틸메타크릴레이트, 폴리이소프로필메타크릴레이트, 폴리이소부틸메타크릴레이트 및 폴리사이클로헥실메타크릴레이트 중 하나 이상을 포함할 수 있고, 반드시 이에 제한되는 것은 아니다. Specifically, the glass transition temperature of the shell can be from about 15 캜 to about 150 캜, specifically from about 35 캜 to about 150 캜, more specifically from about 50 캜 to about 140 캜. 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. For example, it is possible to use polymethylmethacrylate (PMMA), polyethylmethacrylate, polypropylmethacrylate, polybutylmethacrylate, polyisopropylmethacrylate, polyisobutylmethacrylate and polycyclohexylmethacrylate Rate, &lt; / RTI &gt; but is not necessarily limited thereto.
코어는 유기 나노입자 중 약 30 중량% 내지 약 99중량%, 구체적으로 약 40중량% 내지 약 95중량%, 더욱 구체적으로 약 50중량% 내지 약 90중량%로 포함될 수 있다. 상기의 범위에서, 넓은 온도 범위에서 점착층의 폴딩성이 좋을 수 있다. 쉘은 유기 나노입자 중 약 1 중량% 내지 약 70 중량%, 구체적으로 약 5 중량% 내지 약 60 중량%, 더욱 구체적으로 약 10 중량% 내지 약 50 중량%로 포함될 수 있다. 상기의 범위에서, 넓은 온도 범위에서 점착층의 폴딩성이 좋을 수 있다.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. Within the above range, 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. Within the above range, the folding property of the adhesive layer may be good in a wide temperature range.
유기 나노입자는 상기 수산기 함유 (메트)아크릴레이트 및 알킬기 함유 (메트)아크릴레이트 총합 100중량부에 대해 약 0.1중량부 내지 약 20중량부, 구체적으로 약 0.5중량부 내지 약 10중량부, 구체적으로 약 0.5중량부 내지 약 8중량부로 포함될 수 있다. 상기 범위에서, 고온에서의 점착층의 모듈러스를 높게 하고, 점착층의 상온 및 고온에서의 폴딩성을 좋게 하고, 점착층의 저온 및/또는 상온 점탄성이 우수하게 할 수 있다.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. Within the above range, 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-
유기 나노입자는 통상의 유화중합, 현탁중합, 용액중합 방법으로 제조될 수 있다.The organic nanoparticles can be prepared by conventional emulsion polymerization, suspension polymerization, or solution polymerization.
점착제 조성물은 실란커플링제를 더 포함할 수 있다. 실란 커플링제는 당업자에게 알려진 통상의 것을 사용할 수 있다. 예를 들면, 3-글리시드옥시프로필트리메톡시실란, 3-글리시드옥시프로필트리에톡시실란, 3-글리시드옥시프로필메틸 디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡실란 등의 에폭시 구조를 갖는 규소 화합물; 비닐 트리메톡시 실란, 비닐 트리에톡시 실란, (메트)아크릴옥시 프로필 트리메톡시실란 등의 중합성 불포화기 함유 규소 화합물; 3-아미노프로필 트리메톡시실란, N-(2-아미노에틸)-3-아미노프로필 트리메톡시실란, N-(2-아미노에틸)-3-아미노프로필 메틸 디메톡시실란 등의 아미노기 함유 규소 화합물; 및 3-클로로 프로필 트리메톡시실란 등으로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있지만, 이들에 제한되는 것은 아니다. 실란커플링제는 상기 수산기 함유 (메트)아크릴레이트 및 알킬기 함유 (메트)아크릴레이트 총합 100 중량부에 대하여 약 0.01 중량부 내지 약 3중량부, 구체적으로 약 0.01 중량부 내지 약 1 중량부로 포함될 수 있다. 상기의 범위에서 상술한 고온 고습에서의 벤딩 상태에서 신뢰성이 확보될 수 있고, 저온, 상온, 고온 간의 박리력 차이가 낮을 수 있다. The pressure-sensitive adhesive composition may further include a silane coupling agent. As the 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-aminopropylmethyldimethoxysilane. ; And 3-chloropropyltrimethoxysilane, and the like, but are not limited thereto. 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.
점착제 조성물은 가교제를 더 포함할 수 있다. 가교제는 점착제 조성물의 가교도를 높여 점착층의 기계적 강도를 높일 수 있다. 가교제는 활성 에너지선으로 경화가 가능한 다관능성 (메트)아크릴레이트, 예를 들면 헥산디올디아크릴레이트 등의 2관능 (메트)아크릴레이트, 또는 3관능 내지 6관능의 (메트)아크릴레이트를 포함할 수 있다. 가교제는 상기 수산기 함유 (메트)아크릴레이트 및 알킬기 함유 (메트)아크릴레이트 총합 100 중량부에 대해 약 0.001 중량부 내지 약 5 중량부, 구체적으로 약 0.003 중량부 내지 약 3 중량부, 구체적으로 약 0.005 중량부 내지 약 1 중량부로 포함될 수 있다. 상기 범위에서 우수한 접착력과 신뢰성 증가의 효과가 있다.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.
점착층은 두께가 약 10㎛ 내지 약 50㎛, 바람직하게는 약 20㎛ 내지 약 30㎛가 될 수 있다. 상기 범위에서, 내충격성과 굴곡성이 동시에 우수한 효과가 있을 수 있다.The adhesive layer may have a thickness of from about 10 占 퐉 to about 50 占 퐉, preferably from about 20 占 퐉 to about 30 占 퐉. Within this range, impact and bending properties may be simultaneously excellent.
점착층의 하부면에는 이형 필름이 더 형성될 수 있다. 이형 필름은 당업자에게 알려진 통상의 필름으로서, 점착층이 외부 이물질에 의해 오염되는 것을 막을 수 있다.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.
이하, 도 2를 참조하여 본 발명의 일 실시예에 따른 광학표시장치를 설명한다. 도 2는 본 발명의 일 실시예에 따른 광학표시장치의 단면도이다.Hereinafter, an optical display device according to an embodiment of the present invention will be described with reference to FIG. 2 is a cross-sectional view of an optical display device according to an embodiment of the present invention.
도 2를 참조하면, 플렉시블 광학표시장치(300)는 디스플레이부(310), 편광판(320), 터치스크린패널(330), 윈도우 필름(340), 광학표시장치용 필름 (350)을 포함하고, 광학표시장치용 필름(350)은 본 발명의 실시예에 따른 광학표시장치용 필름을 포함할 수 있다.2, 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.
디스플레이부(310)는 플렉시블 광학표시장치(300)를 구동시키기 위한 것으로, 기판 및 기판 상에 형성된 OLED, LED, QLED(quantum dot light emitting diode) 또는 LCD 소자를 포함하는 광학 소자를 포함할 수 있다. 도 2에서 도시되지 않았지만, 디스플레이부(310)는 하부기판, 박막 트랜지스터, 유기발광다이오드, 평탄화층, 보호막, 절연막을 포함할 수 있다.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 . Although not shown in FIG. 2, 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.
편광판(320)은 내광의 편광을 구현하거나 또는 외광의 반사를 방지하여 디스플레이를 구현하거나 디스플레이의 명암비를 높일 수 있다. 편광판은 편광자 단독으로 구성될 수 있다. 또는 편광판은 편광자 및 편광자의 일면 또는 양면에 형성된 보호필름을 포함할 수 있다. 또는 편광판은 편광자 및 편광자의 일면 또는 양면에 형성된 보호코팅층을 포함할 수 있다. 편광자, 보호필름, 보호코팅층은 당업자에게 알려진 통상의 것을 사용할 수 있다.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. Or the polarizing plate may include a polarizing film and a protective film formed on one or both sides of the polarizing film. Or 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.
터치스크린패널(330)은 인체나 스타일러스(stylus)와 같은 도전체가 터치할 때 발생되는 커패시턴스의 변화를 감지하여 전기적 신호를 발생시키는 것으로, 이러한 신호에 의해 디스플레이부(310)가 구동될 수 있다. 터치스크린패널(330)은 플렉시블하고 도전성이 있는 도전체를 패턴화하여 형성되는 것으로, 제1센서 전극 및 제1센서 전극 사이에 형성되어 제1센서 전극과 교차하는 제2센서 전극을 포함할 수 있다. 터치스크린패널(330)을 위한 도전체는 금속나노와이어, 전도성 고분자, 탄소나노튜브 등을 포함할 수 있지만 이에 제한되지 않는다. 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.
윈도우 필름(340)은 플렉시블 광학표시장치(300)의 외곽에 형성되어 광학표시장치를 보호할 수 있다. 윈도우 필름(340)은 윈도우 코팅층 단독 또는 기재층에 윈도우 코팅층이 형성된 필름일 수 있다. 기재층은 폴리에틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리부틸렌테레프탈레이트, 폴리부틸렌나프탈레이트 등을 포함하는 폴리에스테르 수지, 폴리카보네이트 수지, 폴리메틸메타아크릴레이트 등을 포함하는 폴리(메트)아크릴레이트 수지, 폴리스티렌 수지, 폴리아미드 수지, 폴리이미드 수지, 시클로올레핀폴리머 중 하나 이상을 포함하는 필름일 수 있다. 기재층은 단일층일 수도 있고, 필름이 점착층에 의해 복수 개 적층된 다중층일 수도 있다. 예를 들면, 기재층은 제1필름, 점착층, 및 제2필름이 순차적으로 적층된 필름 적층체일 수 있다. 상기 점착층은 상기에서 상술한 OCA 점착제 조성물로 형성될 수 있다. 윈도우 코팅층은 실리콘 수지, 가교제, 및 개시제를 포함하는 윈도우 코팅층용 조성물로 형성될 수 있다.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. For example, 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.
도 2에서 도시되지 않았지만, 편광판(320)과 터치스크린패널(330) 사이 및/또는 터치스크린패널(330)과 윈도우 필름(340) 사이에는 점착필름이 더 형성됨으로써 편광판, 터치스크린패널, 윈도우 필름 간의 결합을 강하게 할 수 있다.Although not shown in FIG. 2, 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.
이하, 도 3을 참조하여 본 발명의 다른 실시예에 따른 광학표시장치를 설명한다. 도 3은 본 발명의 다른 실시예에 따른 광학표시장치의 단면도이다.Hereinafter, an optical display device according to another embodiment of the present invention will be described with reference to FIG. 3 is a cross-sectional view of an optical display device according to another embodiment of the present invention.
도 3을 참조하면, 플렉시블 광학표시장치(400)는 디스플레이부(310), 편광판(320), 터치스크린패널(330), 윈도우 필름(340'), 보호 필름(350')을 포함하고, 윈도우 필름(340')은 본 발명의 실시예에 따른 광학표시장치용 필름을 포함할 수 있다. 광학표시장치용 필름(350')은 통상적으로 사용되는 윈도우 필름용 보호필름을 포함할 수 있다. 그러나, 보호 필름(350')으로 본 발명의 일 실시예에 따른 광학표시장치용 필름을 포함하는 경우도 본 발명의 범위에 포함될 수 있다.3, 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. However, the case where 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.
이상, 플렉시블한 광학표시장치를 나타내었으나, 본 발명의 광학표시장치는 비-플렉시블한 광학표시장치도 포함할 수 있다.Although the flexible optical display device has been described above, the optical display device of the present invention can also include a non-flexible optical display device.
본 발명의 광학 부재는 본 발명의 광학표시장치용 필름을 포함할 수 있다. The optical member of the present invention may comprise a film for an optical display device of the present invention.
일 구체예에서, 광학 부재는 윈도우 필름 및 윈도우 필름 상에 형성된 보호 필름을 포함하고, 보호 필름은 본 발명의 실시예들에 따른 광학표시장치용 필름을 포함할 수 있다. 윈도우 필름과 보호 필름은 직접적으로 접하여 형성될 수 있다. 윈도우 필름은 특별히 제한되지 않지만, 폴딩성을 위해 기재층과 실리콘 수지로 형성된 윈도우 코팅층을 포함할 수 있다.In one embodiment, the optical member comprises a window film and a protective film formed on the window film, and 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.
다른 구체예에서, 광학 부재는 본 발명의 광학표시장치용 필름; 및 상기 광학표시장치용 필름의 일면에 형성된 윈도우 코팅층을 포함하는 윈도우 필름을 의미할 수 있다.In another embodiment, 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.
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 이는 본 발명의 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석될 수는 없다.Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
하기 실시예와 비교예에서 사용된 제1코팅층(내충격층)용 조성물의 각 성분은 다음과 같다.The components of the composition for the first coating layer (impact resistant layer) used in the following Examples and Comparative Examples are as follows.
(A)(A1)제1우레탄 (메트)아크릴레이트: SUO-4130(신아티앤시社, 2관능 (메트)아크릴레이트계, 신율: 20%)(A) (A1) First urethane (meth) acrylate: SUO-4130 (Shinatan Co., Ltd., difunctional (meth) acrylate type, elongation: 20%
(A2)제2우레탄 (메트)아크릴레이트: CHTF-9696BN(켐톤社, 중량평균분자량: 3850g/mol, 신율: 2.9%)(A2) Second urethane (meth) acrylate: CHTF-9696BN (Chemton, weight average molecular weight: 3850 g / mol, elongation: 2.9%
(B)N-비닐피롤리돈: 1-Vinyl-2-pyrrolidinone (시그마알드리치社)(B) N-vinylpyrrolidone: 1-Vinyl-2-pyrrolidinone (Sigma Aldrich)
(C)개시제: Irgacure 184 (BASF社)(C) Initiator: Irgacure 184 (BASF)
*우레탄 (메트)아크릴레이트의 신율은 Instron 측정 방법으로 평가하였다.* The elongation of urethane (meth) acrylate was evaluated by Instron measurement method.
하기 실시예와 비교예에서 사용된 제2코팅층(하드코팅층)용 조성물의 각 성분은 다음과 같다.The components of the composition for the second coating layer (hard coat layer) used in the following examples and comparative examples are as follows.
(A)(A1)제3우레탄 (메트)아크릴레이트: UA11064(Entis社, 10관능 (메트)아크릴레이트계, 중량평균분자량: 2,000g/mol, 신율:6%, 고형분:100%)(A) (A1) Third urethane (meth) acrylate: UA11064 (Entis, 10-functional (meth) acrylate type, weight average molecular weight: 2,000 g / mol, elongation: 6%, solid content:
(A2)제4우레탄 (메트)아크릴레이트: CHTF-9696AN(켐톤社, 6관능 (메트)아크릴레이트계, 중량평균분자량:4,500g/mol, 신율:16%, 고형분 83%)(A2) 4 urethane (meth) acrylate: CHTF-9696AN (6-functional (meth) acrylate system, weight average molecular weight: 4,500 g / mol, elongation: 16%, solid content: 83%
(A3)제5우레탄 (메트)아크릴레이트: SUO-1500T(신아티앤씨社, 15관능(메트)아크릴레이트계, 사이클로프로필렌기를 가짐)(A3) Fifth urethane (meth) acrylate: SUO-1500T (having a 15-functional (meth) acrylate-based, cyclopropylene group)
(B)(메트)아크릴레이트 모노머: (B) (Meth) acrylate monomer:
(B1)SR499(Sartomer社, 3관능 (메트)아크릴레이트계, 고형분 100%)(B1) SR499 (Sartomer, trifunctional (meth) acrylate series, 100% solids)
(B2)DPEA-12(일본화약社, 에틸렌옥사이드기 포함)(B2) DPEA-12 (Japan Epoxy Resin Co., Including ethylene oxide group)
(C)지르코니아 입자: SZK330A(Ranco社, 평균입경(D50):20nm 내지 50nm, 고형분 30%)(C) Zirconia particles: SZK330A (Ranco, average particle size (D50): 20 nm to 50 nm, solid content 30%)
(D)실리콘계 첨가제: BYK-3500(BYK社, 고형분 10%)(D) Silicone-based additive: BYK-3500 (BYK, 10% solids)
(E)개시제: (E) Initiator:
(E1)Irgacure 184(BASF社, 고형분 25%)(E1) Irgacure 184 (BASF, solids content 25%)
(E2)Omnirad 184(IGM社)(E2) Omnirad 184 (IGM)
(F)용제: 메틸에틸케톤(삼전순약社)(F) Solvent: methyl ethyl ketone (Samseon Pure Chemical Co.)
(G)염료: PANAX GD-16(욱성화학社, 최대흡수파장: 337nm)(G) Dyestuff: PANAX GD-16 (Yukseong Chemical Co., maximum absorption wavelength: 337 nm)
(H)대전 방지제: FC-4400(3M社, 트리부틸메틸암모늄 비스(트리플루오로메탄술포네이트)이미드, 이온성 액체)(H) Antistatic agent: FC-4400 (3M Company, tributylmethylammonium bis (trifluoromethanesulfonate) imide, ionic liquid)
(I)실리카 입자: SSK330(Ranco社, 평균입경:20내지 50nm)(I) Silica particles: SSK330 (Ranco, average particle diameter: 20 to 50 nm)
*우레탄 (메트)아크릴레이트의 신율은 Instron 측정 방법으로 평가하였다.* The elongation of urethane (meth) acrylate was evaluated by Instron measurement method.
제조예Manufacturing example 1: 제1코팅층용 조성물 제조 1: Preparation of Composition for First Coating Layer
고형분 기준으로, (A1)제1우레탄 (메트)아크릴레이트 46중량부, (A2)제2우레탄 (메트)아크릴레이트 46중량부, (B)N-비닐피롤리돈5중량부, (C)개시제 3중량부가 되도록 혼합하여 무용제 형으로 제1코팅층용 조성물을 제조하였다.(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.
제조예Manufacturing example 2: 제2코팅층용 조성물 제조 2: Preparation of Composition for Second Coating Layer
고형분 기준으로, (A1)제3우레탄 (메트)아크릴레이트 30.1중량부, (A2)제4우레탄 (메트)아크릴레이트 16.5중량부, (B1)(메트)아크릴레이트 모노머 7.50중량부, (C)지르코니아 입자 4중량부, (D)실리콘계 첨가제 0.05중량부, (E1)개시제 1.5중량부가 되도록 상기 성분들을 혼합하고, 용제로 메틸에틸케톤 40.7중량부에 혼합하여 제2코팅층용 조성물을 제조하였다.(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.
제조예Manufacturing example 3:  3: 점착층Adhesive layer 제조 Produce
코어는 폴리부틸 아크릴레이트(PBA), 쉘은 폴리메틸 메타크릴레이트(PMMA)로 이루어진 코어-쉘 구조이고, 쉘은 유기 나노입자 중 40 중량%이고, 평균입경은 230 nm이고, 굴절률은 1.48인 유기 나노입자를 제조하였다. 2-에틸헥실아크릴레이트 70 중량%, 4-히드록시부틸아크릴레이트 30 중량%를 포함하는 단량체 혼합물 100 중량부에 대하여 상기 제조한 유기 나노입자 4 중량부 및 광중합 개시제(이르가큐어 651) 0.005 중량부를 유리 용기 내에서 잘 혼합하였다. 유리 용기 내의 용해된 산소를 질소 기체로 교체하고, 수분 동안 저압 램프(Sankyo사에서 제조된 BL Lamp)를 사용하여 자외선을 조사함으로써 혼합물을 중합시켜 약 1000 CPS의 점도를 갖는 수산기를 갖는 부분 중합 (메트)아크릴계 공중합체 함유 용액을 수득하였다. 생성된 수산기를 갖는 (메트)아크릴계 공중합체에 부가적 광중합 개시제(c2)(이르가큐어 184)를 0.35중량부를 첨가하여 점착제 조성물을 제조하였다. 생성된 점착제 조성물을 이형처리된 PET(폴리에틸렌 테레프탈레이트 필름, 두께 50㎛) 상에 코팅하여 소정 두께를 갖는 점착필름을 형성하였다. 상부에 75㎛ 두께의 이형필름을 커버한 후, 양 면에 6분 동안 저압 램프(Sankyo사에서 제조된 BL Lamp)를 사용하여 조사하여 투명 점착 시트를 수득하였다. 상기 투명 점착 시트에서 PET 필름을 제거하여 소정 두께를 갖는 점착층을 얻었다.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. 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. 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.
제조예Manufacturing example 4: 제2코팅층용 조성물 제조 4: Preparation of Composition for Second Coating Layer
고형분 기준으로, (A1)제3우레탄 (메트)아크릴레이트 27중량부, (A2)제4우레탄 (메트)아크릴레이트 13.5중량부, (B1) (메트)아크릴레이트 모노머 4.5 중량부, (C)지르코니아 입자 4중량부, (D)실리콘계 첨가제 0.05중량부, (E1)개시제 1.5중량부가 되도록 상기 성분들을 혼합하고, 용제 메틸에틸케톤을 첨가하여 고형분 농도 50중량%로 희석시켰다. (G)염료 0.1중량부, (H)대전 방지제 11중량부를 되도록 염료와 대전 방지제를 첨가하여, 제2코팅층용 조성물을 제조하였다.(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.
제조예Manufacturing example 5: 코팅층용 조성물 제조 5: Preparation of composition for coating layer
고형분 기준으로, (A1)제1우레탄 (메트)아크릴레이트 46중량부, (A2)제2우레탄 (메트)아크릴레이트 51중량부, (C)개시제 3중량부가 되도록 혼합하여 무용제 형으로 코팅층용 조성물을 제조하였다.(A2), 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 .
실시예Example 1 One
기재층으로 폴리에틸렌테레프탈레이트(PET) 필름(두께:23㎛, 제조사:Toray, 제품명:U403)을 사용하였다. 기재층 일면에 제조예 1의 제1코팅층용 조성물을 소정의 두께로 도포하고, 기재층 다른 일면에 제조예 2의 제2코팅층용 조성물을 소정의 두께로 도포하고, 80℃에서 2분 동안 건조시키고, 질소 퍼징 조건에서 광원(metal halide 램프) 하에 300mJ/cm2의 광량을 조사하여 제1코팅층과 제2코팅층을 형성하였다. 상기 제1코팅층의 다른 일면에 상기 제조예 3의 점착층(두께:30㎛)을 점착시켜, 점착층, 제1코팅층, 기재층, 제2코팅층이 순차적으로 형성된 광학표시장치용 필름을 제조하였다.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 캜 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. 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 .
실시예Example 2 내지  2 to 실시예Example 3 3
실시예 1에서 제1코팅층의 두께를 하기 표 1과 같이 변경한 것을 제외하고는 동일한 방법으로 광학표시장치용 필름을 제조하였다.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.
실시예4Example 4
기재층으로 폴리에틸렌테레프탈레이트(PET) 필름(두께:23㎛, 제조사:Toray, 제품명:U403)을 사용하였다. 기재층 일면에 제조예 1의 제1코팅층용 조성물을 소정의 두께로 도포하고, 기재층 다른 일면에 제조예 4의 제2코팅층용 조성물을 소정의 두께로 도포하고, 80℃에서 2분 동안 건조시키고, 질소 퍼징 조건에서 광원(metal halide 램프) 하에 300mJ/cm2의 광량을 조사하여 제1코팅층과 제2코팅층을 형성하였다. 상기 제1코팅층의 다른 일면에 제조예 3의 점착층(두께:30㎛)을 점착시켜 광학표시장치용 필름을 제조하였다. 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.
비교예Comparative Example 1  One
기재층으로 열가소성 폴리우레탄(TPU) 필름(두께:50㎛, 제조사:Okura)을 사용하였다. 기재층 일면에 제조예 2의 제2코팅층용 조성물을 코팅하고, 80℃에서 2분 동안 건조시키고, 질소 퍼징 조건에서 광원(metal halide 램프) 하에 300mJ/cm2의 광량을 조사하여 실시예 1과 동일 두께의 제2코팅층을 형성하였다. 기재층의 다른 일면에 제조예 3의 점착층(두께:30㎛)을 형성하고, 열가소성 폴리우레탄(TPU) 필름(두께:50㎛, Okura社)을 적층시키고, 다시 제조예 3의 점착층(두께:30㎛)을 형성하여, 점착층, 열가소성 폴리우레탄(TPU) 필름(두께:50㎛, Okura社), 점착층, 열가소성 폴리우레탄(TPU) 필름, 제2코팅층이 순차적으로 적층된 광학표시장치용 필름을 제조하였다. A 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 &lt; 2 &gt; under a light source (metal halide lamp) A second coating layer having the same thickness was formed. (Thickness: 30 mu m) of Production Example 3 was formed on the other surface of the substrate layer, and a thermoplastic polyurethane (TPU) film (thickness: 50 mu m, Okura) (TPU) film (thickness: 50 mu m, manufactured by Okura), an adhesive layer, a thermoplastic polyurethane (TPU) film, and a second coating layer were sequentially laminated on a glass substrate To prepare a film for the device.
비교예Comparative Example 2 내지  2 to 비교예Comparative Example 4 4
비교예 1에서 TPU 필름의 두께를 하기 표 1과 같이 변경한 것을 제외하고는 동일한 방법으로 광학표시장치용 필름을 제조하였다.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.
비교예Comparative Example 5 5
제1코팅층으로 열가소성 폴리우레탄(TPU) 필름(두께:150㎛, 제조사:Sheedom , XUS2093)을 사용하였다. 제1코팅층 일면에 제조예 2의 제2코팅층용 조성물을 코팅하고, 80℃에서 2분 동안 건조시키고, 질소 퍼징 조건에서 광원(metal halide 램프) 하에 300mJ/cm2의 광량을 조사하여 실시예 1과 동일 두께의 제2코팅층을 형성하였다. 제1코팅층의 다른 일면에 제조예 3의 점착층(두께:30㎛)을 형성하여, 점착층, 열가소성 폴리우레탄(TPU) 필름(두께:150㎛, 제조사:Sheedom, XUS2093), 제2코팅층을 순차적으로 적층시켜 광학표시장치용 필름을 제조하였다.A 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 &lt; 2 &gt; under a light source (metal halide lamp) A second coating layer having the same thickness as the first coating layer was formed. (Thickness: 30 占 퐉) of Production Example 3 was formed on the other surface of the first coating layer and a pressure-sensitive adhesive layer, a thermoplastic polyurethane (TPU) film (thickness: 150 占 퐉, manufacturer: Sheedom, XUS2093) And sequentially laminated to produce a film for an optical display device.
비교예Comparative Example 6 6
기재층으로 폴리에틸렌테레프탈레이트 필름(두께:23㎛, 제조사:Toray, 제품명:U403)을 사용하였다. 기재층 일면에 제조예 2의 제2코팅층용 조성물을 소정의 두께로 도포하고, 80℃에서 2분 동안 건조시키고, 질소 퍼징 조건에서 광원(metal halide 램프) 하에 300mJ/cm2의 광량을 조사하여 실시예 1과 동일 두께의 제2코팅층을 형성하였다. 기재층의 다른 일면에, 제조예 3의 점착층(두께:30㎛), 열가소성 폴리우레탄(TPU) 필름(두께:50㎛, 제조사:Okura), 제조예 3의 점착층을 순차적으로 형성한 것을 제외하고는 동일한 방법으로 광학표시장치용 필름을 제조하였다.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 &lt; 2 &gt; A second coating layer having the same thickness as in Example 1 was formed. (Thickness: 30 占 퐉), a thermoplastic polyurethane (TPU) film (thickness: 50 占 퐉, manufactured by Okura) and 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.
비교예Comparative Example 7 7
기재층으로 폴리에틸렌테레프탈레이트 필름(두께:23㎛, 제조사:Toray, 제품명:U403)을 사용하였다. 기재층 일면에 제조예 1의 제1코팅층용 조성물을 소정의 두께로 도포하고, 80℃에서 2분 동안 건조시키고, 질소 퍼징 조건에서 광원(metal halide 램프) 하에 300mJ/cm2의 광량을 조사하여 실시예 1과 동일 두께의 제1코팅층을 형성하였다. 제1코팅층의 다른 일면에, 제조예 2의 제2코팅층용 조성물을 도포하고 동일한 방법으로 경화시켜 실시예 1과 동일 두께의 제2코팅층을 형성하였다. 기재층의 다른 일면에 제조예 3의 점착층을 적층시켜, 제2코팅층, 제1코팅층, 기재층, 점착층이 순차적으로 형성된 광학표시장치용 필름을 제조하였다.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 &lt; 2 &gt; under a nitrogen purge condition under a light source A first coating layer having the same thickness as in Example 1 was formed. On the other surface of the first coating layer, 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.
비교예Comparative Example 8 8
실시예 1에서, 제조예 1의 제1코팅층용 조성물 대신에 제조예 5의 코팅층용 조성물을 사용한 것을 제외하고는 동일한 방법으로 광학표시장치용 필름을 제조하였다.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.
제2코팅층The second coating layer 기재층The substrate layer 점착층Adhesive layer 제1코팅층 또는 TPU 필름The first coating layer or TPU film 점착층Adhesive layer 필름 총 두께Film Thickness
실시예 1Example 1 제조예 2Production Example 2 PET 필름PET film -- 제조예 1Production Example 1 제조예 3Production Example 3 108108
(두께:5)(Thickness: 5) (두께:23)(Thickness: 23) (두께:50)(Thickness: 50) (두께:30)(Thickness: 30)
실시예 2Example 2 제조예 2Production Example 2 PET 필름PET film -- 제조예 1Production Example 1 제조예 3Production Example 3 158158
(두께:5)(Thickness: 5) (두께:23)(Thickness: 23) (두께:100)(Thickness: 100) (두께:30)(Thickness: 30)
실시예 3Example 3 제조예 2Production Example 2 PET 필름PET film -- 제조예 1Production Example 1 제조예 3Production Example 3 208208
(두께:5)(Thickness: 5) (두께:23)(Thickness: 23) (두께:150)(Thickness: 150) (두께:30)(Thickness: 30)
실시예 4Example 4 제조예 4Production Example 4 PET 필름PET film -- 제조예 1Production Example 1 제조예 3Production Example 3 208208
(두께:5)(Thickness: 5) (두께:23)(Thickness: 23) (두께:150)(Thickness: 150) (두께:30)(Thickness: 30)
비교예 1Comparative Example 1 제조예 2Production Example 2 TPU 필름TPU film 제조예 3Production Example 3 TPU 필름TPU film 제조예 3Production Example 3 165165
(두께:5)(Thickness: 5) (두께:50)(Thickness: 50) (두께:30)(Thickness: 30) (두께:50)(Thickness: 50) (두께:30)(Thickness: 30)
비교예 2Comparative Example 2 제조예 2Production Example 2 TPU 필름TPU film 제조예 3Production Example 3 TPU 필름TPU film 제조예 3Production Example 3 215215
(두께:5)(Thickness: 5) (두께:50)(Thickness: 50) (두께:30)(Thickness: 30) (두께:100)(Thickness: 100) (두께:30)(Thickness: 30)
비교예 3Comparative Example 3 제조예 2Production Example 2 TPU 필름TPU film 제조예 3Production Example 3 TPU 필름TPU film 제조예 3Production Example 3 215215
(두께:5)(Thickness: 5) (두께:100)(Thickness: 100) (두께:30)(Thickness: 30) (두께:50)(Thickness: 50) (두께:30)(Thickness: 30)
비교예 4Comparative Example 4 제조예 2Production Example 2 TPU 필름TPU film 제조예 3Production Example 3 TPU 필름TPU film 제조예 3Production Example 3 365365
(두께:5)(Thickness: 5) (두께:150)(Thickness: 150) (두께:30)(Thickness: 30) (두께:150)(Thickness: 150) (두께:30)(Thickness: 30)
비교예 5Comparative Example 5 제조예 2Production Example 2 -- -- TPU 필름TPU film 제조예 3Production Example 3 185185
(두께:5)(Thickness: 5) (두께:150)(Thickness: 150) (두께:30)(Thickness: 30)
비교예 6Comparative Example 6 제조예 2Production Example 2 PET 필름PET film 제조예 3Production Example 3 TPU 필름TPU film 제조예 3Production Example 3 138138
(두께:5)(Thickness: 5) (두께:23)(Thickness: 23) (두께:30)(Thickness: 30) (두께:50)(Thickness: 50) (두께:30)(Thickness: 30)
비교예 7Comparative Example 7 제조예 2Production Example 2 PET 필름PET film -- 제조예 1Production Example 1 제조예 3Production Example 3 108108
(두께:5)(Thickness: 5) (두께:23)(Thickness: 23) (두께:50)(Thickness: 50) (두께:30)(Thickness: 30)
비교예 8Comparative Example 8 제조예 2Production Example 2 PET 필름PET film -- 제조예 5Production Example 5 제조예 3Production Example 3 108108
(두께:5)(Thickness: 5) (두께:23)(Thickness: 23) (두께:50)(Thickness: 50) (두께:30)(Thickness: 30)
*표 1에서 두께 단위는 ㎛이다.* In Table 1, the thickness unit is μm.
*비교예 7은 실시예 1 대비 각 층의 적층 순서가 다름.Comparative Example 7 is different from Example 1 in the stacking order of the layers.
실시예와 비교예의 광학표시장치용 필름에 대해 하기 물성을 평가하고, 그 결과를 하기 표 2, 표 3에 나타내었다.The following properties of the films for optical display devices of Examples and Comparative Examples were evaluated, and the results are shown in Tables 2 and 3 below.
(1)내스크래치성(Scuff test): 실시예와 비교예의 광학표시장치용 필름의 점착층 하부면에 유리판(두께:75㎛)을 적층시켜 시편을 제조하였다. 제조한 시편을 표면 물성 측정기(Heidon사)에 고정시키고, 스틸울(steel wool) #0000을 장착하고 1.5kg의 추를 올린 후 제2코팅층 표면에서 50mm 스케일로 왕복 10회 후 스크래치가 생긴 개수를 평가하였다. 개수가 낮을수록 내스크래치성이 높음을 의미한다. 내스크래치성 평가시 개수 5개 이하로는 내스크래치성이 높아서 사용 가능하다.(1) Scuff test: A glass plate (thickness: 75 占 퐉) 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.
(2)내충격성(Pen Drop Test): 실시예와 비교예의 광학표시장치용 필름의 점착층 하부면에 폴리에틸렌테레프탈레이트 필름(두께:125㎛)을 적층시켜 시편을 제조하였다. 제조한 시편 중 제2코팅층 위에서 볼펜(제조사:Bic사)을 소정의 높이에서 자유 낙하시켜 제2코팅층 표면에 크랙이 생기는 최초의 높이를 평가하였다. 크랙은 광학현미경으로 확인하였다. 높이가 높을수록 Pen Drop 내충격성이 우수함을 의미한다. (2) Pen Drop Test: A specimen was prepared by laminating a polyethylene terephthalate film (thickness: 125 탆) 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.
(3)폴딩성: 실시예와 비교예의 광학표시장치용 필름의 점착층 하부면에 폴리에틸렌테레프탈레이트 필름(두께:75㎛)을 적층시켜 시편(길이 x 폭: 10cm x 5cm)을 제조하였다. 상온(25℃)에서 상기 제조한 시편을 곡률반경 1mm로서 길이 방향의 1/2이 되도록 접었을 때 접히는 부분에서 발생하는 크랙의 개수를 평가하였다. 크랙이 발생하지 않은 경우 '양호', 크랙이 1개라도 발생한 경우 '크랙, 각 층 간의 들뜸이 생긴 경우 '들뜸'으로 평가하였다. 시편 중 폴리에틸렌테레프탈레이트 필름 쪽으로 접는 것을 아웃 폴딩 방향(인장 방향)으로 하고, 제2코팅층 쪽으로 접는 것을 인 폴딩 방향(압축 방향)으로 하였다. (3) Foldability: 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 캜) 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'. Among the specimens, 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).
(4)벤딩 스티프니스: 벤딩 스티프니스는 TA-XT plus(Texture Technologies)로 측정하였다. 실시예와 비교예의 광학표시장치용 필름은 가로 x 세로(18cm x 10cm)의 직사각형으로 절단하여 시편을 제조하였다. 벤딩 스티프니스는 25℃에서 측정하였다. (4) 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 占 폚.
도 4의 (A)를 참조하면, 상기 시편의 가로 방향 및 상기 시편 중 제1코팅층 방향으로 상기 시편을 반으로 구부린 다음 TA-XT plus의 상부 지그(jig)와 이와 대향하는 하부 지그(jig) 사이에 고정시켰다. 고정시 상기 시편의 말단을 TA-XT plus에 접히는 부분 이외의 부분을 아크릴 점착제 테이프를 사용하여 고정시켰다. 이때 상기 시편이 구부러지는 부위와 TA-XT plus의 상부 지그 및 하부 지그의 중심이 서로 일치하도록 하였다. 상부 지그를 누르기 전 상부 지그와 하부 지그 사이의 간격은 20mm이 되도록 하였다.4A, 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. At the time of fixation, 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. At this time, 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.
도 4의 (B)를 참조하면, 하부 지그는 고정시키고 상부 지그를 10.2mm/sec의 속도로 누르면서 상기 상부 지그와 하부 지그 사이의 간격이 2mm(곡률반경 1mm에 해당함)이 될 때까지 화살표 방향으로 각각 누르면서 시편에 걸리는 힘을 측정하였다.4B, 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.
(5)헤이즈: NDH-9600(Nippon denshoku사)에 실시예와 비교예의 광학표시장치용 필름을 넣고 제2코팅층이 광원을 향하도록 하여 헤이즈를 측정하였다.(5) Haze: 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.
(6) 광 투과율: CM-3600A(Konica Minolta사)에 실시예와 비교예의 광학표시장치용 필름을 넣고 제2코팅층이 광원을 향하도록 하여 전광선 투과율을 측정하였다.(6) 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.
(7)압입 탄성율: 실시예와 비교예의 광학표시장치용 필름에서 제1코팅층 또는 필름 하부면에 형성된 점착층을 제거하였다. 25℃ 및 55% 상대습도에서, 제1코팅층 또는 중 일 부분(단위면적:1mm2)에, 나노 인덴테이션(Nano indentation) 장비(TI750 Ubi, hysitron사)를 사용하여 나노 인덴터(nano indentor)(Vicker 압자)로 10mN의 힘으로 5초 동안 가하고, 2초 동안 크립(creep), 그리고 5초동안 relaxation하여 측정하여 압입 탄성율을 측정하였다. 동일한 방법으로 제2코팅층 또는 그 중 일 부분에 대하여 압입 탄성율을 측정하였다.(7) 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.
(8)황색 지수(YI)와 △YI: CM-3600A(Konica Minolta사)에 실시예와 비교예의 광학표시장치용 필름을 넣고 제2코팅층이 광원을 향하도록 하여 황색 지수를 측정하였다. 광학표시장치용 필름을 UV-B 램프로 72시간 방치한 후 동일한 방법으로 황색 지수를 측정하고, 그 차이를 △YI로 계산하였다.(8) 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.
(9)면저항: 실시예와 비교예의 광학표시장치용 필름에서 제2코팅층 면에 면저항 측정기 MCP-HT450의 프로브를 놓고 10초 후의 면저항을 측정하였다.(9) Surface resistance: In the films for optical display devices of Examples and Comparative Examples, the surface resistance of the sheet resistance measuring device MCP-HT450 was measured on the surface of the second coating layer after 10 seconds.
(10)부착력: 실시예와 비교예의 광학표시장치용 필름에서 제2코팅층 면에서 가로 10개 세로 10개의 선을 컷팅하여 총 100개의 시편을 얻고 3M사의 점착 테이프를 제2코팅층에 붙인 후 떼었을 때 박리된 시편의 개수를 확인하였다. 박리된 시편 개수가 5개 이하인 경우 양호, 박리된 시편 개수가 5개 초과인 경우 불량으로 평가하였다.(10) 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.
내스크래치성Scratch resistance 내충격성Impact resistance 폴딩성(in-folding)In-folding 폴딩성(out-folding)Out-folding 밴딩 스티프니스(N)Bending Stiffness (N) 헤이즈(%)Haze (%)
실시예 1Example 1 1One 66 양호Good 양호Good 2.72.7 0.310.31
실시예 2Example 2 1One 77 양호Good 양호Good 3.33.3 0.360.36
실시예 3Example 3 1One 88 양호Good 양호Good 4.54.5 0.410.41
실시예 4Example 4 33 88 양호Good 양호Good 4.34.3 0.620.62
비교예 1Comparative Example 1 1010 1010 양호Good 양호Good 5.35.3 1.281.28
비교예 2Comparative Example 2 1010 1212 크랙crack 크랙crack 6.26.2 1.161.16
비교예 3Comparative Example 3 1010 1212 크랙crack 크랙crack 6.36.3 1.351.35
비교예 4Comparative Example 4 1010 1515 크랙crack 크랙crack 7.17.1 1.141.14
비교예 5Comparative Example 5 1010 1010 양호Good 양호Good 3.63.6 0.930.93
비교예 6Comparative Example 6 88 66 양호Good 양호Good 5.15.1 0.980.98
비교예 7Comparative Example 7 1010 55 양호Good 양호Good 3.13.1 1.311.31
비교예 8Comparative Example 8 1010 55 들뜸Lifting 들뜸Lifting 3.23.2 1.341.34
광투과율(%)Light transmittance (%) 압입 탄성율@제1코팅층(MPa)Indentation elastic modulus @ First coating layer (MPa) 압입 탄성율@제2코팅층(GPa)(GPa) &lt; SEP &gt; YIYI △YI△ YI 면저항(Ω/□)Sheet resistance (Ω / □) 부착력Adhesion
실시예 1Example 1 91.691.6 1212 1010 0.650.65 0.860.86 -- 양호Good
실시예 2Example 2 91.891.8 1818 9.89.8 0.620.62 0.840.84 -- 양호Good
실시예 3Example 3 91.891.8 2222 9.69.6 0.720.72 0.780.78 -- 양호Good
실시예 4Example 4 90.990.9 2323 9.49.4 0.540.54 0.820.82 3.6×1011 3.6 × 10 11 양호Good
비교예 1Comparative Example 1 91.691.6 6565 9.29.2 0.690.69 0.720.72 -- 양호Good
비교예 2Comparative Example 2 91.691.6 7070 9.29.2 0.720.72 0.710.71 -- 양호Good
비교예 3Comparative Example 3 91.591.5 6565 9.29.2 0.800.80 0.690.69 -- 양호Good
비교예 4Comparative Example 4 91.691.6 6969 9.19.1 0.860.86 0.700.70 -- 양호Good
비교예 5Comparative Example 5 91.791.7 7272 9.39.3 0.720.72 0.750.75 -- 양호Good
비교예 6Comparative Example 6 91.791.7 6464 9.49.4 0.750.75 0.720.72 -- 양호Good
비교예 7Comparative Example 7 90.690.6 6464 9.59.5 0.690.69 0.900.90 -- 양호Good
비교예 8Comparative Example 8 90.290.2 6262 9.69.6 0.700.70 0.880.88 -- 불량Bad
상기 표 2 내지 표 3에서와 같이, 본 발명의 실시예에 따른 광학표시장치용 필름은 열가소성 폴리우레탄 필름을 포함하지 않더라도 제1코팅층 면에서 측정한 압입 탄성율 10MPa 내지 60MPa를 만족함으로써 내충격성이 우수하고 폴딩성, 내스크래치성이 우수하며, 헤이즈도 낮아서 광학 특성이 우수하였다. As shown in Tables 2 to 3, 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.
또한, 염료, 대전방지제를 포함하는 실시예 4는 UV 조사에 의해 황변이 적어서 신뢰성이 우수하고 면저항이 낮아서 광학표시장치용 필름으로 사용할 수 있게 하였다.In addition, 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.
반면에, 본 발명의 제1코팅층을 포함하지 않는 대신에 열가소성 폴리우레탄 필름을 포함하고, 기재층으로 폴리우레탄 필름을 포함하는 비교예는 압입 탄성율 높아서 폴딩성, 내스크래치성 중 하나 이상이 좋지 않거나 헤이즈도 높았다. On the other hand, 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.
실시예Example 5 5
고형분 기준으로, (A3)제5우레탄 (메트)아크릴레이트 54중량부, (B2)(메트)아크릴레이트 모노머 36중량부, (I)실리카 입자 10중량부, (D)실리콘계 첨가제 0.2 중량부, (E2)개시제 3중량부가 되도록 상기 성분들을 혼합하고, 용제로 메틸에틸케톤 55 중량부에 혼합하여 제2코팅층용 조성물을 제조하였다.(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.
기재층으로 폴리에틸렌테레프탈레이트(PET) 필름(두께: 40㎛, 제조사:SKC, 제품명:TU94-40)을 사용하였다. 기재층 일면에 제조예 1의 제1코팅층용 조성물을 소정의 두께로 도포하고, 기재층 다른 일면에 상기 제조한 제2코팅층용 조성물을 소정의 두께로 도포하고, 80℃에서 2분 동안 건조시키고, 질소 퍼징 조건에서 광원(metal halide 램프) 하에 300mJ/cm2의 광량을 조사하여 제1코팅층(두께:100㎛)과 제2코팅층을 형성하였다. 상기 제1코팅층의 다른 일면에 상기 제조예 3의 점착층(두께:30㎛)을 점착시켜, 점착층, 제1코팅층, 기재층, 제2코팅층이 순차적으로 형성된 광학표시장치용 필름을 제조하였다.As the base 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 μm) and a second coating layer. 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 .
실시예Example 6 내지  6 - 실시예Example 14 14
실시예 5에서 제2코팅층용 조성물 중 각 성분을 하기 표 4와 같이 변경하여 제2코팅층용 조성물을 제조하였다. In Example 5, 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.
기재층으로 하기 표 4의 기재층을 사용하였다. 제1코팅층용 조성물로 제조예 1의 제1코팅층용 조성물을 사용하였다. 제2코팅층의 두께를 하기 표 4와 같이 변경하였다. 실시예 5와 동일한 방법으로 광학표시장치용 필름을 제조하였다.As the base layer, the base layer shown in Table 4 was used. 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.
기재층The substrate layer 제2코팅층(중량부)The second coating layer (parts by weight) 고형분(중량%)Solid content (% by weight) 제2코팅층 두께(㎛)The thickness of the second coating layer (mu m)
종류Kinds 두께(㎛)Thickness (㎛) (A3)(A3) (B2)(B2) (I)(I) (E2)(E2) (D)(D)
실시예 5Example 5 PETPET 4040 5454 3636 1010 33 0.20.2 -- 1.51.5
실시예 6Example 6 PETPET 4040 6363 2727 1010 33 0.20.2 -- 1.51.5
실시예 7Example 7 PETPET 4040 7070 2020 1010 33 0.20.2 -- 1.51.5
실시예 8Example 8 PETPET 4040 6363 2727 1010 33 0.20.2 -- 33
실시예 9Example 9 PETPET 4040 5454 3636 1010 33 0.20.2 -- 33
실시예 10Example 10 PIPI 3030 6363 2727 1010 33 0.20.2 -- 1.51.5
실시예 11Example 11 PCPC 5050 6363 2727 1010 33 0.20.2 -- 1.51.5
실시예 12Example 12 PIPI 5050 5454 3636 1010 33 0.20.2 4545 55
실시예 13Example 13 PIPI 5050 5454 3636 1010 33 0.20.2 3333 55
실시예 14Example 14 PIPI 5050 5454 3636 1010 33 0.20.2 2020 55
*PET 필름(폴리에틸렌테레프탈레이트 필름, 두께:40㎛, 제조사:SKC, 제품명:TU94-40)* PET film (polyethylene terephthalate film, thickness: 40 mu m, manufacturer: SKC, product name: TU94-40)
*PI 필름(폴리이미드 필름, 두께:30㎛, 제조사:Kolon, 제품명:K-PI30)* PI film (polyimide film, thickness: 30 占 퐉, manufacturer: Kolon, product name: K-PI30)
*PC 필름(폴리카보네이트 필름, 두께:50㎛, 제조사:Teijin, 제품명:WRS148)* PC film (polycarbonate film, thickness: 50 mu m, manufacturer: Teijin, product name: WRS148)
*PI 필름(폴리이미드 필름, 두께:50㎛, 제조사:Kolon, 제품명:K-PI50)PI film (polyimide film, thickness: 50 占 퐉, manufacturer: Kolon, product name: K-PI50)
*고형분: 제2코팅층용 조성물 중 고형분 함량* Solid content: Solid content in the composition for the second coating layer
상기 실시예 5 내지 실시예 14에서 제조한 광학표시장치용 필름에 대해 하기 표 5의 물성을 평가하였다.The properties of the films shown in Table 5 below were evaluated for the films for optical display devices prepared in Examples 5 to 14 above.
압입 탄성율, 헤이즈, 광투과율, YI, 내스크래치성, 폴딩성(아웃 폴딩 방향)은 앞에서와 동일한 방법으로 평가하였다.The indentation elastic modulus, haze, light transmittance, YI, scratch resistance, and foldability (outfolding direction) were evaluated in the same manner as described above.
(11)크랙 스트레인: 광학표시장치용 필름에 대해 UTM(Instron 3344)을 사용하여 측정하였다. 제조한 광학표시장치용 필름을 폭 x 길이 (1cm x 10cm)로 커팅하여 시편을 제조하고, UTM에 상기 시편을 장착하고, 시편을 길이 방향으로 잡아당겼을 때 제2코팅층에 크랙이 생겼을 때의 스트레인을 평가하였다.(11) Crack Strain: Film for optical display was measured using UTM (Instron 3344). The produced optical display device film was cut into a width x length (1 cm x 10 cm) to prepare a specimen, the specimen was mounted on a UTM, and when the specimen was pulled in the longitudinal direction, a crack was generated in the second coating layer Strain was evaluated.
(12)버퍼층 형성 여부: SEM 혹은 TEM(현미경)으로 버퍼층의 단면 두께를 측정하는 방법으로 평가하였다. 버퍼층의 단면 두께가 2㎛ 미만인 경우 버퍼층이 형성되지 않은 것으로 X 로 평가하고, 버퍼층의 단면 두께가 2㎛ 이상인 경우 버퍼층이 형성되지 않은 것으로 O 로 평가하였다.(12) Whether or not the buffer layer is formed: 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,
압입탄성율@제1코팅층(MPa)Indentation elastic modulus @ First coating layer (MPa) 압입탄성율@제2코팅층(GPa)(GPa) &lt; SEP &gt; 헤이즈(%)Haze (%) 광투과율(%)Light transmittance (%) YIYI 내스크래치성Scratch resistance 폴딩성 Folding ability 크랙 스트레인(%)Crack Strain (%) 버퍼층 형성 여부Whether the buffer layer is formed
실시예 5Example 5 1818 8.98.9 0.980.98 90.7890.78 0.720.72 22 양호Good 13.013.0 XX
실시예 6Example 6 2020 9.09.0 0.850.85 90.4290.42 0.820.82 33 양호Good 11.511.5 XX
실시예 7Example 7 1919 8.98.9 0.940.94 90.5490.54 0.880.88 00 양호Good 9.509.50 XX
실시예 8Example 8 1919 9.39.3 0.970.97 90.6490.64 0.860.86 00 양호Good 7.707.70 XX
실시예 9Example 9 2121 9.49.4 0.890.89 90.2190.21 0.840.84 00 양호Good 6.506.50 XX
실시예 10Example 10 1818 8.88.8 1.011.01 89.9889.98 0.910.91 22 양호Good -- OO
실시예 11Example 11 1919 9.19.1 0.780.78 90.1490.14 0.760.76 00 양호Good -- XX
실시예 12Example 12 1919 9.39.3 0.790.79 89.7789.77 0.920.92 00 양호Good 4.54.5 OO
실시예 13Example 13 1919 9.29.2 0.810.81 89.8389.83 0.930.93 00 양호Good 1010 OO
실시예 14Example 14 1919 9.09.0 0.860.86 89.7989.79 0.970.97 33 양호Good 1818 OO
상기 표 5에서와 같이, 본 발명의 광학표시장치용 필름은 열가소성 폴리우레탄 필름을 포함하지 않더라도 제1코팅층 면에서 측정한 압입 탄성율 10MPa 내지 60MPa를 만족함으로써 내충격성이 우수하고 폴딩성, 내스크래치성이 우수하며, 헤이즈도 낮아서 광학 특성이 우수하였다. 또한, 기재층으로 폴리이미드 필름을 사용하는 경우 버퍼층이 형성됨을 확인하였다.As shown in Table 5, 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.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (22)

  1. 제1코팅층, 기재층 및 제2코팅층이 순차적으로 형성된 광학표시장치용 필름이고, A film for an optical display device in which a first coating layer, a base layer and a second coating layer are sequentially formed,
    상기 제1코팅층은 우레탄 (메트)아크릴레이트, N-비닐피롤리돈 및 개시제를 포함하는 제1코팅층용 조성물로 형성되고, Wherein the first coating layer is formed of a composition for a first coating layer comprising urethane (meth) acrylate, N-vinyl pyrrolidone and an initiator,
    상기 광학표시장치용 필름에 대하여 상기 제1코팅층 면에서 측정된 압입 탄성율(indentation modulus)이 약 10Ma 내지 약 60MPa인 것인, 광학표시장치용 필름.Wherein the indentation modulus measured on the surface of the first coating layer with respect to the film for an optical display is about 10Ma to about 60Mpa.
  2. 제1코팅층, 기재층, 제2코팅층이 순차적으로 형성된 광학표시장치용 필름이고,A film for an optical display device in which a first coating layer, a base layer and a second coating layer are sequentially formed,
    상기 제1코팅층은 우레탄 (메트)아크릴레이트를 포함하는 제1코팅층용 조성물로 형성되고, Wherein the first coating layer is formed of a composition for a first coating layer containing urethane (meth) acrylate,
    상기 광학표시장치용 필름에 대하여, 상기 제1코팅층 면에서 측정된 압입 탄성율이 약 10Ma 내지 약 60MPa 이고, 상기 제2코팅층 면에서 측정된 압입 탄성율이 약 5GPa 내지 약 12GPa 인 것인, 광학표시장치용 필름.Wherein the film for an optical display device has an indentation modulus measured from the surface of the first coating layer of about 10 to about 60 MPa and an indentation modulus measured from the surface of the second coating layer of about 5 GPa to about 12 GPa. Film.
  3. 제2항에 있어서, 상기 제1코팅층용 조성물은 N-비닐피롤리돈 및 개시제를 더 포함하는 것인, 광학표시장치용 필름.The film for an optical display device according to claim 2, wherein the composition for the first coating layer further comprises N-vinyl pyrrolidone and an initiator.
  4. 제1항 또는 제2항에 있어서, 상기 제2코팅층은 우레탄 (메트)아크릴레이트; (메트)아크릴레이트 모노머; 지르코니아 입자; 실리콘계 첨가제; 및 개시제를 포함하는 제2코팅층용 조성물로 형성된 것인, 광학표시장치용 필름.3. The composition of claim 1 or 2, wherein the second coating layer comprises urethane (meth) acrylate; (Meth) acrylate monomers; Zirconia particles; Silicone additive; And a second coating layer containing an initiator.
  5. 제1항 또는 제2항에 있어서, 상기 제1코팅층은 두께가 약 50㎛ 내지 약 150㎛인 것인, 광학표시장치용 필름.The film for an optical display device according to claim 1 or 2, wherein the first coating layer has a thickness of from about 50 탆 to about 150 탆.
  6. 제1항 또는 제2항에 있어서, 상기 제2코팅층은 두께가 약 10㎛ 이하인 것인, 광학표시장치용 필름.The film for an optical display device according to claim 1 or 2, wherein the second coating layer has a thickness of about 10 mu m or less.
  7. 제1항 또는 제2항에 있어서, 상기 기재층은 비 우레탄계 수지 필름이고, 두께가 약 50㎛ 이하인 것인, 광학표시장치용 필름. The film for an optical display device according to claim 1 or 2, wherein the base layer is a urethane-based resin film and has a thickness of about 50 탆 or less.
  8. 제1항 또는 제2항에 있어서, 상기 기재층은 등방성 필름 또는 위상차 필름인 것인, 광학표시장치용 필름.The film for an optical display device according to claim 1 or 2, wherein the base layer is an isotropic film or a phase difference film.
  9. 제1항에 있어서, 상기 우레탄 (메트)아크릴레이트, N-비닐피롤리돈, 개시제의 총합 100중량부 중 상기 우레탄 (메트)아크릴레이트 약 80중량부 내지 약 99중량부, 상기 N-비닐피롤리돈 약 0.1중량부 내지 약 10중량부, 상기 개시제 약 0.0001 중량부 내지 약 10중량부를 포함하는 것인, 광학표시장치용 필름.The ink composition according to claim 1, which comprises about 80 parts by weight to about 99 parts by weight of the urethane (meth) acrylate in 100 parts by weight of the total of the urethane (meth) acrylate, N-vinylpyrrolidone, From about 0.1 parts by weight to about 10 parts by weight of the initiator, and from about 0.0001 to about 10 parts by weight of the initiator.
  10. 제1항 또는 제2항에 있어서, 상기 우레탄 (메트)아크릴레이트는 신율이 약 2% 내지 약 20%인 것인, 광학표시장치용 필름.The film for an optical display device according to claim 1 or 2, wherein the urethane (meth) acrylate has an elongation of from about 2% to about 20%.
  11. 제4항에 있어서, 상기 제2코팅층은 상기 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부 중, 상기 우레탄 (메트)아크릴레이트 약 40중량부 내지 약 85중량부, 상기 (메트)아크릴레이트 모노머 약 5중량부 내지 약 50중량부, 상기 지르코니아 입자 약 0.01중량부 내지 약 10중량부, 상기 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 지르코니아 입자의 총합 100중량부에 대해, 상기 실리콘계 첨가제 약 0.01중량부 내지 약 5중량부, 상기 개시제 약 0.01중량부 내지 약 10중량부를 포함하는 것인, 광학표시장치용 필름.5. The composition of claim 4, wherein the second coating layer comprises about 100 parts by weight of the urethane (meth) acrylate, about (meth) acrylate, about 85 parts by weight About 5 to about 50 parts by weight of the (meth) acrylate monomer, about 0.01 to about 10 parts by weight of the zirconia particles, and the urethane (meth) acrylate, (meth) acrylate monomer, From about 0.01 to about 5 parts by weight of the silicone additive, and from about 0.01 to about 10 parts by weight of the initiator, based on 100 parts by weight of the total.
  12. 제1항 또는 제2항에 있어서, 상기 제2코팅층은 염료 및 대전 방지제를 더 포함하는 것인, 광학표시장치용 필름.The film for an optical display device according to claim 1 or 2, wherein the second coating layer further comprises a dye and an antistatic agent.
  13. 제12항에 있어서, 상기 제2코팅층 중 상기 염료는 약 0.05중량% 내지 약 0.1중량%, 상기 대전 방지제는 약 11중량% 이상 포함되는 것인, 광학표시장치용 필름.13. The film according to claim 12, wherein the dye in the second coating layer comprises about 0.05 wt% to about 0.1 wt%, and the antistatic agent comprises about 11 wt% or more.
  14. 제13항에 있어서, 상기 광학표시장치용 필름은 YI가 약 1.0 이하, 하기 식 1의 △YI가 약 1.0 이하인 것인, 광학표시장치용 필름:14. The film for an optical display device according to claim 13, wherein the film for an optical display device has a YI of about 1.0 or less and a DELTA YI of the following formula (1) is about 1.0 or less:
    <식 1><Formula 1>
    △YI = Y1 - Y2YI = Y1 - Y2
    (상기 식 1에서, Y2는 상기 광학표시장치용 필름에 대해 측정한 황색 지수,(In the above formula (1), Y2 represents the yellow index measured on the film for an optical display device,
    Y1는 Y2를 측정한 상기 광학표시장치용 필름을 UV-B 램프 72시간 방치한 후 동일한 방법으로 측정한 황색 지수). And 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).
  15. 제1항 또는 제2항에 있어서, 상기 제2코팅층은 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 실리카 입자, 실리콘계 첨가제 및 개시제를 포함하는 제2코팅층용 조성물로 형성되는 것인, 광학표시장치용 필름.3. The composition according to claim 1 or 2, wherein the second coating layer is formed of a composition for a second coating layer comprising urethane (meth) acrylate, (meth) acrylate monomer, silica particles, silicone additive and initiator. Film for optical display devices.
  16. 제15항에 있어서, 상기 (메트)아크릴레이트 모노머는 알킬렌옥사이드기를 갖는 (메트)아크릴레이트 모노머를 포함하는 것인, 광학표시장치용 필름.The film for an optical display device according to claim 15, wherein the (meth) acrylate monomer comprises a (meth) acrylate monomer having an alkylene oxide group.
  17. 제15항에 있어서, 상기 우레탄 (메트)아크릴레이트는 11관능 내지 20관능의 우레탄(메트)아크릴레이트를 포함하는 것인, 광학표시장치용 필름.The film for an optical display device according to claim 15, wherein the urethane (meth) acrylate comprises urethane (meth) acrylate having from 11 to 20 functional groups.
  18. 제16항에 있어서, 상기 제2코팅층은 상기 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 실리카 입자의 총합 100중량부 중, 상기 우레탄 (메트)아크릴레이트 약 40중량부 내지 약 85중량부, 상기 (메트)아크릴레이트 모노머 약 5중량부 내지 약 50중량부, 상기 실리카 입자 약 0.01중량부 내지 약 10중량부, 상기 우레탄 (메트)아크릴레이트, (메트)아크릴레이트 모노머, 실리카 입자의 총합 100중량부에 대해 상기 실리콘계 첨가제 약 0.01중량부 내지 약 5중량부 상기 개시제 약 0.01중량부 내지 약 10중량부를 포함하는 것인, 광학표시장치용 필름.The composition of claim 16, wherein the second coating layer comprises about 100 parts by weight of the urethane (meth) acrylate, from about 40 parts by weight to about 85 parts by weight of the urethane (meth) acrylate, About 5 to about 50 parts by weight of the (meth) acrylate monomer, about 0.01 to about 10 parts by weight of the silica particles, the urethane (meth) acrylate, the (meth) acrylate monomer, From about 0.01 to about 5 parts by weight of said silicone additive to about 100 parts by weight of said total amount of said initiator, and from about 0.01 to about 10 parts by weight of said initiator.
  19. 제15항에 있어서, 상기 기재층은 폴리이미드 필름이고, 상기 기재층과 상기 제2코팅층 사이에 버퍼층이 더 형성된 것인, 광학표시장치용 필름.The film for an optical display device according to claim 15, wherein the base layer is a polyimide film, and a buffer layer is further formed between the base layer and the second coating layer.
  20. 제1항 또는 제2항에 있어서, 상기 제1코팅층 일면에 점착층이 더 형성된 것인, 광학표시장치용 필름.The film for an optical display device according to claim 1 or 2, wherein an adhesive layer is further formed on one surface of the first coating layer.
  21. 제1항 또는 제2항의 광학표시장치용 필름을 포함하는 광학 부재.An optical member comprising the film for an optical display device according to claim 1 or 2.
  22. 제1항 또는 제2항의 광학표시장치용 필름을 포함하는 광학표시장치.An optical display device comprising the film for an optical display device according to claim 1 or 2.
PCT/KR2018/014907 2017-11-29 2018-11-29 Film for optical display apparatus, optical member comprising same, and optical display apparatus comprising same WO2019107950A2 (en)

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