WO2018004094A1 - Film pour fenêtre de dispositif d'affichage et dispositif d'affichage flexible le comprenant - Google Patents

Film pour fenêtre de dispositif d'affichage et dispositif d'affichage flexible le comprenant Download PDF

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Publication number
WO2018004094A1
WO2018004094A1 PCT/KR2017/000605 KR2017000605W WO2018004094A1 WO 2018004094 A1 WO2018004094 A1 WO 2018004094A1 KR 2017000605 W KR2017000605 W KR 2017000605W WO 2018004094 A1 WO2018004094 A1 WO 2018004094A1
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Prior art keywords
coating layer
window film
film
meth
display device
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PCT/KR2017/000605
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English (en)
Korean (ko)
Inventor
박시균
김주희
이은수
이정효
최진희
김성한
Original Assignee
삼성에스디아이 주식회사
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Priority claimed from KR1020170004435A external-priority patent/KR102018362B1/ko
Application filed by 삼성에스디아이 주식회사 filed Critical 삼성에스디아이 주식회사
Publication of WO2018004094A1 publication Critical patent/WO2018004094A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a window film for a display device and a flexible display device including the same.
  • the window film is located at the outermost side of the display (display) device, the hardness and the optical characteristics should be good. Recently, a flexible display device having a flexibility to be folded and unfolded while replacing a glass substrate or a high hardness substrate with a film in a display device has been developed. In the flexible display device, various elements included in the device as well as the substrate should have flexibility. Window films should also be flexible.
  • the window film When the window film is mounted on the display device, the window film may directly receive an external shock. Therefore, a window film having poor impact resistance may cause damage to a display device such as an OLED panel due to external impact.
  • the hardness of the window coating layer may be increased or an additional layer may be added to the laminate of the base layer and the window coating layer.
  • the window film to which an additional layer is added may also be limited in increasing impact resistance or the hardness of the window film may be degraded due to the addition of the layer, and the folding property may be poor, or delamination may occur during folding.
  • the window film since the window film is manufactured by coating and curing the composition for the window film on the base layer, curling may occur. Therefore, the window film should also have low curling.
  • the problem to be solved by the present invention is to provide a window film for a display device that is excellent in impact resistance and can suppress damage to a display device, for example, an OLED panel due to external impact when mounted on the display device.
  • Another object of the present invention is to provide a window film for a display device having excellent flexibility and excellent hardness due to low curvature radius.
  • Another object of the present invention is to provide a window film for a display device that can be minimized curling.
  • Another object of the present invention is to provide a window film for a display device excellent in reliability because there is no peeling between layers during repeated folding.
  • Another object of the present invention is to provide a window film for a display device that can be used in an optical display device having excellent optical characteristics.
  • the window film for a display device of the present invention comprises a first coating layer; And a laminate of a base layer and a second coating layer formed on one surface of the first coating layer, wherein the first coating layer includes a siloxane resin having an alicyclic epoxy group, a glycidyl group, an alicyclic epoxy group-containing functional group, or a glycidyl group-containing functional group; It is formed of a composition for a first coating layer comprising an initiator, the second coating layer may have a thickness of about 100 ⁇ m or more.
  • the flexible display device of the present invention may include the window film for the display device.
  • the present invention provides a window film for a display device that is excellent in impact resistance and can suppress damage to a display device such as an OLED panel due to external impact when mounted on a display device.
  • the present invention provides a window film for a display device having a low curvature radius and excellent flexibility and excellent hardness.
  • the present invention provides a window film for a display device that can be minimized curling.
  • the present invention provides a window film for a display device excellent in reliability because there is no peeling between layers during repeated folding.
  • the present invention provides a window film for a display device that can be used in an optical display device with excellent optical properties.
  • FIG. 1 is a cross-sectional view of a window film for a display device according to an exemplary embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a window film for a display device according to another exemplary embodiment of the present invention.
  • FIG 3 is a cross-sectional view of a window film for a display device according to still another embodiment of the present invention.
  • FIG. 4 is a cross-sectional view of a window film for a display device according to still another embodiment of the present invention.
  • FIG. 5 is a cross-sectional view of a flexible display device according to an exemplary embodiment of the present invention.
  • FIG. 6 is a cross-sectional view of a flexible display device according to another exemplary embodiment of the present invention.
  • FIG. 7 is a cross-sectional view of a flexible display device according to still another embodiment of the present invention.
  • (meth) acryl refers to acrylic and / or methacryl.
  • substituted means, unless specifically stated, that at least one hydrogen atom of the functional group is a hydroxyl group, an unsubstituted C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C3 to C10 cycloalkyl group, an unsubstituted C6 to It means substituted with an alkyl group of C1 to C10 substituted with an aryl group of C20, an arylalkyl group of C7 to C20, a C6 to C20 aryl group substituted with an alkyl group of C1 to C10, or an alkoxy group of C1 to C10.
  • alicyclic epoxy group means an epoxidized C4 to C20 cycloalkyl group.
  • an alicyclic epoxy group-containing functional group means a C1 to C20 alkyl group having an epoxidized C4 to C20 cycloalkyl group, or a C5 to C20 cycloalkyl group having a epoxidized C4 to C20 cycloalkyl group.
  • a "glycidyl group-containing functional group” refers to a glycidoxy group, a C1 to C20 alkyl group having a glycidyl group, a C1 to C20 alkyl group having a glycidyl group, a C5 to C20 cycloalkyl group having a glycidyl group, or C5 to C20 cycloalkyl group having a glycidoxy group.
  • crosslinkable functional group means an alicyclic epoxy group, an alicyclic epoxy group-containing functional group, a glycidyl group, a glycidyl group-containing functional group, an oxetane group or an oxetane group-containing functional group.
  • halogen means fluorine, chlorine, bromine or iodine.
  • Ec is an epoxycyclohexylethyl group
  • Gp is a glycidoxypropyl group
  • Me is a methyl group
  • Et is an ethyl group.
  • the impact resistance evaluation by "BALL DROP TEST” is a stainless steel plate, aluminum foil, PET film (thickness: 100 ⁇ m), adhesive film (thickness: 50 ⁇ m), the window film is sequentially laminated, 1
  • the impact resistance evaluation by “PEN DROP TEST” is performed by dropping a pen having a weight of 5.8 g and a ball size of PEN of 0.7 mm at a predetermined height from the first coating layer of the specimen and visualizing it on the surface of the aluminum foil and the first coating layer. This is an estimate of the initial height at which a mark is identified. The average value was obtained by repeating five times.
  • the "modulus" of the adhesive layer is storage modulus, and is used as an auto strain condition at a shear rate of 1 rad / sec and strain of 1% using ARES (Anton Paar Co., Ltd. MCR-501), a dynamic viscoelasticity measuring device. Viscoelasticity was measured. After removing the release film, the pressure-sensitive adhesive layer was laminated to a thickness of 500 ⁇ m, and the laminate was punched out using a perforator having a diameter of 8 mm to be used as a specimen. The measurement was performed at a temperature rising rate of 5 ° C./min in a temperature range of ⁇ 60 ° C. to 90 ° C. using a jig of 8 mm, and modulus was recorded at ⁇ 20 ° C., 25 ° C., and 80 ° C.
  • the "average particle diameter" of the organic nanoparticles is a particle size and a scanning electron microscope (TEM / TEM) of the organic nanoparticles expressed as Z-average values measured in a water-based or organic solvent with a Zetasizer nano-ZS device manufactured by Malvern. Transmission electron microscope
  • FIG. 1 is a cross-sectional view of a window film for a display device according to an exemplary embodiment of the present invention.
  • the window film 100 for a display device may include a base layer 110, a second coating layer 120, and a first coating layer 130. 1 illustrates that the base layer 110, the second coating layer 120, and the first coating layer 130 are sequentially stacked.
  • the window film 100 for a display device includes a second coating layer 120, and thus has high impact resistance, thereby preventing damage to a display device, for example, an OLED panel, by external shock when mounted on the display device.
  • a display device for example, an OLED panel
  • the window film 100 for a display device includes the first coating layer 130 and the second coating layer 120, so that there is no peeling between layers even in repeated folding, so that the reliability is excellent and the hardness is excellent.
  • the radius of curvature is low and excellent in flexibility, it can be used as a window film of a flexible display device as well as a general flat non-flexible display device.
  • the window film 100 for a display device according to the present exemplary embodiment may be used in an optical display device because the curling is minimized and optically transparent.
  • the first coating layer 130 and the second coating layer 120 may be formed of different compositions, respectively, to provide functions independent of the window film 100 for the display device.
  • the base layer 110 may support the window film 100 for the display device, the second coating layer 120, and the first coating layer 130 to increase the mechanical strength of the window film 100 for the display device.
  • 1 illustrates a case in which the second coating layer 120 is directly formed on the base layer 110.
  • the base layer 110 may be formed of an optically transparent, non-flexible resin or a flexible resin.
  • the resins include polyester resins including polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate and the like, polycarbonate resins, polyimide resins, polystyrene resins, polymethylmethacrylates, and the like. It may include at least one of poly (meth) acrylate resin, cycloolefin polymer resin.
  • the resin may include a polyimide resin or a polyester resin to increase heat resistance of the window film for a display device and to facilitate bonding with the first coating layer 130 and / or the second coating layer 120.
  • the resin may be included in the base layer 110 alone or in combination.
  • the base layer 110 has a thickness of about 10 ⁇ m to about 200 ⁇ m, specifically about 20 ⁇ m to about 150 ⁇ m, more specifically about 30 ⁇ m to about 100 ⁇ m, for example about 10, 20, 30, 40, 50 , 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200 ⁇ m. It can be used for the window film for display devices in the said range.
  • a functional layer may be further formed on one or both surfaces of the base layer 110 to provide additional functions to the base layer 110.
  • the functional layer may be a primer layer, an antireflection layer, an antiglare layer, a hard coating layer, an anti-fingerprint layer, or the like.
  • the functional layer may be replaced by a functional treatment on the surface of the base layer 110 without separately forming a functional layer.
  • an adhesive layer may be further formed on the other surface of the base layer 110 to facilitate adhesion between the window film 100 for the display device and the touch screen panel, the polarizing plate, or the display unit.
  • the pressure-sensitive adhesive layer may be formed of a pressure-sensitive adhesive layer containing a pressure-sensitive resin such as a (meth) acrylic resin, a urethane resin, a silicone resin, an epoxy resin, a curing agent, a photoinitiator, and a silane coupling agent.
  • the adhesive layer composition is known to those skilled in the art.
  • the adhesive layer may have a thickness of about 10 ⁇ m to about 100 ⁇ m.
  • Optical elements, such as a window film for display devices, and a polarizing plate, can fully be adhesive in the said range.
  • the second coating layer 120 is formed on the base layer 110 and on the first coating layer 130 to increase the mechanical strength of the window film 100 for the display device, and to form the base layer 110 and the first coating layer ( 130) can be combined.
  • the second coating layer 120 is formed directly on the base layer 110.
  • the second coating layer 120 may increase flexibility in both directions of the base layer 110 and the first coating layer 130 of the window film 100 for the display device so that the second coating layer 120 may be used in the flexible display device.
  • a plurality of viewers can simultaneously view the screen of the display device, thereby increasing the usability.
  • the window film 100 for the display device is well folded in the direction of the first coating layer 130, the screen of the display device can be viewed without invading privacy.
  • the window film 100 for the display device may have a radius of curvature of about 5 mm or less, specifically about 3.5 mm to about 4.5 mm when folded in the direction of the base layer 110.
  • the window film 100 for the display device may have a radius of curvature of about 1.5 mm or less, specifically about 0.5 mm to about 1.5 mm when folded in the direction of the first coating layer 130. Within this range, it can be used for a flexible display device.
  • the second coating layer 120 increases the flexibility of the window film 100 for the display device as described above, and minimizes the decrease in hardness compared to the window film having the two-layer structure of the base layer 110 and the first coating layer 130. Can be maintained.
  • the hardness of the window film for the display device is generally lowered, but the second coating layer 120 is the window film for the display device. It is possible to minimize or reduce the hardness of the hardness.
  • the window film 100 for the display device may have a pencil hardness of about 3H or more, and more specifically, about 3H to about 5H. In the above range, it can be used as a window film for a display device.
  • the second coating layer 120 is a non-adhesive layer and increases the impact resistance of the window film 100 for the display device, and thus, when the window film 100 for the display device is attached to the display device, Various display device elements, for example, OLED panels, disposed under the window film 100 may be protected.
  • the window film 100 for the display device may have an impact resistance of about 15 cm or more when the impact resistance is evaluated by ball drop test.
  • the window film 100 for the display device may have an impact resistance of about 4.5 cm or more when the impact resistance is evaluated by PEN DROP TEST. Within this range, damage to the OLED panel can be sufficiently prevented even in external impact when used in the display device.
  • the second coating layer 120 may have a thickness of about 100 ⁇ m or more. In the above range, it can be used in the display device and the impact resistance can be enhanced. Specifically, the second coating layer 120 has a thickness of about 100 ⁇ m to about 300 ⁇ m, specifically about 100 ⁇ m to about 250 ⁇ m, more specifically about 100 ⁇ m to about 150 ⁇ m, for example about 100, 110, 120 , 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300 ⁇ m. Within this range, flexibility and hardness in both directions of the window film for display device can be increased.
  • the second coating layer 120 may increase impact resistance, flexibility, and hardness of the display device window film 100, and may prevent peeling between layers even during folding. Thickness of the second coating layer: The thickness of the first coating layer may be about 2: 1 to about 25: 1, specifically about 10: 1 to about 15: 1. In the above range, the impact resistance, flexibility and hardness of the window film for display element can be increased, and there can be no peeling between layers.
  • 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.
  • Composition for the second coating layer is a resin for the coating layer of at least one of polyurethane resin, urethane (meth) acrylate resin; And organic nanoparticles.
  • the resin for the coating layer may form a matrix of the second coating layer and impregnate the organic nanoparticles.
  • the polyurethane resin may comprise a urethane group as a non- (meth) acrylate-based resin without a (meth) acrylate group.
  • Polyurethane resins can be synthesized using commercially available products or by conventional methods.
  • Urethane (meth) acrylate resins have a weight average molecular weight of about 1,000 to about 7,000, specifically about 1,000 to about 5,000, more specifically about 1,000 to about 3,500, for example about 1000, 1500, 2000, 2500, 3000, 3500 , 4000, 4500, 5000, 5500, 6000, 6500, 7000.
  • the urethane (meth) acrylate resin may include a bifunctional or more than trifunctional to six functional urethane (meth) acrylate resin.
  • urethane (meth) acrylate resins can be prepared by the reaction of polyhydric alcohols, polyisocyanates and hydroxy (meth) acrylates.
  • a polyol and a diisocyanate may be reacted to prepare an intermediate having an isocyanate terminal, and hydroxy (meth) acrylate may be prepared by reacting with an isocyanate, but is not necessarily limited thereto.
  • polyhydric alcohols include neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and tricyclodecane dimethyl Ol, bis- [hydroxymethyl] -cyclohexane and the like.
  • the polyester polyol obtained by reaction of the said polyhydric alcohol and polybasic acid the polycaprolactone polyol obtained by reaction of the said polyhydric alcohol and (epsilon) -caprolactone, a polycarbonate polyol, a polyether polyol, etc.
  • a polycarbonate polyol polycarbonate diol obtained by the reaction of 1,6-hexanediol and diphenyl carbonate may be used.
  • the polyether polyol polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A, and the like may be used, but are not necessarily limited thereto.
  • the polyisocyanate may include an isocyanate having 2 to 6 isocyanate groups. Specifically, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'- diisocyanate, dicyclopentanyl diisocyanate, etc. are mentioned, It is not necessarily limited to this.
  • hydroxy (meth) acrylate 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth ) Acrylate, 6-hydroxyhexyl (meth) acrylate, 1,3,5-pentanetriol di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, penta Erythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, and the like. It is not necessarily limited thereto.
  • the organic nanoparticles are included in the second coating layer 120 to increase the impact resistance of the window film 100 for the display device, to reduce the hardness of the first coating layer by PEN during pencil hardness and PEN DROP, and to improve flexibility in both directions. It can make an effect.
  • the second coating layer formed of the resin alone may have problems of lowering hardness, lowering impact resistance and lowering flexibility of the window film itself.
  • the organic nanoparticles have an average particle diameter of about 10 nm to about 400 nm, specifically about 10 nm to about 300 nm, more specifically about 30 nm to about 280 nm, more specifically about 50 nm to about 280 n, for example about 10, 20, 30, 40 , 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290 , 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400nm.
  • the light properties of the window film may be good with a total light transmittance of about 88% or more in the visible light region.
  • the organic nanoparticles have a refractive index difference of 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, for example, about 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1.
  • the optical properties of the window film may be excellent.
  • the organic nanoparticles may have a refractive index of about 1.35 to about 1.70, specifically about 1.40 to about 1.60, for example about 1.35, 1.40, 1.45, 1.50, 1.55, 1.60, 1.65, 1.70. In the above range, the optical properties of the window film may be excellent.
  • the organic nanoparticles may include simple nanoparticles such as bead type as well as core-shell type, but preferably include core-shell type particles.
  • the core and the shell may satisfy the following formula 1: That is, the core and the shell may be core-shell nanoparticles of an organic core and an organic shell, both of which are organic materials.
  • the impact resistance of the window film may be good and flexibility may be good.
  • Tg (c) is the glass transition temperature (unit: ° C) of the core
  • Tg (s) is the glass transition temperature (unit: ° C) of the shell).
  • shell refers to the outermost layer of organic nanoparticles.
  • the core may be one spherical particle.
  • the core may further comprise an additional layer surrounding the spherical particles if it has the above glass transition temperature.
  • the glass transition temperature of the core is -150 °C to 10 °C, specifically -150 °C to -5 °C, more specifically -150 °C to -20 °C, for example about -150, -140, -130, -120, -110, -100, -90, -80, -70, -60, -50, -40, -30, -20, -10, 0, 10 ° C.
  • the core may include at least one of polyalkyl (meth) acrylate, polysiloxane or polybutadiene having the above glass transition temperature.
  • Polyalkyl (meth) acrylates are polymethylacrylate, polyethylacrylate, polypropylacrylate, polybutylacrylate, polyisopropylacrylate, polyhexyl acrylate, polyhexyl methacrylate, polyethylhexyl acrylate And polyethylhexyl methacrylate, polysiloxane, but are not necessarily limited thereto.
  • the polysiloxane can be, for example, an organosiloxane (co) polymer.
  • the organosiloxane (co) polymer may be one which is not crosslinked, or a crosslinked (co) polymer may be used.
  • Crosslinked organosiloxane (co) polymers can be used for impact resistance and colorability. This is a crosslinked organosiloxane, specifically, crosslinked dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane or a mixture of two or more thereof may be used.
  • the refractive index of 1.41 to 1.50 can be adjusted by using a form in which two or more organosiloxanes are copolymerized.
  • the crosslinking state of the organosiloxane (co) polymer can be judged with the degree to be dissolved by various organic solvents. The deeper the crosslinking state, the smaller the degree of dissolution by the solvent. Acetone, toluene, or the like may be used as a solvent for determining the crosslinking state.
  • the organosiloxane (co) polymer may have a portion that is not dissolved by acetone or toluene.
  • the insoluble component of the organosiloxane copolymer to toluene may be 30% or more.
  • the organosiloxane (co) polymer may further include an alkylacrylate crosspolymer.
  • alkylacrylate crosspolymer methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the like can be used.
  • n-butyl acrylate or 2-ethylhexyl acrylate having a low glass transition temperature can be used.
  • the glass transition temperature of the shell is about 15 ° C. to about 150 ° C., specifically about 35 ° C. to about 150 ° C., more specifically about 50 ° C. to about 140 ° C., for example about 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150 ° C. In the above range, the dispersibility of the organic nanoparticles may be excellent.
  • the shell may comprise a polyalkyl methacrylate having the glass transition temperature.
  • PMMA polymethyl methacrylate
  • polyethyl methacrylate polypropyl methacrylate
  • polybutyl methacrylate polyisopropyl methacrylate
  • polyisobutyl methacrylate polycyclohexyl methacrylate It may include one or more of the rate, but is not necessarily limited thereto.
  • the core is about 30% to about 99% by weight, specifically about 40% to about 95%, more specifically about 50% to about 90% by weight of the organic nanoparticles, for example about 30, 35, 40 , 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99% by weight.
  • the folding property of the window film may be good.
  • the shell is about 1% to about 70% by weight, specifically about 5% to about 60%, more specifically about 10% to about 50% by weight of the organic nanoparticles, for example about 5, 10, 15 , 20, 25, 30, 35, 40, 45, 50, 55, 60% by weight. In the above range, the folding property of the window film may be good.
  • the organic nanoparticles are about 0.1 parts by weight to about 20 parts by weight, specifically about 0.5 parts by weight to about 10 parts by weight, specifically about 0.5 parts by weight to about 8 parts by weight, based on 100 parts by weight of the coating layer resin.
  • 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 11, 12, 13, 14, 15, 16 , 17, 18, 19, 20 parts by weight may be included. In the above range, there may be an effect of improving impact resistance and hardness.
  • Organic nanoparticles can be prepared by conventional emulsion polymerization, suspension polymerization, solution polymerization method.
  • the composition for the second coating layer may further include a solvent to increase the applicability of the composition for the second coating layer.
  • the solvent may include one or more of methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, but is not limited thereto.
  • the composition for the second coating layer may further include conventional additives known to those skilled in the art.
  • the second coating layer may include one or more of a UV absorber, a reaction inhibitor, an adhesion enhancer, a thixotropic imparting agent, a conductivity imparting agent, a stabilizer, an antistatic agent, an antioxidant, and a leveling agent, but is not limited thereto. Do not.
  • Composition for the second coating layer may include a silicone-based rubber, a curing agent.
  • the silicone rubber may be cured to form a matrix of the second coating layer and to increase impact resistance, flexibility, and hardness of the window film for the display device.
  • the silicone rubber may include a linear silicone rubber having a curable functional group such as a vinyl group.
  • the silicone rubber may be a vinyl group-containing polydimethylsiloxane resin.
  • the vinyl group-containing polydimethylsiloxane resin may be prepared from a silicone rubber composition including vinyl methyldimethoxysilane which is a vinyl group-containing silicone monomer and dimethyldimethoxysilane having no vinyl group.
  • the silicone rubber composition may further include other conventional silicone monomers other than dimethyldimethoxysilane as a silicone monomer having no vinyl group.
  • the silicone rubber may be prepared by hydrolysis, condensation and end capping reaction of the silicone rubber composition. End capping is to cap the Si terminal portion after hydrolysis and condensation of the silicone rubber composition, and the end capping agent is 1,3-divinyltetramethyldisiloxane or hexamethyldilsiloxane. Can be used.
  • the curing agent may include a silicone-based compound having two or more Si—H groups in order to hydrosilylation with the curable functional group of the silicone-based rubber.
  • the curing agent may hydrosilylate with heat and / or UV.
  • the curing agent may include linear silicone based molecules or oligomers thereof, or cyclic silicone based compounds.
  • Silicon-based monomolecular or its oligomer of linear may include a linear silicone compound having the unit (HRSiO 2/2) (R is an alkyl group or an aryl group having 6 to 10 carbon atoms having 1 to 10 carbon atoms).
  • the cyclic silicone compound may include tetramethyltetravinyl cyclotetrasiloxane, derivatives made from tetravinyltetramethyl cyclotetrasiloxane, derivatives made from tetramethylcyclotetrasiloxane, and the like.
  • the curing agent is about 0.1 parts by weight to about 20 parts by weight, specifically about 0.5 parts by weight to about 18 parts by weight, specifically about 0.7 parts by weight to about 15 parts by weight, for example about 0.1, 0.5 parts by weight of 100 parts by weight of the silicone rubber , 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 11, 12, 13, 14, 15, 16, 17, 18 , 19, 20 parts by weight may be included. In the above range, there may be an effect of the degree of curing that can exhibit an impact resistance effect.
  • the composition for the second coating layer may further include inorganic particles.
  • the inorganic particles may further increase the mechanical strength of the second coating layer.
  • the inorganic particles may be surface treated to react with the silicone rubber and the curing agent to increase the mixing between the organic component and the inorganic component and further increase the mechanical strength of the second coating layer.
  • the surface treatment may include treating the inorganic particle surface with a non-curable functional group such as trimethyl group, or a curable functional group such as vinyl group or vinyl group-containing alkyl group (eg, dimethylvinyl group).
  • the inorganic particles may include silica, but are not limited thereto.
  • the inorganic particles may have an average particle diameter (D50) of 10 nm to 500 nm, specifically 50 nm to 300 nm.
  • composition for the second coating layer may further include the solvent described above to improve applicability.
  • Composition for the second coating layer is at least one of the above-described resin for the coating layer, silicone rubber; And organic nanoparticles and a curing agent. Details of this are as described above.
  • the first coating layer 130 is formed on the second coating layer 120 to protect the display element, the base layer 110 and the second coating layer 120 as well as to improve the hardness of the window film for the display device. Can be.
  • the first coating layer 130 may be positioned on the outermost side and function as a window coating layer.
  • the first coating layer 130 is formed directly on the second coating layer 120.
  • the first coating layer 130 may have a thickness of about 10 ⁇ m to about 35 ⁇ m, for example, about 10, 15, 20, 25, 30, 35 ⁇ m. It may be used in the window film for the display device in the above range, it may be low in curl.
  • the first coating layer 130 may be formed of a composition for the first coating layer.
  • a composition for the first coating layer will be described.
  • the composition for the first coating layer may include a siloxane resin (hereinafter referred to as "siloxane resin") and an initiator having an alicyclic epoxy group, a glycidyl group, or a functional group containing them. Since the siloxane resin is included in the first coating layer 130, the pencil hardness of the window film 100 for the display device may be significantly increased, and the curl value may be significantly lowered. In addition, the siloxane resin strengthens the bond with the second coating layer 120 or the base layer 110, so that the first coating layer 130 and the second coating layer 120 may be used for repeated folding of the window film 100 for the display device. The peeling of the liver may be prevented, and even when the first coating layer 130 and the base layer 110 are directly formed as shown in FIG. 2, the peeling between the first coating layer 130 and the base layer 110 may be prevented. .
  • siloxane resin a siloxane resin
  • the siloxane resin may include a siloxane resin represented by Formula 1 below:
  • R 1 is an alicyclic epoxy group, glycidyl group, alicyclic epoxy group-containing functional group or glycidyl group-containing functional group,
  • R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, a crosslinkable functional group, unsubstituted or substituted C1 to C20 alkyl group, unsubstituted or substituted C5 to C20 cycloalkyl group, or unsubstituted or substituted C6 to C30 is an aryl group,
  • R 7 is hydrogen, unsubstituted or substituted C1 to C20 alkyl group, or unsubstituted or substituted C5 to C20 cycloalkyl group,
  • the siloxane resin may be represented by Chemical Formula 1 as a binder for forming a window film.
  • the siloxane resin can increase the hardness of the window film and lower the radius of curvature to improve the flexibility of the window film.
  • the siloxane resin contains R 2 and R 3 groups, crosslinking and flexibility can be provided to further increase the hardness and flexibility of the window film.
  • the siloxane resin contains R 4 , R 5 and R 6 groups, the crosslinking density of the window film can be further improved.
  • the siloxane resin may be included in the composition for a window film alone or in mixture of two or more thereof.
  • the siloxane resin has a weight average molecular weight of about 2,000 to about 20,000, specifically about 4,500 to about 10,000, for example about 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000 , 15000, 16000, 17000, 18000, 19000, 20000. There may be an effect of supporting the coating layer of the window film in the above range.
  • the siloxane resin has a polydispersity (PDI) of about 1.0 to about 3.0, specifically about 1.5 to about 2.5, epoxy equivalent weight of about 0.1 mol / 100 g to about 1.0 mol / 100 g, specifically about 0.3 mol / 100 g to about 0.8 mol / 100g.
  • PDI polydispersity
  • the siloxane resin may be a siloxane resin represented by Formula 1-1:
  • R 1 may be C1 to C20 alkyl group having epoxidized C4 to C20 cycloalkyl group, C1 to C20 alkyl group having glycidyl group, C1 to C20 alkyl group having glycidoxy group. More specifically, R 1 may be an epoxycyclohexylethyl group. Specifically, R 2 and R 3 may each independently be an unsubstituted or substituted C1 to C20 alkyl group. At this time, the flexibility of the window film can be improved.
  • R 2 and R 3 are each independently a methyl group, an ethyl group, a (3,4-epoxycyclohexyl) methyl group, a (3,4-epoxycyclohexyl) ethyl group, a (3,4-epoxycyclohexyl) propyl group or And glycidoxypropyl groups.
  • the siloxane resin may be represented by any one of the following Chemical Formulas 1-1A to 1-1H:
  • the siloxane resin can be prepared by hydrolysis and condensation reaction of a monomer mixture comprising a first silicon monomer and a second silicon monomer.
  • the first silicon monomer is about 20 mol% to about 99.9 mol%, about 20 mol% to about 99 mol%, or about 50 mol% to about 99 mol% in the monomer mixture
  • the second silicon monomer is about 0.1 mol% to about 80 mol in the monomer mixture %, About 1 mol% to about 80 mol%, or about 1 mol% to about 50 mol%.
  • the flexibility may be increased while securing hardness in the above range.
  • the first silicon monomer is represented by the following Chemical Formula 2
  • the second silicon monomer is represented by the following Chemical Formula 3, and these may be used alone or in combination of two or more kinds:
  • R 1 is as defined in Chemical Formula 1, and R 8 , R 9 and R 10 are each independently a halogen, a hydroxyl group, or an alkoxy group of C1 to C10).
  • R 2 and R 3 are as defined in Chemical Formula 1, and R 11 and R 12 are each independently a halogen, a hydroxyl group, or an alkoxy group of C1 to C10).
  • the first silicon monomer is a trialkoxysilane compound, for example (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.
  • a trialkoxysilane compound for example (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.
  • the second silicon monomer is a dialkoxysilane compound, for example dimethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, (3-glycidoxypropyl) methyldie Oxysilane, and the like, but is not limited thereto.
  • Hydrolysis and condensation reaction of the monomer may be carried out according to a conventional method for producing siloxane resin.
  • Hydrolysis may comprise reacting a first silicon monomer and a second silicon monomer in water and a mixture of one or more of the desired acids, bases.
  • the acid is a strong acid, such as HCl, HNO 3 , acetic acid
  • the base may be used as a strong base NaOH, KOH, NH 4 OH and the like.
  • Hydrolysis may be performed at about 20 ° C. to about 100 ° C. for about 10 minutes to about 7 hours. Within this range, the hydrolysis efficiency of the first silicon monomer and the second silicon monomer can be increased.
  • the condensation reaction may be performed at about 20 ° C. to about 100 ° C. for about 10 minutes to about 12 hours under the same conditions as hydrolysis. It is possible to increase the condensation reaction efficiency of the first silicon monomer and the second silicon monomer in the above range.
  • the siloxane resin may be a siloxane resin represented by Formula 1-2:
  • 0.50 ⁇ x1 ⁇ about 0.99, 0.01 ⁇ x2 ⁇ 0.50 The hardness and flexibility of the window film in the above range may be good.
  • An initiator hardens a siloxane resin, and can use one or more of a photocationic initiator and an optical radical initiator.
  • the initiator may be used alone or in combination of two or more thereof.
  • Photocationic initiators can be used those commonly known to those skilled in the art. Specifically, onium salts containing cations and anions can be used. As a specific example of a cation, diaryl, such as diphenyl iodonium, 4-methoxy diphenyl iodonium, bis (4-methylphenyl) iodonium, bis (4-tert- butylphenyl) iodonium, bis (dodecylphenyl) iodonium, etc.
  • diaryl such as diphenyl iodonium, 4-methoxy diphenyl iodonium, bis (4-methylphenyl) iodonium, bis (4-tert- butylphenyl) iodonium, bis (dodecylphenyl) iodonium, etc.
  • Triaryl sulfoniums such as iodonium, triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, and the like.
  • Hexafluoro Specific examples of the anionic phosphate (PF 6 -), tetrafluoroborate (BF 4 -), hexafluoroantimonate (SbF 6 -), hexafluoroantimonate are Senate (AsF 6 -), hexachloro Antimonate (SbCl 6 ⁇ ) and the like.
  • the initiator may be included in an amount of about 1 part by weight to about 15 parts by weight, specifically about 1 part by weight to about 10 parts by weight, and more specifically about 1 part by weight to about 5 parts by weight, based on 100 parts by weight of the siloxane resin.
  • the siloxane resin can be sufficiently cured and a residual amount of initiator can be left to prevent the transparency of the window film from decreasing.
  • the first coating layer composition may further include nanoparticles.
  • Nanoparticles can further increase the hardness of the window film.
  • Nanoparticles may include, but are not limited to, one or more inorganic nanoparticles of silica, aluminum oxide, zirconium oxide, titanium oxide.
  • the nanoparticles may be surface treated with some or all of the surface with a silicone compound for mixing with the siloxane resin.
  • Nanoparticles are not limited in shape and size.
  • the nanoparticles may include particles having a spherical shape, a plate shape, an amorphous shape, and the like.
  • the nanoparticles may have an average particle diameter (D50) of about 1 nm to about 200 nm, specifically about 10 nm to about 50 nm.
  • the hardness of the window film can be increased without affecting the surface roughness and transparency of the window film.
  • the nanoparticles may be included in an amount of about 0.1 parts by weight to about 60 parts by weight, specifically about 10 parts by weight to about 50 parts by weight, based on 100 parts by weight of the siloxane resin. In the above range, the hardness of the window film can be increased without affecting the surface roughness and transparency of the window film.
  • the first coating layer composition may further include an additive.
  • the additive may provide additional functionality to the window film.
  • the additives may include additives that are typically added to the window film.
  • the additive may include, but is not limited to, at least one of a UV absorber, a reaction inhibitor, an adhesion enhancer, a thixotropic imparting agent, a conductivity imparting agent, a stabilizer, an antistatic agent, an antioxidant, and a leveling agent.
  • the reaction inhibitor may include ethynylcyclohexane.
  • An adhesion promoter may include a silane compound having an epoxy or alkoxysilyl group.
  • the thixotropic agent may include fumed silica and the like.
  • the conductivity providing agent may include metal powder such as silver and copper aluminum.
  • the additive may be included in an amount of about 0.01 part by weight to about 5 parts by weight, specifically about 0.1 part by weight to about 2.5 parts by weight, based on 100 parts by weight of the siloxane resin. In the above range can improve the hardness and flexibility of the window film and implement the additive effect.
  • the composition for the first coating layer may further include a solvent in order to facilitate coating, coating, or processability.
  • the solvent may include one or more of methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, but is not limited thereto.
  • composition for the first coating layer according to another embodiment may include a siloxane resin, an initiator and a crosslinking agent. It is substantially the same as the composition for the first coating layer according to one embodiment except that it further comprises a crosslinking agent. Thus, only the crosslinking agent will be described.
  • the crosslinking agent may be cured with the siloxane resin by containing a crosslinkable functional group to further increase the hardness of the window film.
  • the crosslinking agent may further increase the flexibility of the window film for a display device by further including at least one of a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and a hydrogenated aromatic hydrocarbon group.
  • the crosslinking agent may include one or more of a chain aliphatic epoxy monomer, a cyclic aliphatic epoxy monomer, a hydrogenated aromatic hydrocarbon epoxy monomer, an oxetane monomer, and these may be included alone or in combination.
  • the crosslinking agent contains a cyclic aliphatic epoxy monomer, thereby increasing the pencil hardness of the window film for display device and significantly lowering the curling.
  • Chain aliphatic epoxy monomers include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, and polyethylene glycol diglycol.
  • the cyclic aliphatic epoxy monomer is a compound having one or more epoxy groups in the alicyclic group, and may specifically include an alicyclic epoxy carboxylate, an alicyclic epoxy (meth) acrylate, and the like. More specifically, (3,4-epoxycyclohexyl) methyl-3 ', 4'-epoxycyclohexanecarboxylate, diglycidyl 1,2-cyclohexanedicarboxylate, 2- (3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclo Hexyl) adipate, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, ⁇ -
  • Aromatic epoxy monomers include, for example, bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, and the like; Novolac type epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, hydroxybenzaldehyde phenol novolac epoxy resins; And polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinyl phenol.
  • bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, and the like
  • Novolac type epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, hydroxybenzaldehyde phenol novolac
  • Oxetane monomers include 3-methyloxetane, 2-methyloxetane, 2-ethylhexyl oxetane, 3-oxetanol, 2-methyleneoxetane, 3,3-oxetane dimethanethiol, 4- (3-methyl Oxetan-3-yl) benzonitrile, N- (2,2-dimethylpropyl) -3-methyl-3-oxetanemethaneamine, N- (1,2-dimethylbutyl) -3-methyl-3- Oxetanemethaneamine, (3-ethyloxetan-3-yl) methyl (meth) acrylate, 4-[(3-ethyloxetan-3-yl) methoxy] butan-1-ol, 3-ethyl- May comprise one or more of 3-hydroxymethyloxetane, xylenebisoxetane, 3- [ethyl-3 [[(3-e
  • the crosslinking agent may be included in an amount of about 0.1 parts by weight to about 50 parts by weight, specifically about 5 parts by weight to about 25 parts by weight, based on 100 parts by weight of the siloxane resin. In the above range, flexibility and hardness of the first coating layer may be increased.
  • the first coating layer 130 is formed only on one surface of the substrate layer 110, but the window film in which the first coating layer 130 is further laminated on the other surface of the substrate layer 110 is also present. It may be included in the range of.
  • a functional layer may be further formed on the other surface of the first coating layer 130 to provide additional functions to the first coating layer 130.
  • the functional layer may include one or more of an antireflective layer, an antiglare layer, and a primer layer.
  • the functional layer may be replaced on the surface of the first coating layer 130 without forming a functional layer.
  • the window film 100 for the display device is optically transparent and can be used for the transparent display device.
  • the window film 100 for the display device may have a total light transmittance of about 88% or more, specifically about 88% to about 100%, and a haze of about 2% or less in the visible light region, particularly in the wavelength range of 400 nm to 800 nm. 0% to about 2%. Within this range, it can be used as a window film for a display device.
  • the window film 100 for the display device may have a curl of about 2.0 mm or less, for example, about 0 mm to about 2.0 mm. Within this range, the curling rate can be low and used as a window film for a display device.
  • the window film 100 for the display device may have a thickness of about 50 ⁇ m to about 400 ⁇ m. It can be used as a window film for display devices in the said range.
  • FIG. 2 is a cross-sectional view of a window film for a display device according to another exemplary embodiment of the present invention.
  • the window film 200 for the display device is an exemplary embodiment of the present invention except that the window film 200 for the display device is stacked in the order of the second coating layer 120, the base layer 110, and the first coating layer 130. It is substantially the same as the window film for display device 100 according to.
  • FIG. 3 is a cross-sectional view of a window film according to another embodiment of the present invention.
  • the flexible window film 150 is substantially the same as the flexible window film 100 according to the present embodiment except that the substrate window 110 includes a substrate layer 110A instead of the substrate layer 110. .
  • the base layer 110A includes a first film 110a, a second film 110b, and an adhesive layer 110c formed between the first film 110a and the second film 110b.
  • the flexible window film may be excellent in flexibility and further improved in impact resistance compared to the flexible window film including the base layer 110.
  • the first film 110a and the second film 110b may respectively support the flexible window film 150.
  • Each of the first film 110a and the second film 110b may be formed of the optically transparent and flexible resin.
  • the first film 110a and the second film 110b may be formed of the same or different resins.
  • the first film 110a and the second film 110b are each formed of at least one resin of polyester resin, polycarbonate resin, polyimide resin, poly (meth) acrylate resin, and cyclic olefin polymer resin. It may be a film.
  • the first film 110a and the second film 110b may have different thicknesses or the same.
  • the first film 110a and the second film 110b may each have a thickness of about 10 ⁇ m to about 100 ⁇ m, preferably about 30 ⁇ m to about 50 ⁇ m. In the above range, there may be an excellent effect of flexibility and impact resistance.
  • the base layer 110A may have a thickness of about 10 ⁇ m to about 275 ⁇ m, specifically about 20 ⁇ m to about 200 ⁇ m, and more specifically about 50 ⁇ m to about 110 ⁇ m. It can be used for the flexible window film in the above range.
  • FIG 3 illustrates a case in which the second coating layer 120 is directly formed on the second film 110b.
  • the second coating layer 120 is directly formed on the first film 110a, that is, the second film 110b.
  • the adhesive layer 110c, the first film 110a, the second coating layer 120, and the first coating layer 130 are sequentially formed may also be included in the scope of the present invention.
  • the adhesive layer 110c may be formed between the first film 110a and the second film 110b to adhere them to each other.
  • the adhesive layer 110c may increase the bending reliability when repeatedly folding the window film, and may increase the impact strength of the window film.
  • the adhesive layer 110c may have a modulus of about 10 kPa to about 1000 kPa at 25 ° C. In the above range, the impact resistance of the window film can be increased, and reliability may be good even once or repeatedly folding the window film at room temperature.
  • the adhesive layer 120 may have a modulus of about 10 kPa to about 800 kPa at 25 ° C.
  • the adhesive layer 110c may have a modulus of about 10 kPa to about 1000 kPa at 80 ° C. In the above range, the impact resistance of the window film can be increased, and reliability may be good even once or repeatedly folding the window film at high temperature and high humidity. Preferably, the adhesive layer 110c may have a modulus of about 10 kPa to about 800 kPa at 80 ° C.
  • the adhesive layer 110c may have a modulus of about 10 kPa to about 1000 kPa at -20 ° C. In the above range, the impact resistance of the window film can be increased, and reliability may be good even once or repeatedly folding the window film at a low temperature. Preferably, the adhesive layer 110c may have a modulus of about 10 kPa to about 500 kPa at -20 ° C.
  • the adhesive layer 110c has a modulus of modulus at 25 ° C: -20 ° C of about 1: 1 to about 1: 4, specifically about 1: 1 to about 1: 3.5, more specifically about 1: 1 to about 1: can be 2.8
  • the adhesive layer has a small change in physical properties due to temperature change in a wide temperature range (-20 ° C. to 25 ° C.)
  • the stress of the adherend is reduced, and no peeling or bubbles occur in the foldable test. It can be used for a flexible optical member.
  • the adhesive layer 110c may have a modulus of modulus at 80 ° C .: ⁇ 20 ° C. of about 1: 1 to about 1:10, specifically about 1: 1 to about 1: 8, and more specifically about 1: 1 to about It can be 1: 5. In the above range, the adhesive layer does not degrade the adhesive strength between the adhesives in a wide temperature range (-20 ° C. to 80 ° C.), and may be used for a flexible optical member.
  • the adhesive layer 110c may have a thickness of about 10 ⁇ m to about 75 ⁇ m. In the above range, there may be an excellent effect of flexibility and impact resistance. Preferably, the adhesive layer 110c may have a thickness of about 10 ⁇ m to about 50 ⁇ m and about 10 ⁇ m to about 30 ⁇ m.
  • the adhesive layer 110c may have a haze of about 5% or less, specifically about 3% or less, and more specifically about 1% or less in the visible light region at a thickness of 100 ⁇ m. In the above range, excellent transparency is exhibited when the adhesive layer is used in an optical display device.
  • the adhesive layer 110c has a glass transition temperature (Tg) of about 0 ° C. or less, for example, about ⁇ 150 ° C. to about 0 ° C., specifically about ⁇ 150 ° C. to about ⁇ 20 ° C., and more specifically about ⁇ 150 ° C. to It may be about -30 °C. In the above range, the adhesive layer is excellent in viscoelastic properties at low and normal temperatures.
  • Tg glass transition temperature
  • the adhesive layer 110c may be formed of an optical clear adhesive (OCA).
  • OCA optical clear adhesive
  • the adhesive layer 110c may include a monomer mixture for a (meth) acrylic copolymer having a hydroxyl group; Initiator; And it may be formed of a composition for pressure-sensitive adhesive layer comprising one or more of macromonomer and organic nanoparticles.
  • the monomer mixture may be included in the pressure-sensitive adhesive composition in a state in which the monomer mixture is not polymerized at all, but the monomer mixture may be included as a partially polymerized partial polymer.
  • the composition for pressure-sensitive adhesive layer is a monomer mixture for a (meth) acrylic copolymer having a hydroxyl group; Initiator; And organic nanoparticles.
  • the monomer mixture may be composed of hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) acrylate.
  • the hydroxyl group-containing (meth) acrylate can provide the adhesive force of the adhesive layer.
  • the hydroxyl group-containing (meth) acrylate may be a (meth) acrylate containing one or more hydroxyl groups.
  • the hydroxyl group-containing (meth) acrylate is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydrate Oxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaery
  • the hydroxyl group-containing (meth) acrylate is about 5% to about 40% by weight of the total of the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate, for example, about 8% to about 30% by weight, About 10% to about 30% by weight. In the above range, the adhesion and durability of the pressure-sensitive adhesive layer can be further improved.
  • the alkyl group-containing (meth) acrylate can be a copolymer to form a matrix of the adhesive layer.
  • the alkyl group-containing (meth) acrylate may include an unsubstituted linear or branched alkyl (meth) acrylic acid ester having 1 to 20 carbon atoms.
  • Alkyl group-containing (meth) acrylate is about 60% to about 95% by weight of the total of the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate, for example, about 65% to about 92% by weight, about 68 weight percent to about 90 weight percent, about 70 weight percent to about 90 weight percent. In the above range, the adhesion and durability of the pressure-sensitive adhesive layer can be further improved.
  • the monomer mixture may further include a copolymerizable monomer.
  • the copolymerizable monomer may be included 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 different from the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate, and includes a monomer having ethylene oxide, a monomer having propylene oxide, a monomer having an amine group, a monomer having an alkoxy group and a monomer having a phosphoric acid group.
  • Monomers having ethylene oxide may be at least one (meth) acrylate monomer containing an ethylene oxide group (-CH 2 CH 2 O-).
  • Monomers with propylene oxide include polypropylene oxide monomethyl ether (meth) acrylate, polypropylene oxide monoethyl ether (meth) acrylate, polypropylene oxide monopropyl ether (meth) acrylate, polypropylene oxide monobutyl ether (meth ) Acrylate, polypropylene oxide monopentyl ether (meth) acrylate, polypropylene oxide dimethyl ether (meth) acrylate, polypropylene oxide diethyl ether (meth) acrylate, polypropylene oxide monoisopropyl ether (meth) acrylic Polypropylene oxide alkylether (meth) acrylates, such as latex, polypropylene oxide monoisobutyl ether (meth) acrylate, polypropylene oxide monotertbutyl ether (meth) acrylate, but are not necessarily limited thereto. no All.
  • Monomers having an amine group include monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth Amine group containing (meth), such as an acrylate, diethylaminoethyl (meth) acrylate, N-tert- butylaminoethyl (meth) acrylate, and (meth) acryloxyethyl trimethylammonium chloride (meth) acrylate It may be an acrylic monomer, but is not necessarily limited thereto.
  • Monomers having an alkoxy group include 2-methoxy ethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 2-butoxypropyl (meth) acrylate, 2 -Methoxypentyl (meth) acrylate, 2-ethoxypentyl (meth) acrylate, 2-butoxyhexyl (meth) acrylate, 3-methoxypentyl (meth) acrylate, 3-ethoxypentyl (meth ), 3-butoxyhexyl (meth) acrylate, but is not necessarily limited thereto.
  • Monomers having a phosphoric acid group include 2-methacryloyloxyethyldiphenyl phosphate (meth) acrylate, trimethacryloyloxyethyl phosphate (meth) acrylate, triacryloyloxyethyl phosphate (meth) acrylate, and the like. It may be an acrylic monomer having a phosphoric acid group, but is not necessarily limited thereto.
  • the monomer having a sulfonic acid group may be an acrylic monomer having a sulfonic acid group such as sodium sulfopropyl (meth) acrylate, sodium 2-sulfoethyl (meth) acrylate and sodium 2-acrylamido-2-methylpropane sulfonate.
  • the present invention is not limited thereto.
  • the monomer having a phenyl group may be an acrylic vinyl monomer having a phenyl group such as p-tert-butylphenyl (meth) acrylate, o-biphenyl (meth) acrylate, phenoxyethyl (meth) acrylate, but is not limited thereto. It doesn't happen.
  • the monomer having a silane group is 2-acetoacetoxyethyl (meth) acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxyethyl) silane, vinyltriacetoxysilane, (meth) acrylic It may be a vinyl monomer having a silane group such as royloxypropyl trimethoxysilane, but is not necessarily limited thereto.
  • Monomers having a carboxylic acid group include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, itaconic acid, crotonic acid, maleic acid, and fumaric acid. And maleic anhydride, and the like, but are not necessarily limited thereto.
  • Amide group-containing (meth) acrylates include (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N, N-methylene Bis (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide.
  • the copolymerizable monomer is about 15 parts by weight or less, specifically about 10 parts by weight or less, and more specifically about 0.05 parts by weight to about 100 parts by weight of the total of the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate. It may be included in 8 parts by weight.
  • the pressure-sensitive adhesive composition in the above range can further improve the adhesion and recovery of the adhesive film.
  • the initiator can be used to cure (partial polymerization) the monomer mixture into a (meth) acrylic copolymer or to cure a viscous liquid into a film.
  • the initiator may comprise one or more of a photopolymerization initiator and a thermal polymerization initiator.
  • a photoinitiator as long as it can induce the polymerization reaction of the radically polymerizable compound mentioned above in the hardening process by light irradiation etc., any can be used.
  • a benzoin type, a hydroxy ketone type, an amino ketone type, or a phosphine oxide type photoinitiator can be used.
  • benzoin benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylanino acetophenone, 2,2-dimethone Methoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1one, 1-hydroxycyclohexylphenylketone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone , p-phenylbenzophenone, 4,4-nondidiaminoaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthr
  • the thermal polymerization initiator is not particularly limited as long as it has the above-described physical properties.
  • a common initiator such as an azo compound, a peroxide compound, or a redox compound can be used.
  • Examples of the azo compound in the above are 2,2-azobis (2-methylbutyronitrile), 2,2-triazobis (isobutyronitrile), 2,2-triazobis (2,4-dimethyl Valeronitrile), 2,2-nitazobis-2-hydroxymethylpropionitrile, dimethyl-2,2-methylazobis (2-methylpropionate) and 2,2-piazobis (4- Methoxy-2,4-dimethylvaleronitrile) and the like
  • examples of the peroxide-based compound include inorganic peroxides such as potassium peroxide, ammonium persulfate or hydrogen peroxide; Or diacyl peroxide, peroxy dicarbonate, peroxy ester, tetramethylbutylperoxy neodecanoate, bis (4-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxy carbonate, butylper Oxy neodecanoate, dipropyl peroxy dicarbonate, di
  • the initiator is about 0.0001 parts by weight to about 5 parts by weight, specifically about 0.001 parts by weight to 100 parts by weight of the total of the hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) acrylate constituting the (meth) acrylic copolymer About 3 parts by weight. In this range, the curing reaction can proceed completely, remaining amount of initiator can remain to prevent the transmittance from decreasing, and also it is possible to lower the bubble generation and have excellent reactivity.
  • Macromonomers have functional groups curable by active energy rays and can be polymerized with hydroxyl group-containing (meth) acrylates and alkyl group-containing (meth) acrylates.
  • the macromonomer may be represented by the following Chemical Formula 4:
  • R 1 is hydrogen or methyl
  • X is a single bond or a divalent bond
  • Y is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl Polymer chain obtained by polymerizing one or two or more selected from (meth) acrylate, t-butyl (meth) acrylate, styrene and (meth) acrylonitrile).
  • the macromonomer may have a number average molecular weight of about 2,000 to about 20,000, specifically about 2,000 to about 10,000, more specifically about 4,000 to about 8,000. In the said range, sufficient adhesive strength can be obtained, it is excellent in heat resistance, and the fall of the workability by the viscosity raise of an adhesive composition can be suppressed.
  • the macromonomer may have a glass transition temperature of about 40 ° C to about 150 ° C, specifically about 60 ° C to about 140 ° C, more specifically about 80 ° C to about 130 ° C. In the above range, the pressure-sensitive adhesive layer can exhibit sufficient cohesion, and can suppress a decrease in stickiness or adhesion.
  • the divalent bond group is C1 to C10 alkylene group, C7 to C13 arylalkylene group, C6 to C12 arylene group, -NR 2- (wherein R 2 is hydrogen or C1 to C5 alkyl group), COO-,- O-, -S-, -SO 2 NH-, -NHSO 2- , -NHCOO-, -OCONH, or a group derived from a heterocycle.
  • divalent linking group may be represented by the following formula (4a) to (4d):
  • Macromonomer can use a commercial item.
  • a macromonomer whose terminal is a methacryloyl group and the segment corresponding to Y is methyl methacrylate the macromonomer where the segment corresponding to Y is the styrene segment, and the segment of the segment Y is the styrene / acryl
  • the macromonomer which is ronitrile, the macromonomer whose segment is butylacrylate, etc. can be used.
  • the macromonomer is about 20 parts by weight or less, specifically about 0.1 parts by weight to about 20 parts by weight, and about 0.1 parts by weight to about 10 parts by weight of 100 parts by weight of the total of the hydroxyl group-containing (meth) acrylate and the alkyl group-containing (meth) acrylate. It can be included in parts by weight, about 0.5 parts by weight to about 5 parts by weight. In the above range, the viscoelasticity and modulus of the pressure-sensitive adhesive layer and the restoring force can be balanced, and the haze of the pressure-sensitive adhesive layer can be prevented from rising.
  • the organic nanoparticles may have an average particle diameter of about 10 nm to about 400 nm, specifically about 10 nm to about 300 nm, more specifically about 30 nm to about 280 nm, and more specifically about 50 nm to about 280 nm. In the above range, the folding of the pressure-sensitive adhesive layer is not affected, and the transparency of the pressure-sensitive adhesive layer may be good as the total light transmittance in the visible region is about 90% or more.
  • the organic nanoparticles may have a refractive index difference of 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, with a (meth) acrylic copolymer having a hydroxyl group. In the above range, the transparency of the pressure-sensitive adhesive layer may be excellent.
  • the organic nanoparticles may have a refractive index of about 1.35 to about 1.70, specifically about 1.40 to about 1.60. In the above range, the transparency of the pressure-sensitive adhesive layer may be excellent.
  • the organic nanoparticles are as described above.
  • the organic nanoparticles are about 0.1 parts by weight to about 20 parts by weight, specifically about 0.5 parts by weight to about 10 parts by weight, specifically 100 parts by weight of the total amount of hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) acrylate. About 0.5 to about 8 parts by weight. Within this range, the modulus of the pressure-sensitive adhesive layer at high temperature can be increased, the folding properties at normal temperature and high temperature of the pressure-sensitive adhesive layer can be improved, and the low-temperature and / or normal temperature viscoelasticity of the pressure-sensitive adhesive layer can be made excellent.
  • Organic nanoparticles can be prepared by conventional emulsion polymerization, suspension polymerization, solution polymerization method.
  • the pressure-sensitive adhesive layer composition may further include a silane coupling agent.
  • Silane coupling agents can be used conventionally known to those skilled in the art. For example, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane, 3-glycidoxy propylmethyl dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Silicon compounds having an epoxy structure such as methoxysilane; Polymerizable unsaturated group-containing silicon compounds such as vinyl trimethoxy silane, vinyl triethoxy silane, and (meth) acryloxy propyl trimethoxysilane; Amino group-containing silicon compounds such as 3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyl dime
  • the silane coupling agent may be included in an amount of about 0.01 part by weight to about 3 parts by weight, specifically about 0.01 part by weight to about 1 part by weight, based on 100 parts by weight of the total amount of hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) acrylate. .
  • reliability can be ensured in the bending state at the high temperature and high humidity described above, and the difference in peeling force between low temperature, room temperature, and high temperature can be low.
  • the adhesive layer composition may further include a crosslinking agent.
  • a crosslinking agent can raise the degree of crosslinking of the composition for adhesion layers, and can raise the mechanical strength of an adhesion layer.
  • the crosslinking agent may include a polyfunctional (meth) acrylate capable of curing with an active energy ray, for example, a bifunctional (meth) acrylate such as hexanediol diacrylate, or a trifunctional to 6 functional (meth) acrylate. Can be.
  • the crosslinking agent is about 0.001 parts by weight to about 5 parts by weight, specifically about 0.003 parts by weight to about 3 parts by weight, specifically about 0.005 parts by weight of 100 parts by weight of the total amount of hydroxyl group-containing (meth) acrylate and alkyl group-containing (meth) acrylate. It may be included in parts by weight to about 1 part by weight. There is an effect of excellent adhesion and increased reliability in the above range.
  • the base layer 110A is a film laminate in which the first film 110a and the second film 110b are laminated by the adhesive layer 110c.
  • the case where the base material layer includes three or more films and at least two or more of them is a film laminate laminated with each other by the adhesive layer 110c may also be included in the scope of the present invention.
  • FIG. 4 is a cross-sectional view of a window film according to another embodiment of the present invention.
  • the flexible window film 250 is substantially the same as the flexible window film 200 according to the present embodiment, except that the flexible window film 250 includes the substrate layer 110A of FIG. 3 instead of the substrate layer 110.
  • the second coating layer 120, the second film 110b, the adhesive layer 110c, the first film 110a, and the first coating layer 130 may be sequentially included in the scope of the present invention.
  • the window film 100 for a display device may be manufactured by coating a composition for a second coating layer on a substrate layer, and coating and curing the composition for a first coating layer thereon.
  • the method of coating the composition for the first coating layer and the composition for the second coating layer, respectively, is not particularly limited.
  • it may be bar coating, spin coating, dip coating, roll coating, flow coating, die coating, or the like.
  • Curing may harden the composition for the first coating layer and the composition for the second coating layer to form the first coating layer and the second coating layer.
  • Curing may include one or more of photocuring and thermosetting. Photocuring may involve irradiation with light intensity of approximately 10mJ / cm 2 to about 1000mJ / cm 2 at a wavelength of 400nm or less.
  • Thermal curing may include treatment at about 40 ° C. to about 200 ° C. for about 1 minute to about 30 hours.
  • the composition for the coating layer can be sufficiently cured in the above range. For example, it may be thermally cured after photocuring, and as a result, the hardness of the coating layer may be further increased.
  • the method may further include drying the first coating layer composition and the second coating layer composition, respectively, after the first coating layer composition and the second coating layer composition are coated and cured.
  • drying may be performed at about 40 ° C. to about 200 ° C. for about 1 minute to about 30 hours, but is not limited thereto.
  • FIG. 5 is a cross-sectional view of a flexible display device according to an exemplary embodiment of the present invention.
  • the flexible display apparatus 300 includes a display unit 350a, an adhesive layer 360, a polarizer 370, a touch screen panel 380, and a flexible window film 390.
  • 390 may include a window film for a display device according to embodiments of the present invention.
  • the display unit 350a is for driving the flexible display apparatus 300 and may include an optical element including a substrate and an OLED, an LED, or an LCD element formed on the substrate.
  • the adhesive layer 360 adheres the display unit 350a and the polarizing plate 370, and may be formed of an adhesive composition including a (meth) acrylate-based resin, a curing agent, an initiator, and a silane coupling agent. Alternatively, the adhesive layer 360 may be an adhesive layer including the organic nanoparticles.
  • the polarizer 370 may implement polarization of internal light or prevent reflection of external light to implement a display or increase a contrast ratio of the display.
  • the polarizing plate may be composed of a polarizer alone.
  • the polarizer may include a polarizer and a protective film formed on one or both sides of the polarizer.
  • the polarizing plate may include a polarizer and a protective coating layer formed on one or both surfaces of the polarizer.
  • the polarizer, the protective film, and the protective coating layer may use a conventional one known to those skilled in the art.
  • the touch screen panel 380 detects a change in capacitance generated when a human body or a conductor such as a stylus touches to generate an electrical signal.
  • the display unit 350a may be driven by the signal.
  • the touch screen panel 380 is formed by patterning a flexible and conductive conductor, and may include a second sensor electrode formed between the first sensor electrode and the first sensor electrode to cross the first sensor electrode. have.
  • the conductor for the touch screen panel 380 may include, but is not limited to, metal nanowires, conductive polymers, carbon nanotubes, and the like.
  • the flexible window film 390 may be formed on the outermost side of the flexible display device 300 to protect the display device.
  • an adhesive layer is further formed between the polarizing plate 370 and the touch screen panel 380 and / or between the touch screen panel 380 and the flexible window film 390 to form a polarizing plate, a touch screen panel, and a flexible display panel.
  • the bond between the window films can be strengthened.
  • the adhesive layer may be formed of an adhesive composition including a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent.
  • a polarizer may be further formed below the display unit 350a to implement polarization of the internal light.
  • FIG. 6 is a cross-sectional view of a flexible display device according to another exemplary embodiment of the present invention.
  • the flexible display device 400 includes a display unit 350a, a touch screen panel 380, a polarizer 370, and a flexible window film 390, and the flexible window film 390 includes the present invention. It may include a window film for a display device according to the embodiments. Flexible display according to an embodiment of the present invention except that the touch screen panel 380 is not directly formed on the flexible window film 390, but the touch screen panel 380 is formed below the polarizer 370. It is substantially the same as the device. In this case, the touch screen panel 380 may be formed together with the display 350a.
  • the touch screen panel 380 since the touch screen panel 380 is formed together with the display unit 350a on the display unit 350a, the display panel 350a may be thinner and brighter than the flexible display device according to the exemplary embodiment of the present invention, and thus may have good visibility.
  • the touch screen panel 380 may be formed by deposition, but is not limited thereto.
  • the pressure-sensitive adhesive layer is further formed therein to increase the mechanical strength of the display device.
  • the adhesive layer may be formed of an adhesive composition including a (meth) acrylate resin, a curing agent, an initiator, and a silane coupling agent.
  • a polarizing plate is further formed below the display unit 350a to induce polarization of internal light to improve a display image.
  • FIG. 7 is a cross-sectional view of a flexible display device according to still another embodiment of the present invention.
  • the flexible display apparatus 500 includes a display unit 350b, an adhesive layer 360, and a flexible window film 390, and the flexible window film 390 according to embodiments of the present invention. It may include a window film for a display device. It is substantially the same as the flexible display device according to the exemplary embodiment of the present invention except that the device may be driven only by the display unit 350b and the polarizer and the touch screen panel are excluded.
  • the display unit 350b may include a substrate and an optical element including an LCD, an OLED, or an LED element formed on the substrate, and the display unit 350b may have a touch screen panel therein.
  • the window film for the display device of the embodiments is used in the flexible display device
  • the window film for the display device can also be used for the non-flexible display device.
  • organic nanoparticles were prepared.
  • the core is polybutylacrylate
  • the shell is polymethylmethacrylate
  • the shell is 35% by weight of the organic nanoparticles
  • the core is 65% by weight of the organic nanoparticles
  • the average particle diameter is 100nm
  • the organic nanoparticles having a refractive index of 1.48 was prepared.
  • Sylgard 184A (Dow coating, solid content: 100% by weight) containing a vinyl group-containing polydimethylsiloxane resin Sylgard 184B (Dow coating, solid content: 100% by weight) containing 100 parts by weight of methyl ethyl ketone 50 Part by weight was added to prepare a composition for a second coating layer.
  • the second coating layer composition of Preparation Example 2 was applied to one surface of a polyimide film (PI film, thickness: 80 ⁇ m, Samsung SDI Co., Ltd.) as a base layer and dried at 80 ° C. for 4 minutes. Applying the composition for the first coating layer of Preparation Example 1 on one side of the second coating layer, dried for 5 minutes at 100 °C, irradiated with UV of 1000mJ / cm 2 , and heated again at 80 °C for 4 minutes, the base layer, A window film for a display device having a three-layer structure in which two coating layers and a first coating layer were sequentially formed was manufactured.
  • PI film thickness: 80 ⁇ m, Samsung SDI Co., Ltd.
  • the first coating layer composition of Preparation Example 1 was applied to one surface of a polyimide film (PI film, thickness: 80 ⁇ m, Samsung SDI) as a substrate layer and dried at 100 ° C. for 5 minutes. Applying the second coating layer composition of Preparation Example 2 on the other side of the polyimide film and dried for 4 minutes at 80 °C, UV irradiation of 1000mJ / cm 2 , and heated again at 80 °C for 4 minutes, A window film for a display device having a three-layer structure in which two coating layers, a substrate layer, and a first coating layer were sequentially formed was manufactured.
  • PI film thickness: 80 ⁇ m, Samsung SDI
  • Example 1 the window film for display devices was manufactured by the same method except the structure of the window film for display devices being changed as Table 1 below.
  • the core is a core-shell structure composed of polybutyl acrylate (PBA), the shell is polymethyl methacrylate (PMMA), the shell is 40% by weight of organic particles, an average particle diameter of 230nm, and an organic nanoparticle having a refractive index of 1.48.
  • Particles were prepared. 4 parts by weight of the prepared organic nanoparticles and 100 parts by weight of a monomer mixture including 70% by weight of 2-ethylhexyl acrylate and 30% by weight of 4-hydroxybutyl acrylate and 0.005% by weight of a photopolymerization initiator (Irgacure 651) The parts were mixed well in a glass vessel.
  • Partial polymerization with hydroxyl groups having a viscosity of about 1000 CPS was achieved by polymerizing the mixture by replacing the dissolved oxygen in the glass vessel with nitrogen gas and irradiating with ultraviolet light using a low pressure lamp (BL Lamp manufactured by Sankyo) for several minutes ( A solution containing a meth) acrylic copolymer was obtained.
  • the pressure-sensitive adhesive composition was prepared by adding 0.35 parts by weight of an additional photopolymerization initiator (c2) (irgacure 184) to the (meth) acrylic copolymer having a hydroxyl group.
  • the resulting pressure-sensitive adhesive composition was coated on a release-treated PET (polyethylene terephthalate film, thickness 50 ⁇ m) to form an adhesive film having a thickness of 25 ⁇ m.
  • a release film having a thickness of 75 ⁇ m on the top After covering a release film having a thickness of 75 ⁇ m on the top, and irradiated on both sides using a low pressure lamp (BL Lamp manufactured by Sankyo) for 6 minutes to obtain a transparent adhesive sheet.
  • the PET film was removed from the transparent adhesive sheet to obtain an adhesive layer having a thickness of 25 ⁇ m.
  • PET film thickness: 40 ⁇ m
  • PET film thickness: 40 ⁇ m
  • PET film thickness: 40 ⁇ m
  • the window film was manufactured by the method similar to Example 1 using the prepared film laminated body as a base material layer.
  • composition for the first coating layer of Preparation Example 1 to one surface of a polyimide film (thickness: 80 ⁇ m, Samsung SDI Co., Ltd.) as a substrate layer, and dried at 100 °C for 5 minutes, and irradiated with UV of 1000mJ / cm 2 , It heated again at 80 degreeC for 4 minutes, and manufactured the window film for display apparatus of the 2-layered structure in which the base material layer and the 1st coating layer were formed sequentially.
  • a window film for a display device was manufactured in the same manner except for changing the thickness of the second coating layer in Example 2 as shown in Table 1 below.
  • Curvature radius The window film (width x length, 3cmx15cm) was wound on the curvature test JIG, and after holding it for 5 seconds or more, it evaluated visually whether the crack generate
  • Adhesion film (thickness: 50 ⁇ m, 3M OCA 8146) was attached to the window films for display elements of Examples and Comparative Examples, and the window film was a polyethylene terephthalate (PET) film (thickness: 100 ⁇ m, Mitsubishi G) The first coating layer was fixed on the top. An aluminum foil and a stainless plate (SUS plate) were sequentially placed on the lower surface of the PET film to prepare a specimen.
  • PET polyethylene terephthalate
  • SUS plate stainless plate
  • BALL DROP TEST evaluated the first height at which a visible steel mark was visible on the aluminum foil by dropping a spherical steel ball weighing 5.5g at a predetermined height from the first coating layer of the specimen. The average value was obtained by repeating five times. The higher the initial height, the higher the impact resistance of the window film. According to the ball drop test, it is confirmed that there is no impact even if the OLED panel is mounted when the initial height of the marks is more than 15cm.
  • PEN DROP TEST is the first to drop a pen with a ball weight (diameter) of 5.8g at a given height from the first coating layer and 0.7mm of PEN from the first coating layer, resulting in visually discernible marks on the surface of the aluminum foil and the first coating layer. The height of was evaluated. The average value was obtained by repeating five times. The higher the initial height, the higher the impact resistance of the window film. According to PEN DROP TEST, if the initial height of the marks is 4.5cm or more, there is no impact even if the OLED panel is mounted.
  • Optical characteristics Measurement of transmittance among optical characteristics was measured by using a CM-3600A (Konica Minolta Co., Ltd.) equipment to direct the first coating surface toward the light source of the equipment, and then measured and recorded the transmittance value Y (total light transmittance). do. The average value was obtained by repeating five times. Haze value is measured by the same method as the total light transmittance using a Hazemeter (NDH2000, Nippon denshoku).
  • the window film 1 prepared in Examples and Comparative Examples is cut in a horizontal width x length (10 cm x 10 cm), and the window film 1 so that the first coating layer faces upward. ) was placed on the bottom 2 and left at 25 ° C. and 40% relative humidity, the highest height H from the bottom 2 surface to the corner of the window film 1 was measured and the average value was calculated.
  • Pencil hardness It measured about the window film for display elements of an Example and a comparative example.
  • the first coating layer of the window film was measured by a JIS K5400 method using a pencil hardness tester (Heidon).
  • Heidon a pencil of 6B to 9H manufactured by Mitsubishi Corporation was used.
  • the load of the pencil on the first coating layer was 1 kg
  • the angle at which the pencil was drawn was 45 °
  • the speed at which the pencil was drawn was 60 mm / min. If the scratch occurs more than one time to evaluate five times, the pencil hardness is measured using the pencil of the step below, the five times the five times the maximum pencil hardness value when there is no scratch.
  • Example Comparative example One 2 3 4 5 6
  • One 2 Window film structure I * ⁇ - ⁇ - - ⁇ - - II * - ⁇ - ⁇ ⁇ - - ⁇ First coating layer thickness ( ⁇ m) 10 10 10 10 10 10 10 10 Second coating layer thickness ( ⁇ m) 100 100 100 100 150 100 - 50 Second coating layer composition
  • Preparation Example 2 Preparation Example 2
  • Preparation Example 3 Preparation Example 3
  • Preparation Example 2 Preparation Example 2
  • Impact resistance (cm) BALL DROP TEST 21 22 25 24 24 26 10 12 PEN DROP
  • the display device is excellent in impact resistance, thereby preventing damage to a display device due to external impact, for example, an OLED panel, when installed in a display device, and having a low curvature radius.
  • a window film for use was provided.
  • Example 6 including the film laminate as the substrate layer significantly improved the impact resistance compared to Examples 1 to 5.

Abstract

L'invention porte sur un film de fenêtre de dispositif d'affichage et sur un dispositif d'affichage flexible le comprenant, le film de fenêtre de dispositif d'affichage comprenant : une première couche de revêtement; et un stratifié d'une couche de base, formé sur une surface de la première couche de revêtement, et d'une seconde couche de revêtement, la première couche de revêtement étant constituée d'une première composition de revêtement comprenant un initiateur et une résine de siloxane ayant un groupe époxy alicyclique, un groupe glycidyle, un groupe fonctionnel contenant un groupe époxy alicyclique, ou un groupe fonctionnel contenant un groupe glycidyle, et la seconde couche de revêtement a une épaisseur d'environ 100 µm ou plus.
PCT/KR2017/000605 2016-06-27 2017-01-18 Film pour fenêtre de dispositif d'affichage et dispositif d'affichage flexible le comprenant WO2018004094A1 (fr)

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KR20200078394A (ko) * 2018-12-21 2020-07-01 한국세라믹기술원 광경화성 폴리카보실란의 제조방법
CN112099120A (zh) * 2020-09-15 2020-12-18 浙江夜光明光电科技股份有限公司 一种超柔软型反光布及其制备方法
CN113936555A (zh) * 2020-07-14 2022-01-14 乐金显示有限公司 盖窗和具有该盖窗的柔性显示装置
WO2023198746A1 (fr) * 2022-04-14 2023-10-19 Optitune Oy Revêtement dur de polysiloxane multicouche souple

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JP2012036313A (ja) * 2010-08-09 2012-02-23 Hitachi Chem Co Ltd 無機酸化物粒子の製造方法、及び当該製造方法により得られる無機酸化物粒子を用いた異方導電接着剤
KR20120036702A (ko) * 2010-10-08 2012-04-18 오점열 폴리우레탄 필름을 이용한 필름 히터 제조 방법
KR20120053621A (ko) * 2010-11-18 2012-05-29 코오롱글로텍주식회사 투명 플렉시블 필름 및 이의 제조방법
WO2016089021A1 (fr) * 2014-12-03 2016-06-09 삼성에스디아이 주식회사 Composition destinée à un film pour fenêtre, film souple pour fenêtre formé à partir de celle-ci, et dispositif d'affichage souple comprenant celui-ci

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KR20200078394A (ko) * 2018-12-21 2020-07-01 한국세라믹기술원 광경화성 폴리카보실란의 제조방법
KR102349496B1 (ko) 2018-12-21 2022-01-11 한국세라믹기술원 광경화성 폴리카보실란의 제조방법
CN113936555A (zh) * 2020-07-14 2022-01-14 乐金显示有限公司 盖窗和具有该盖窗的柔性显示装置
US20220020298A1 (en) * 2020-07-14 2022-01-20 Lg Display Co., Ltd. Cover Window and Flexible Display Device Having the Same
CN113936555B (zh) * 2020-07-14 2024-01-02 乐金显示有限公司 盖窗和具有该盖窗的柔性显示装置
US11978370B2 (en) * 2020-07-14 2024-05-07 Lg Display Co., Ltd. Cover window and flexible display device having the same
CN112099120A (zh) * 2020-09-15 2020-12-18 浙江夜光明光电科技股份有限公司 一种超柔软型反光布及其制备方法
WO2023198746A1 (fr) * 2022-04-14 2023-10-19 Optitune Oy Revêtement dur de polysiloxane multicouche souple

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