WO2022154144A1 - 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름, 이를 포함한 커버윈도우 및 디스플레이 장치 - Google Patents
플렉서블 디스플레이 장치의 커버 윈도우용 보호필름, 이를 포함한 커버윈도우 및 디스플레이 장치 Download PDFInfo
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- WO2022154144A1 WO2022154144A1 PCT/KR2021/000625 KR2021000625W WO2022154144A1 WO 2022154144 A1 WO2022154144 A1 WO 2022154144A1 KR 2021000625 W KR2021000625 W KR 2021000625W WO 2022154144 A1 WO2022154144 A1 WO 2022154144A1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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Images
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Definitions
- the present invention relates to a protective film for a cover window of a flexible display device, a cover window including the same, and a display device.
- Such a cover window for a flexible display is a layer applied to the outermost layer of the flexible display, and at the same time exhibits high hardness and scratch resistance, and at the same time, excellent flexibility is required to satisfy characteristics such as bendable, foldable, and rollable.
- glass is used as a cover panel to satisfy such high hardness.
- the present invention simultaneously satisfies the balance of properties of flexibility, high hardness and scratch resistance, and in particular, there is little damage to the film even by repeated bending or folding operations, and improves the impact resistance of the glass panel, and the glass panel
- a protective film for a cover window of a flexible display device that prevents scattering when broken.
- the present invention includes the protective film, and exhibits flexibility, flexibility, high hardness, scratch resistance, and high transparency. , or a cover window of a flexible display device that can be easily applied to a foldable mobile device or a display device.
- the present invention provides a flexible display device including the cover window.
- the first hard coating layer comprising 3 parts by weight or less of inorganic particles relative to 100 parts by weight of the first binder resin;
- a second hard coating layer comprising 10 to 45 parts by weight of inorganic particles relative to 100 parts by weight of the binder resin; and a light-transmitting substrate are sequentially stacked, and the thickness ratio of the first hard coating layer and the second hard coating layer is 10:90 to 40:60. It provides a protective film for a cover window of a flexible display device.
- the present specification provides a cover window for a flexible display device including a protective film for the cover window of the flexible display device.
- the present specification provides a flexible display device including a cover window of the flexible display device.
- flexible means a state having a degree of flexibility that does not cause cracks with a length of 3 mm or more when wound on a cylindrical mandrel having a diameter of 8 mm or less, Therefore, the flexible plastic film of the present invention can be applied as a cover film of a bendable, flexible, rollable, or foldable display.
- (meth)acrylate is meant to include both acrylates and methacrylates.
- the term “light-transmitting substrate” refers to a substrate having a light transmittance of 50% or more in the visible ray region, for example, 380 to 780 nm.
- the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method.
- a commonly known analyzer and a detector such as a differential refraction detector and a column for analysis may be used, and the temperature at which it is normally applied Conditions, solvents, and flow rates can be applied.
- the measurement conditions using a Polymer Laboratories PLgel MIX-B 300 mm long column and Waters PL-GPC220 instrument, the evaluation temperature is 160° C., and 1,2,4-trichlorobenzene is used as a solvent.
- the flow rate was 1 mL/min, and the sample was prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 ⁇ L, and the value of Mw can be obtained using a calibration curve formed using a polystyrene standard.
- the molecular weight of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.
- the first hard coating layer comprising 3 parts by weight or less of inorganic particles relative to 100 parts by weight of the binder resin;
- a second hard coating layer comprising 10 to 45 parts by weight of inorganic particles relative to 100 parts by weight of the binder resin;
- the present inventors conducted research on an optical laminate applicable to a protective film for a cover window of a flexible display device, and in an optical laminate having a hard coat layer having a two-layer structure on one surface of a light-transmitting substrate
- the lower hard coat layer (hereinafter referred to as the second hard coat layer.) is thicker than the upper hard coat layer (hereinafter referred to as the first hard coat layer.), for example, the thickness ratio of the first hard coat layer and the second hard coat layer 10:90 to 40:60, and when inorganic particles are included in a specific content in the first and second hard coating layers, wound on a mandrel having a diameter of 8 mm or less while having high hardness and excellent scratch resistance
- the invention was completed after confirming that it can be used as a protective film for a cover window of a flexible display device because cracks do not occur when using the device.
- the protective film for the cover window of such a flexible display device realizes to satisfy the balance of properties of flexibility and high hardness at the same time, and at the same time exhibits excellent scratch resistance and high hardness characteristics.
- the invention was completed after confirming that it can be easily applied to a bendable, flexible, rollable, or foldable mobile device or a display device because there is little damage.
- the physical properties of the protective film for a cover window of the flexible display device are components included in the first hard coating layer and the second hard coating layer, in particular, a component of the binder resin. And, it may be according to whether inorganic particles are included in the binder resin and the content thereof. Alternatively, the above-described physical properties may also be related to a thickness ratio of the first hard coating layer and the second hard coating layer.
- a hard coating layer having a two-layer structure may be formed on the light-transmitting substrate included in the protective film for a cover window of the flexible display device, and as described above, a second hard coating layer is formed on the light-transmitting substrate, and the first A first hard coat layer is formed on the second hard coat layer, and the protective film may sequentially include a first hard coat layer, a second hard coat layer, and a substrate.
- the protective film includes a light-transmitting substrate and a hard coat layer having a two-layer structure, excellent bendability, hardness, and scratch resistance properties can be simultaneously implemented.
- this structure it is possible to satisfy the balance of properties of flexibility, scratch resistance and high hardness at the same time, and it is possible to prevent damage to the internal structure even by repeated bending or folding operations, and also with excellent mechanical properties and heat resistance. It may have optical properties such as high transparency.
- the second hard coating layer as the lower layer is 100 parts by weight of the binder resin, and 10 to 45 parts by weight, 10 to 40 parts by weight, 15 to 35 parts by weight of inorganic particles relative to 100 parts by weight of the binder resin, or 20 to 30 parts by weight.
- the upper layer may contain 100 parts by weight of the binder resin, and 3 parts by weight or less, 1 part by weight or less, 0.1 parts by weight or less of inorganic particles compared to 100 parts by weight of the binder resin, or may not contain inorganic particles. have.
- the inorganic particles may serve to improve the hardness of the hard coating layer, but when inorganic particles are present on the surface of the hard coating layer due to a rather weak interaction with the binder resin, the scratch resistance decreases due to surface roughness can be
- the first hard coating layer which is an upper layer, is 3 parts by weight or less, 1 part by weight or less, 0.1 to 100 parts by weight of the binder resin. It may be included in parts by weight or less, or inorganic particles may not be included.
- the first hard coating layer contains more than 3 parts by weight of inorganic particles based on 100 parts by weight of the binder resin, the scratch resistance of the protective film is lowered and thus it is easily damaged by external impact. Scratch can occur
- the second hard coating layer which is the lower layer, contains 10 to 45 parts by weight, 10 to 40 parts by weight, 15 to 45 parts by weight of inorganic particles based on 100 parts by weight of the binder resin. 35 parts by weight, 20 to 30 parts by weight may be included.
- the protective film simultaneously satisfies the balance of properties of flexibility and high hardness, and can prevent damage to the internal structure even by repeated bending or folding operations, and high transparency with excellent mechanical properties and heat resistance. may have optical properties of
- the inorganic particles for example, silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, metal oxide particles formed of cerium oxide and the like; metal fluoride particles formed of magnesium fluoride, sodium fluoride, or the like; metal sulfide particles; metal nitride particles; And it may be at least one selected from the group consisting of metal particles.
- the diameter of the inorganic particles may be 1 to 300 nm, 10 to 200 nm, or 30 to 100 nm.
- the protective film for a cover window of the flexible display device simultaneously satisfies the balance of physical properties of flexibility, high hardness and scratch resistance, and can prevent damage to the internal structure even by repeated bending or folding operations. , high mechanical properties and heat resistance as well as optical properties such as high transparency.
- the physical property balance and excellent optical properties may be related to the thickness of the first hard coating layer and the second hard coating layer.
- the first hard coating layer as the upper layer may be thinner than the second hard coating layer as the lower layer, and specifically, the thickness ratio of the first hard coating layer and the second hard coating layer is 10:90 to 40:60, 15:85 to 35:65, or 20:80 to 30:70.
- the thickness ratio of the first hard coat layer and the second hard coat layer is less than 10:90 Scratch resistance may be deteriorated, and if it exceeds 40:60, there is a problem in that bending properties are lowered.
- the thickness of the first hard coating layer is 1 ⁇ m to 10 ⁇ m, 1 ⁇ m to 9 ⁇ m, or 2 ⁇ m to 7 ⁇ m.
- the thickness of the first hard coating layer is too thick, bending properties may be deteriorated, and if it is too thin, scratch resistance may be deteriorated.
- the thickness of the second hard coating layer is 1 ⁇ m to 10 ⁇ m, 2 ⁇ m to 9 ⁇ m, or 3 ⁇ m to 8 ⁇ m.
- the thickness of the second hard coating layer is too thick, the bending property may be deteriorated, and when the thickness of the second hard coating layer is too thin, there is a problem in that the film hardness is reduced.
- the total thickness of the first hard coat layer and the second hard coat layer may be 2 ⁇ m to 17 ⁇ m, 3 ⁇ m to 16 ⁇ m, or 4 ⁇ m to 15 ⁇ m.
- the first hard coat layer and the second hard coat layer having the above-described components and properties are sequentially stacked, a high level of hardness is secured, and better scratch resistance than when a hard coat layer of the same thickness is included It has properties, flexibility, and elasticity, and furthermore, it has less curl (curl) generation, so it may have excellent curl properties.
- a gap of 4 mm is placed in the middle of the protective film for the cover window of the flexible display device, and cracks do not occur when both sides of the protective film are folded and unfolded at 90 degrees with respect to the bottom surface 100,000 times at room temperature.
- Repeating the folding and unfolding of a gap of 4 mm in the middle of the protective film may be, for example, a bending test performed with a rod having a diameter of 4 mm on the protective film.
- FIG. 1 schematically shows a method for evaluating dynamic bending properties.
- the gap between the folds in the middle of the protective film is 4 mm, and both sides of the protective film are folded and unfolded at 90 degrees with respect to the bottom surface at 25° C.
- the durability against bending can be measured by repeating 100,000 times at a rate of once per 1.5 seconds.
- a rod having a diameter (R) of 4 mm was placed so that a rod of 4 mm in diameter was placed in contact with the protective film, the rest of the protective film was fixed, and both sides of the protective film were folded around the rod. You can take the method of repeating the unfolding.
- the folded portion is not particularly limited as long as it is inside the protective film, and for convenience of measurement, the central portion of the protective film may be folded so that both sides of the protective film are symmetrical except for the folded portion.
- cracks of 1 cm or more or 3 mm or more do not occur in the protective film even after bending 100,000 times, and cracks may not occur substantially.
- cracks do not occur even when the protective film is bent to either side of the inner and outer sides, and for example, cracks do not occur even when the light-transmitting substrate of the protective film is folded inward or the first hard coating layer is folded inward. it may not be Therefore, the possibility of cracks occurring even in actual use conditions such as repeated folding, rolling, or bending is very low, and thus it can be suitably applied as a protective film for a cover window of a flexible display device.
- the protective film for the cover window of the flexible display device may have a pencil hardness measured on the surface of the first hard coating layer of H or more based on a 750 g load.
- the protective film for a cover window of the flexible display device may have a water contact angle of 105° or more on the surface of the first hard coating layer.
- the first hard coating layer may function as a touch surface. Since the protective film has a water contact angle of 105° or more, the touch panel can be freely operated by sliding a finger or pen on the touch surface.
- the protective film for a cover window of the flexible display device of the embodiment has a light transmittance of 90.0% or more, 92.0% or more, or 94.0% or more, and a haze of 1.0% or less, or 0.7% with respect to light in a wavelength region of 550 nm. or less, or 0.5% or less.
- the protective film for the cover window of the flexible display device of the one embodiment includes a hard coating layer that can secure durability against repeated bending or folding operations while having high hardness, and these characteristics of the hard coating layer are included in the hard coating layer.
- the composition of the binder resin and as described above It may be related to the presence or absence of inorganic particles and their content.
- the binder resin included in the first hard coating layer and the second hard coating layer may each independently include a polyfunctional (meth)acrylate-based compound.
- the polyfunctional (meth)acrylate-based compound may be, for example, a polyfunctional (meth)acrylate-based monomer, a polyfunctional (meth)acrylate-based oligomer, or a mixture thereof.
- the first hard coating layer and the second hard coating layer may include the same polyfunctional (meth)acrylate-based compound, or may include different polyfunctional (meth)acrylate-based compounds.
- the binder resin of the first hard coating layer may contain 3 parts by weight or less, 1 part by weight or less, 0.1 parts by weight or less of inorganic particles, or may not contain inorganic particles, based on 100 parts by weight of the binder resin.
- the second hard coating layer with respect to 100 parts by weight of the binder resin, 10 to 45 parts by weight, 10 to 40 parts by weight, 15 to 35 parts by weight, 20 to 30 parts by weight of inorganic particles may be included.
- the polyfunctional (meth)acrylate-based compound has 2 to 10 (meth)acrylate functional groups, and has a weight average molecular weight of 50 to 2,000 g/mol, 10 to 1,000 g/mol, or 100 to 700 g /mol, and the acrylate equivalent weight may be from 50 to 1000 g/mol, from 100 to 900 g/mol, or from 150 to 800 g/mol.
- first hard coat layer and the second hard coat layer are each independently, with respect to 100 parts by weight of the binder resin, 50 parts by weight or more of the polyfunctional (meth)acrylate-based compound, 60 parts by weight to 100 parts by weight, Alternatively, it may be included in an amount of 70 parts by weight to 95 parts by weight, whereby the flexibility of the hard coating layer including the binder resin may be improved.
- the polyfunctional (meth) acrylate-based compound ethylene oxide (ethylene oxide), propylene oxide (propylene oxide), urethane (urethane), caprolactone (caprolactone), epoxy (epoxy) and ester (ester) It may be modified with one or more selected from the group.
- the polyfunctional (meth) acrylate-based compound has excellent flexibility and can impart flexibility to a hard coating layer using the same, and further, the above-mentioned modified polyfunctional (meth) acrylate-based oligomer has more flexibility. In the case of a hard coating layer using the same, curl characteristics and flexibility may be increased.
- the polyfunctional (meth)acrylate-based oligomer has an acrylate functional group 2 to 10, the weight average molecular weight may be 200 to 2,000 g / mol, 300 to 1,000 g / mol, or 350 to 500 g / mol, the acrylate equivalent weight (equivalent weight) of 100 to 1000 g / mol, 200 to 900 g/mol, or 300 to 800 g/mol.
- the (meth)acrylate-based oligomer is not limited thereto, but may include, for example, one or more functional groups selected from the group consisting of urethane, epoxy, ether, alkylene oxide, and ester.
- the polyfunctional (meth) acrylate-based monomer has an acrylate functional group have 2 to 6, weight average molecular weight 50 to 600 g/mol, 50 to 500 g/mol, or 50 to 300 g/mol.
- the polyfunctional (meth) acrylate-based monomer has an acrylate equivalent weight 50 to 300 g/mol, 70 to 250 g/mol, or 100 to 200 g/mol.
- the polyfunctional (meth) acrylate-based monomer is not limited thereto, but trimethylolpropane triacrylate (TMPTA), trimethylolpropaneethoxy triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PETA) or dipentaerythritol hexaacrylate (DPHA); and the like.
- TMPTA trimethylolpropane triacrylate
- TMPEOTA trimethylolpropaneethoxy triacrylate
- GPTA glycerin propoxylated triacrylate
- PETA pentaerythritol tetraacrylate
- DPHA dipentaerythritol hexaacrylate
- the first hard coating layer may further include one or more additives selected from the group consisting of a fluorine-based additive, a silicone-based additive, and a fluorine-silicone-based additive.
- the additive may enhance finger sliding properties, stain resistance and stain wipeability.
- 0.5 to 5 parts by weight, 1 to 4 parts by weight, or 2 to 3 parts by weight of the additive may be included with respect to 100 parts by weight of the binder resin. remind If the content of the additive is too small, finger sliding properties, stain resistance, and wiping property against stains may be reduced, and if the content of the additive is too large, the content of other components may decrease, thereby reducing strength and scratch resistance.
- the fluorine-based additive is not limited thereto, but may be a fluoropolyether, a fluoropolyalkyl, or a mixture thereof.
- the silicone-based additive is not limited thereto, but may be a silicone resin modified with various organic groups such as polyether, alkyl, acryl, and epoxy.
- the fluorine-silicone-based additive is not limited thereto, but may be a polydialkylsiloxane-based polymer in which at least one silicone is substituted with one or more fluorine, for example, a siloxane-fluoropolyalkyl-based compound.
- the protective film for the cover window of the flexible display device has excellent optical properties in order to realize the above-described properties, and simultaneously satisfies the balance of properties of flexibility, high hardness and high scratch resistance, and it can be applied to the internal structure even by repeated bending or folding operations. It is preferable to include a light-transmitting substrate capable of preventing damage from occurring.
- the light-transmitting substrate means a substrate having a light transmittance of 50% or more in a visible light region, for example, 380 to 780 nm.
- the yellow index of the light-transmitting substrate measured on the basis of ASTM D1925 is 4.5 or less or 3.8 or less
- the haze of the light-transmitting substrate measured according to ASTM D1003 is 1.1% or less, or 0.4 to 0.8% , and thus may have colorless and transparent optical properties.
- the type of the light-transmitting substrate is not particularly limited as long as it satisfies the above-described characteristics, but more specific examples include polyimide (PI), polyimideamide, polyetherimide (PEI), polyethylene Terephthalate (polyethyleneterephtalate, PET), polyethylenenaphthalate (PEN), polyetheretherketone (PEEK), cyclic olefin polymer (COP), polyacrylate (PAC), polymethyl It may include at least one selected from the group consisting of methacrylate (polymethylmethacrylate, PMMA), and triacetylcellulose (TAC).
- PI polyimide
- PEI polyimideamide
- PEI polyetherimide
- PET polyethylene Terephthalate
- PEN polyethylenenaphthalate
- PEEK polyetheretherketone
- COP cyclic olefin polymer
- PAC polyacrylate
- polymethyl It may include at least one selected from the group consisting of methacrylate (polymethylmethacryl
- the thickness of the light-transmitting substrate may be 5 ⁇ m to 150 ⁇ m, 10 ⁇ m to 130 ⁇ m, or 20 ⁇ m to 100 ⁇ m. If the thickness of the light-transmitting substrate is too thin, there is a risk of breakage or curling during the coating layer forming process, and it may be difficult to achieve high hardness. On the other hand, if the thickness is too thick, the flexibility may be low and it may be difficult to form the flexible film.
- the total thickness of the first hard coating layer, the second hard coating layer, and the light-transmitting substrate may be 40 ⁇ m to 150 ⁇ m, 50 ⁇ m to 140 ⁇ m, 60 ⁇ m to 130 ⁇ m, or 60 ⁇ m to 120 ⁇ m.
- a structure in which a first hard coating layer and a second hard coating layer having predetermined components and properties are sequentially stacked a high level of hardness is ensured, and a hard coating layer of the same thickness is included. It has superior scratch resistance, flexibility, and elasticity, and may have excellent curl characteristics due to less occurrence of curl. Accordingly, protection for the cover window of the flexible display device without significantly increasing the thickness of the light-transmitting substrate It is possible to secure the mechanical properties or elastic properties required for the film.
- the total thickness of the first hard coating layer, the second hard coating layer, and the light-transmitting substrate is excessively thick, crack resistance against repeated bending or folding operations may be reduced or flexibility may be reduced, and the above-described total thickness may be If it is excessively thin, the hardness may be lowered, and scratches or curls may occur due to external impact.
- the protective film for a cover window of the flexible display device is formed by applying a coating composition for forming a second hard coating layer on at least one surface of the light-transmitting substrate and photocuring to form a second hard coating layer, and the second hard coating layer is applied to the second hard coating layer.
- a coating composition for forming a hard coat layer and photocuring may be provided by applying a coating composition for forming a hard coat layer and photocuring.
- the method of applying the coating composition is not particularly limited as long as it can be used in the technical field to which the present technology belongs, for example, bar coating method, knife coating method, roll coating method, blade coating method, die coating method, micro gravure coating method, comma coating method, slot die coating method, lip coating method, solution casting method, etc. can be used.
- a plastic resin film between the light-transmitting substrate and the second hard coating layer, between the first hard coating layer and the second hard coating layer, or on the first hard coating layer, a plastic resin film, an adhesive film, a release film, a conductive film, a conductive layer, a liquid crystal layer , a coating layer, a cured resin layer, a non-conductive film, a layer such as a metal mesh layer or a patterned metal layer, a film, or a film may further include one or more.
- a second hard coating layer is formed thereon to give an anti-static function, or a low refractive index layer on the first hard coating layer It is also possible to implement a low reflection function by introducing it.
- the layer, film, film, or the like may be in any form of a single layer, a double layer, or a laminate type.
- the layer, film, or film may be laminated on the coating layer by lamination, coating, vapor deposition, sputtering, etc., of a freestanding film using an adhesive or adhesive film, but the present invention However, the present invention is not limited thereto.
- the first and second hard coating layers are, in addition to the binder resin and inorganic fine particles, a photoinitiator, an organic solvent, a surfactant, a UV absorber, a UV stabilizer, an anti-yellowing agent, a leveling agent, an antifouling agent, a dye for improving color value, etc. It may further include components commonly used in the technical field to which the present invention pertains. In addition, since the content can be variously adjusted within the range that does not degrade the physical properties of the hard coating layer, it is not particularly limited, but for example, it may be included in an amount of about 0.01 to about 30 parts by weight based on 100 parts by weight of the hard coating layer.
- the surfactant may be a fluorine-based acrylate, a fluorine-based surfactant, or a silicone-based surfactant having 1-2 functional properties.
- the surfactant may be included in a dispersed or cross-linked form in the hard coating layer.
- the additive may include a UV absorber or a UV stabilizer
- the UV absorber may include a benzophenone-based compound, a benzotriazole-based compound, or a triazine-based compound
- the UV stabilizer includes tetramethyl p and peridine (tetramethyl piperidine).
- the photoinitiators include 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1-[4-(2-hydroxyethoxy )phenyl]-2-methyl-1-propanone, methylbenzoylformate, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, 2-benzoyl-2-(dimethylamino)-1-[4-(4-) Morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone diphenyl (2,4, 6-trimethylbenzoyl)-phosphine oxide, or bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like, but are not limited thereto.
- products currently on the market include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, Esacure KIP 100F, and the like.
- photoinitiators may be used alone or in mixture of two or more different types.
- the organic solvent examples include an alcohol-based solvent such as methanol, ethanol, isopropyl alcohol, and butanol, an alkoxy alcohol solvent such as 2-methoxyethanol, 2-ethoxyethanol, and 1-methoxy-2-propanol, acetone, and methyl Ketone solvents such as ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, and cyclohexanone, propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Ether solvents such as diethylene glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol monopropyl ether, diethyl glycol monobutyl ether, diethylene glycol-2-ethylhexyl ether, benzene, toluene,
- a cover window for a flexible display device including a protective film for a cover window of the flexible display device may be provided.
- the cover window for the flexible display device may further include a glass cover or a plastic film cover formed on one surface of the protective film for the cover window and having a thickness of 20 ⁇ m to 180 ⁇ m. That is, the cover window for the flexible display device includes a cover and a protective film for the cover window formed on one surface of the cover, and the cover may be a glass cover or a plastic film cover.
- the glass cover and the plastic film cover may have a transparent property, thereby allowing light output from the display panel inside the flexible display device to pass therethrough.
- the glass cover may have high hardness and excellent scratch resistance, but may be easily broken due to reduced impact resistance.
- the glass cover may include, for example, glass having a high refractive index (eg, a refractive index of 1.65 or more), but is not limited thereto.
- the cover window for a flexible display device improves the impact resistance of the glass panel by forming the protective film on the glass panel, and prevents scratches or dents caused by external impact. It can be prevented, and when the glass panel is broken, scattering can be prevented, thereby preventing a risk in handling by the user.
- the plastic film cover may have high hardness and excellent scratch resistance, for example, a polyimide film, a polyimideamide film, a polyetherimide film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyether ether. It may include at least one selected from the group consisting of a ketone film, a cyclic olefin polymer film, a polyacrylate film, a polymethyl methacrylate film, and a triacetyl cellulose film.
- the thickness of the glass cover and the plastic film cover may each independently be 20 ⁇ m to 180 ⁇ m.
- the thickness is too thin, there is a problem in that hardness characteristics are deteriorated, and when the thickness is too thick, there is a problem in that cracks occur as a result of the dynamic bending test.
- the glass cover may have a thickness of 20 ⁇ m to 180 ⁇ m, 25 ⁇ m to 150 ⁇ m, 30 ⁇ m to 120 ⁇ m, or 30 ⁇ m to 100 ⁇ m.
- the plastic film cover may have a thickness of 20 ⁇ m to 180 ⁇ m, 30 ⁇ m to 170 ⁇ m, 40 ⁇ m to 150 ⁇ m, or 50 ⁇ m to 130 ⁇ m.
- the cover window for the flexible display device may further include an adhesive layer.
- the adhesive layer may be disposed between the cover and the protective film.
- the adhesive layer can attach the cover and the protective film by pressure (pressing force) at room temperature.
- the pressure-sensitive adhesive layer may be implemented as an adhesive or a pressure-sensitive adhesive film, and is not particularly limited as long as it is known in the art. Meanwhile, the adhesive film is not particularly limited as long as it is known in the art, but a double-sided adhesive film such as an optically clear adhesive (OCA) film may be used.
- OCA optically clear adhesive
- a display device including a cover window of the flexible display device may be provided.
- the display device may be a flexible display device.
- the flexible display device may have a curved, bendable, flexible, rollable, or foldable shape. of a mobile communication terminal, a smart phone, a touch panel of a tablet PC, a wearable device, and various displays.
- the wearable device is an accessory type (eg, a watch, a ring, a bracelet, an anklet, a necklace, glasses, a contact lens, or a head-mounted-device (HMD)), a fabric or a clothing integrated type ( It may include at least one of, for example, electronic clothing), a body attachable type (eg, a skin pad or tattoo), or a bioimplantable type (eg, an implantable circuit).
- HMD head-mounted-device
- the flexible display device may include a display panel and a cover window.
- the cover window may include a cover and a protective film, and may further include an adhesive layer between the cover and the protective film.
- the flexible display device is, for example, a liquid crystal display (LCD) device, a light emitting diode (LED) display device, an organic light emitting diode (OLED) display device, a microelectromechanical system (MEMS) display device or a rollable display device (rollable display or foldable display).
- LCD liquid crystal display
- LED light emitting diode
- OLED organic light emitting diode
- MEMS microelectromechanical system
- rollable display device rollable display or foldable display
- the cover window of the flexible organic light emitting diode display device may be located in an outer portion in a direction in which light or a screen is emitted, and a cathode providing electrons;
- An electron transport layer, an emission layer, a hole transport layer, and an anode providing holes may be sequentially formed.
- the organic light emitting diode (OLED) display may further include a hole injection layer (HIL) and an electron injection layer (EIL).
- the cathode and anode electrodes and each component may be used as a material having a predetermined elasticity.
- Another example of the flexible display device may be a rollable display or foldable display.
- the retractable display device may have various structures depending on the field of application and specific form, for example, including a cover window, a touch panel, a polarizing plate, a barrier film, a light emitting device (OLED device, etc.), a transparent substrate, etc. can be a structure.
- a protective film for a cover window of a flexible display device that prevents scattering when the cover is broken may be provided.
- cover window and the flexible display device including the protective film for the cover window of the flexible display device exhibit flexibility, flexibility, high hardness, scratch resistance, and high transparency. It can be usefully applied to bendable, flexible, rollable, or foldable mobile devices, display devices, front panels of various instrument panels, display parts, etc.
- 1 is an experimental example 3 schematically shows how to conduct the bending durability test.
- CN9013 100 g of CN9013, a polyfunctional acrylate-based compound (manufacturer: Sartomer, 9-functional, urethane-modified), 2 g of RS-537 (manufacturer: DIC), a fluorine-based additive, 2 g of I907 (manufacturer: Ciba), a photoinitiator, and a solvent
- a coating solution for forming the first hard coating layer was prepared by mixing 100 g of methyl isobutyl ketone.
- pentaerythritol triacrylate manufactured by the manufacturer: Kyoeisha, weight average molecular weight: 298 g/mol, acrylate group equivalent: 100 g/mol
- a polyfunctional acrylate-based compound MEK-AC-2140Z (silica sol), an inorganic particle , manufacturer: Nissan Chemical, diameter: 12 nm, solid content 40%) 125 g
- photoinitiator I184 manufactured by Ciba
- solvent methyl isobutyl ketone 100 g were mixed to prepare a coating solution for forming a second hard coat layer .
- the coating solution for forming the second hard coating layer described in Table 1 below was applied to one surface of the polyethylene terephthalate film, which is a light-transmitting substrate, in a bar coating method, and dried at 60° C. for 2 minutes in an air atmosphere.
- a second hard coating layer was prepared by photo-curing in a nitrogen atmosphere with a mercury lamp (light quantity: 100 mJ/cm 2 ).
- the coating solution for forming a hard coating layer was applied by a bar coating method, and dried at 60° C. for 2 minutes in an air atmosphere.
- a first hard coating layer was prepared by photocuring with a mercury lamp (light quantity: 200 mJ/cm 2 ) in a nitrogen atmosphere to prepare a protective film for a cover window.
- the thickness of the first hard coat layer and the second hard coat layer and the thickness of the polyethylene terephthalate film were measured using a digital micrometer, and the results are shown in Table 1 below.
- Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 1st hard coating layer coating solution Preparation 1-1 Preparation 1-1 Preparation Example 1-2 Preparation 1-1 Production Example 1-3 Preparation Example 1-4 Preparation 1-1 - Preparation 1-1 Preparation 1-1 Thickness ( ⁇ m) 2 1.5 3 2 5 2 5 - 2 2 2nd hard coating layer coating solution Preparation 2-1 Preparation 2-2 Preparation 2-2 Preparation 2-3 - Preparation 2-2 Preparation 2-2 Preparation 2-1 Preparation 2-4 Preparation Example 2-5 Thickness ( ⁇ m) 5 6 10 5 - 5 3 5 5 5 5 Light-transmitting substrate thickness ( ⁇ m) 75 100 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75
- the minimum diameter at which a crack of 3 mm or longer does not occur was measured after being wound around a cylindrical mandrel of various diameters.
- FIG. 1 is a view schematically illustrating a method of performing a bending durability and bending stability test for a protective film according to an embodiment of the present invention.
- the protective films of Examples and Comparative Examples were cut, but laser cut to a size of 80 x 140 mm to minimize microcracks in the edge region. Place the laser-cut film on the measuring device, put the light-transmitting substrate inside, and make the gap (inner curvature diameter) of the folded part 4 mm, and at room temperature, both sides of the protective film were folded and unfolded at 90 degrees with respect to the bottom was repeated 10,000 times as a continuous operation (the film folding rate was once per 1.5 seconds).
- Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 pencil hardness 2H 2H 2H 2H 2H 2H H 2H 3H flexibility (mm) 6 5 6 8 12 6 10 4 10 16 bending durability Good Good Good Good error Good error Good error error scratch resistance Good Good Good Good Good error Good error Good Transmittance (%) 92.0 92.1 92.0 92.1 92.2 92.0 92.1 92.0 Haze (%) 0.3 0.4 0.3 0.3 0.3 0.3 0.4 0.3 0.3 0.3 0.3 0.4 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
- the protective film for the cover window of the flexible display device of the embodiments exhibits excellent scratch resistance and optical properties regarding transmittance and haze while exhibiting high hardness and satisfying sufficient flexibility at the same time. It has been confirmed that the film can be easily applied to bendable, flexible, rollable, or foldable mobile devices or display devices because there is little damage to the film even by repeated bending or folding operations.
- the protective films of Comparative Examples did not exhibit relatively low scratch resistance, or bending durability enough to be used as a protective film of a flexible display device, unlike in Examples.
- Comparative Example 1 including only the first hard coating layer, Comparative Example 3 in which the first hard coating layer is thicker than the second hard coating layer, and 45 parts by weight of nano silica in the second hard coating layer relative to 100 parts by weight of the binder resin
- Comparative Examples 5 and 6 containing an excess of part, it was confirmed that the bending durability was not sufficient to be used as a protective film of a flexible display device.
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Abstract
Description
실시예1 | 실시예2 | 실시예3 | 실시예4 | 비교예 1 | 비교예 2 | 비교예 3 | 비교예 4 | 비교예 5 | 비교예6 | ||
제1하드코팅층 | 코팅액 | 제조예1-1 | 제조예1-1 | 제조예1-2 | 제조예1-1 | 제조예1-3 | 제조예1-4 | 제조예1-1 | - | 제조예1-1 | 제조예1-1 |
두께 (㎛) | 2 | 1.5 | 3 | 2 | 5 | 2 | 5 | - | 2 | 2 | |
제2하드코팅층 | 코팅액 | 제조예2-1 | 제조예2-2 | 제조예2-2 | 제조예2-3 | - | 제조예2-2 | 제조예2-2 | 제조예2-1 | 제조예2-4 | 제조예2-5 |
두께 (㎛) | 5 | 6 | 10 | 5 | - | 5 | 3 | 5 | 5 | 5 | |
광투과성 기재 두께 (㎛) | 75 | 100 | 75 | 75 | 75 | 75 | 75 | 75 | 75 | 75 |
실시예1 | 실시예2 | 실시예3 | 실시예4 | 비교예1 | 비교예2 | 비교예3 | 비교예4 | 비교예5 | 비교예6 | |
연필경도 | 2H | 2H | 2H | 2H | 2H | 2H | 2H | H | 2H | 3H |
굴곡성
(mm) |
6 | 5 | 6 | 8 | 12 | 6 | 10 | 4 | 10 | 16 |
굽힘 내구성 | 양호 | 양호 | 양호 | 양호 | 불량 | 양호 | 불량 | 양호 | 불량 | 불량 |
내스크래치성 | 양호 | 양호 | 양호 | 양호 | 양호 | 불량 | 양호 | 불량 | 양호 | 양호 |
투과율(%) | 92.0 | 92.1 | 92.0 | 92.1 | 92.2 | 92.0 | 92.1 | 92.2 | 92.1 | 92.0 |
헤이즈(%) | 0.3 | 0.4 | 0.3 | 0.3 | 0.3 | 0.3 | 0.4 | 0.3 | 0.3 | 0.3 |
Claims (17)
- 바인더 수지 100 중량부 대비 무기 입자 3 중량부 이하를 포함하는 제1 하드코팅층;바인더 수지 100 중량부 대비 무기 입자 10 내지 45 중량부를 포함하는 제2 하드코팅층; 및광투과성 기재;가 순차적으로 적층되고,상기 제1 하드코팅층 및 제2 하드코팅층의 두께비는 10:90 내지 40:60인, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 커버 윈도우용 보호필름 중간에 4 mm의 간격을 두고 상기 커버 윈도우용 보호필름의 양 쪽을 바닥면에 대하여 90도로 접었다 폈다를 상온에서 10만회 반복하였을 때 크랙이 발생하지 않는, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 제1 하드코팅층은 750 g의 하중에서 H 이상의 연필 경도를 갖는, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 제1 하드코팅층의 표면은 수접촉각이 105° 이상인, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 커버 윈도우용 보호필름은 550 nm의 파장 영역의 빛에 대하여 90.0 % 이상의 투과율을 가지며, 1.0 % 이하의 헤이즈 값을 갖는, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 제1 하드코팅층의 두께는 1 ㎛ 내지 10 ㎛인, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 제2 하드코팅층의 두께는 1 ㎛ 내지 10 ㎛인, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 제1 하드코팅층 및 제2 하드코팅층의 총 두께 합은 2 ㎛ 내지 17 ㎛인, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 제1 하드코팅층 및 제2 하드코팅층에 각각 포함된 바인더 수지는, 다관능 (메트)아크릴레이트계 화합물을 포함하는, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제9항에 있어서,상기 제1 하드코팅층 및 제2 하드코팅층은 각각 독립적으로, 상기 바인더 수지 100 중량부에 대해, 상기 다관능 (메트)아크릴레이트계 화합물을 50 중량부 이상 포함하는, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제9항에 있어서,상기 다관능 (메트)아크릴레이트계 화합물은 에틸렌 옥사이드, 프로필렌 옥사이드, 우레탄, 카프로락톤, 에폭시 및 에스터로 이루어진 군에서 선택된 1종 이상으로 변성된, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 제1 하드코팅층은 불소계 첨가제, 실리콘계 첨가제 및 불소-실리콘계 첨가제로 이루어진 군에서 선택된 하나 이상의 첨가제를 더 포함하는, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 광투과성 기재는 폴리이미드(polyimide, PI), 폴리이미드아미드(polyimideamide), 폴리에테르이미드(polyetherimide, PEI), 폴리에틸렌테레프탈레이트(polyethyleneterephtalate, PET), 폴리에틸렌나프탈레이트(polyethylenenaphthalate, PEN), 폴리에테르에테르케톤(polyetheretherketon, PEEK), 사이클릭 올레핀 중합체(cyclic olefin polymer, COP), 폴리아크릴레이트(polyacrylate, PAC), 폴리메틸메타크릴레이트(polymethylmethacrylate, PMMA), 및 트리아세틸셀룰로오스(triacetylcellulose, TAC)로 이루어진 군으로부터 선택되는 1종 이상을 포함하는, 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름.
- 제1항에 있어서,상기 제1 하드코팅층, 제2 하드코팅층 및 광투과성 기재의 총 두께 합은 40 ㎛ 내지 150 ㎛인, 플렉서블 디스플레이 장치용 커버 윈도우.
- 제1항의 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름을 포함하는, 플렉서블 디스플레이 장치용 커버 윈도우.
- 제15항에 있어서,상기 커버 윈도우용 보호필름의 일면에 형성되고, 20 ㎛ 내지 180 ㎛의 두께를 갖는 글래스(Glass) 커버 또는 플라스틱 필름 커버를 더 포함하는, 플렉서블 디스플레이 장치용 커버 윈도우.
- 제15항의 플렉서블 디스플레이 장치용 커버 윈도우를 포함하는, 디스플레이 장치.
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JP2023524196A JP2023546592A (ja) | 2021-01-15 | 2021-01-15 | フレキシブルディスプレイ装置のカバーウィンドウ用保護フィルム、これを含むカバーウィンドウおよびディスプレイ装置 |
PCT/KR2021/000625 WO2022154144A1 (ko) | 2021-01-15 | 2021-01-15 | 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름, 이를 포함한 커버윈도우 및 디스플레이 장치 |
US18/255,733 US20230407026A1 (en) | 2021-01-15 | 2021-01-15 | Protecting film for cover window of flexible display device, cover window and flexible display device comprising the same |
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PCT/KR2021/000625 WO2022154144A1 (ko) | 2021-01-15 | 2021-01-15 | 플렉서블 디스플레이 장치의 커버 윈도우용 보호필름, 이를 포함한 커버윈도우 및 디스플레이 장치 |
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Citations (6)
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JP2000052472A (ja) * | 1998-08-04 | 2000-02-22 | Toppan Printing Co Ltd | ハードコートフィルムもしくはシート、及び機能性無機薄膜付きハードコートフィルムもしくはシート |
JP2008094105A (ja) * | 2007-11-29 | 2008-04-24 | Toppan Printing Co Ltd | ハードコートフィルムもしくはシート |
JP2017033031A (ja) * | 2015-07-17 | 2017-02-09 | 大日本印刷株式会社 | タッチパネル用ハードコートフィルム、及び、折り畳み式画像表示装置 |
KR20180027317A (ko) * | 2016-09-05 | 2018-03-14 | 동우 화인켐 주식회사 | 하드코팅 필름 및 이를 구비한 화상표시장치 |
KR102147367B1 (ko) * | 2019-09-30 | 2020-08-24 | 에스케이이노베이션 주식회사 | 윈도우 커버 필름 및 이를 포함하는 플렉서블 디스플레이 패널 |
KR102151694B1 (ko) * | 2018-07-19 | 2020-09-03 | 도레이첨단소재 주식회사 | 디스플레이용 하드코팅 필름 |
-
2021
- 2021-01-15 US US18/255,733 patent/US20230407026A1/en active Pending
- 2021-01-15 WO PCT/KR2021/000625 patent/WO2022154144A1/ko active Application Filing
- 2021-01-15 JP JP2023524196A patent/JP2023546592A/ja active Pending
Patent Citations (6)
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JP2000052472A (ja) * | 1998-08-04 | 2000-02-22 | Toppan Printing Co Ltd | ハードコートフィルムもしくはシート、及び機能性無機薄膜付きハードコートフィルムもしくはシート |
JP2008094105A (ja) * | 2007-11-29 | 2008-04-24 | Toppan Printing Co Ltd | ハードコートフィルムもしくはシート |
JP2017033031A (ja) * | 2015-07-17 | 2017-02-09 | 大日本印刷株式会社 | タッチパネル用ハードコートフィルム、及び、折り畳み式画像表示装置 |
KR20180027317A (ko) * | 2016-09-05 | 2018-03-14 | 동우 화인켐 주식회사 | 하드코팅 필름 및 이를 구비한 화상표시장치 |
KR102151694B1 (ko) * | 2018-07-19 | 2020-09-03 | 도레이첨단소재 주식회사 | 디스플레이용 하드코팅 필름 |
KR102147367B1 (ko) * | 2019-09-30 | 2020-08-24 | 에스케이이노베이션 주식회사 | 윈도우 커버 필름 및 이를 포함하는 플렉서블 디스플레이 패널 |
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