WO2014193199A1 - Film barrière à gaz et son procédé de préparation - Google Patents

Film barrière à gaz et son procédé de préparation Download PDF

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WO2014193199A1
WO2014193199A1 PCT/KR2014/004874 KR2014004874W WO2014193199A1 WO 2014193199 A1 WO2014193199 A1 WO 2014193199A1 KR 2014004874 W KR2014004874 W KR 2014004874W WO 2014193199 A1 WO2014193199 A1 WO 2014193199A1
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layer
stress relaxation
gas barrier
barrier film
barrier layer
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PCT/KR2014/004874
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English (en)
Korean (ko)
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이대규
강세영
김병수
김성국
이은화
정유정
최우석
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제일모직 주식회사
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Publication of WO2014193199A1 publication Critical patent/WO2014193199A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
    • B32B37/203—One or more of the layers being plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
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    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/246—Vapour deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
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    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2483/14—Characterised by the use of 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; Derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a gas barrier film and a method of manufacturing the same.
  • Plate glass has conventionally been used as a display substrate of an electrode substrate for a liquid crystal display panel, a plasma display, an electroluminescence (EL), a fluorescent display tube, and a light emitting diode.
  • plate glass is not easy to be broken, has no flexibility, has a specific gravity, and is thin and light.
  • plastic film is attracting attention as a material instead of flat glass. Since plastic films are light and difficult to break, and thin films are easily formed, they are effective materials that can cope with the increase in size of display elements.
  • the display device using the plastic film as a substrate has a problem in that the light emitting performance of the display device is easily degraded due to oxygen or water vapor permeation. Accordingly, attempts have been made to minimize the effects of oxygen or water vapor by forming a gas barrier film of an organic or inorganic material on a plastic film.
  • inorganic materials such as silicon oxide (SiOx), aluminum oxide (AlxOy), tantalum oxide (TaxOy), titanium oxide (TiOx) and the like are mainly used as the gas barrier film.
  • These gas barrier thin films are coated on the surface of the plastic film by a vacuum deposition method such as plasma enhanced chemical vapor deposition (PECVD), sputtering or the sol-gel method in a high vacuum state.
  • Japanese Patent Nos. 1994-0031850 and 2005-0119148 disclose the case where the inorganic layer is directly coated on the surface of the plastic film by sputtering.
  • the elastic modulus, thermal expansion coefficient, bending radius, etc. of the plastic film and the inorganic layer are greatly different, if heat or repetitive force is applied or bent from the outside, cracks are generated due to stress at the interface, which causes easy peeling.
  • Japanese Patent No. 2004-0082598 discloses a method of using a multilayer gas barrier thin film composed of an organic layer and an inorganic layer.
  • the presence of several layers having different physical properties may cause cracking or peeling of the thin film at each interface. It resulted in a further increase.
  • the formation of the gas barrier thin film used in the prior art requires a deposition process performed under high vacuum, an expensive device is required, and it takes a long time to reach a high vacuum, which is not economical.
  • the gas barrier film used in the solar cell is used for a long time outdoors, especially since the organic solar cell absorbs ultraviolet rays due to the photoactive layer itself, the gas barrier film used in the solar cell has excellent transparency and ultraviolet absorbing ability. Weather resistance and flexibility are required.
  • An object of the present invention is to provide a gas barrier film having excellent gas barrier properties.
  • Another object of the present invention is to provide a gas barrier film having excellent flexibility, transparency and ultraviolet absorption.
  • Still another object of the present invention is to provide a gas barrier film having a short manufacturing time and excellent flexibility and transparency by enabling non-vacuum wet coating.
  • Still another object of the present invention is to provide a display member to which the gas barrier film is applied.
  • One aspect of the invention is a stress relief layer on a substrate; Barrier layer; And a UV blocking layer; sequentially formed, the barrier layer includes silica (SiO x , 1.5 ⁇ x ⁇ 2.5), the stress relaxation layer is an inorganic layer or an organic-inorganic mixed layer, and the UV blocking layer is a metal. It relates to a gas barrier film comprising oxide fine particles and having a water permeability of about (5 ⁇ 10 ⁇ 4 ) g / (m 2 ⁇ day) or less measured according to ASTM F-1249.
  • Another aspect of the invention is to form a stress relaxation layer by physical or chemical vapor deposition on one side of the substrate; Forming a barrier layer by coating and curing a coating solution including hydrogenated polysilazane or hydrogenated polysiloxane residue on the stress relaxation layer; It relates to a method for producing a gas barrier film comprising forming an ultraviolet blocking layer containing metal oxide fine particles on the barrier layer.
  • Another aspect of the present invention relates to a solar cell module including a transparent front substrate on which solar light is incident, a solar cell element, an EVA filler filling the solar cell element, and the gas barrier film.
  • the gas barrier film of the present invention is excellent in gas barrier properties, non-vacuum wet coating is possible, the production time is short, has excellent flexibility, transparency, and ultraviolet absorption, it is excellent in crack prevention effect.
  • FIG. 1 is a schematic cross-sectional view of a gas barrier film according to one embodiment of the present invention.
  • FIG. 1 is a cross-sectional view of a gas barrier film of the present invention, wherein the gas barrier film 100 includes a substrate 110; A stress relaxation layer 120 sequentially formed on one surface of the substrate 110; Barrier layer 130; And an ultraviolet blocking layer 140.
  • the substrate 110 is not particularly limited, but a high heat resistant plastic substrate having excellent heat resistance and low thermal expansion rate may be used.
  • a high heat resistant plastic substrate having excellent heat resistance and low thermal expansion rate may be used.
  • it may be one or more selected from the group consisting of polyethersulfone, polycarbonate, polyimide, polyetherimide, polyacrylate, polyethylenenaphthalate and polyester film, but is not limited thereto.
  • the thickness of the substrate 110 may be about 20 to 190 ⁇ m, for example, about 70 to 100 ⁇ m. Within this range, mechanical strength, flexibility, transparency, heat resistance, and the like may be excellent as a substrate of the gas barrier film.
  • the substrate 110 may further include an inorganic filler.
  • an inorganic filler for example, one or more particles or glass cloths selected from the group consisting of silica, plate or sphere glass flakes and nanoclays can be used.
  • the coefficient of thermal expansion of the substrate may be about 10 to 100 ppm / ° C.
  • the stress relaxation layer 120 may be formed on the substrate 110 to minimize cracking of the barrier film manufactured by alleviating the stress of the substrate 110 and the barrier layer 130.
  • the stress relaxation layer 120 may prevent cracking and deformation of the barrier film and provide improved thermal stability, processability, gas permeability, surface hardness, and affinity with the substrate.
  • SiO 2 silica
  • a stress is generated due to densification and shrinkage or expansion, which causes cracks in the barrier layer (Macro Crack). Or Micro Crack), and it is necessary to relieve stress of the barrier layer because cracks may cause moisture and gas to pass through and impair barrier characteristics.
  • the stress relaxation layer 120 may be an organic-inorganic mixed layer or an inorganic layer having a smaller thermal expansion coefficient (CTE) than the substrate 110 and a larger thermal expansion coefficient than the barrier layer 130.
  • the stress relaxation layer 120 may have a larger modulus than the substrate 110 to mitigate the occurrence of cracks due to the difference in modulus between the substrate 110 and the barrier layer 130. That is, the stress relaxation layer 120 may be more effective in stress relaxation as the coefficient of thermal expansion (CTE) is smaller and the modulus value is larger.
  • the stress relaxation layer 120 may have a thermal expansion coefficient of about 20 ppm / ° C. or less, such as about 5 ppm / ° C. or less, and a modulus of about 10 Gpa or more, such as about 13 Gpa or more.
  • the stress relaxation layer 120 may be an organic-inorganic mixed layer formed by curing a coating solution including silica nanoparticles, siloxane, silazane or siloxaneoxane.
  • the stress relaxation layer 120 may be an organic-inorganic mixed layer including a single or a mixture thereof selected from polyepoxy resin, polyester resin, polyacrylic resin and polyurethane resin.
  • the silica nanoparticles, silica sol, siloxane, silazane or siloxanexazan may be formed by blending with an acrylic compound to cure or curing the siloxane, silazane or siloxaneox modified acrylic copolymer.
  • the urethane hybrid polysilazane may be cured to form an organic-inorganic mixed layer.
  • the organic-inorganic mixed layer thus formed can prevent cracking and deformation of the barrier film, which is an inorganic layer, and can provide improved thermal stability, fairness, gas permeability, surface hardness, and affinity with the inorganic layer.
  • the curing method may be thermal curing or uv curing, for example UV curing may be applied.
  • inventions include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, or tantalum; Or oxides, oxynitrides or nitrides thereof; Or an inorganic layer comprising a mixture thereof. Specifically, it may be an inorganic layer including AlOx (1.0 ⁇ x ⁇ 2.0) or SiOx (1.0 ⁇ x ⁇ 2.5).
  • the stress relaxation layer 120 may have a thickness of about 10 to 2,000 nm, for example, about 40 to 1,000 nm. Specifically, the stress relaxation layer 120 may be about 10 to 100 nm when the inorganic layer, and about 500 to 2,000 nm when the organic-inorganic mixed layer is used. Within this range, the coefficient of thermal expansion (CTE) is small and the modulus is sufficiently secured to be effective for stress relaxation.
  • CTE coefficient of thermal expansion
  • the barrier layer 130 may be formed on the stress relaxation layer 120.
  • the barrier layer 130 is an organic-inorganic mixed layer including silica (SiOx) after applying a coating solution containing a hydrogenated polysiloxane or polysilazane, and an organic solvent to the surface of the stress relaxation layer 120 through a drying process and a curing process. It can be formed as.
  • the silica (SiO 2 ) of the organic-inorganic mixed layer may move to the surface or inside the inorganic layer, which is the stress relaxation layer 120, through the coating process to fill voids present in the inorganic layer.
  • the coating solution in order to form an organic-inorganic mixed layer containing silica, the coating solution is applied, and then subjected to a baking process and a curing process.
  • siloxane compounds such as hydrogenated polysilazane or hydrogenated polysiloxane, which are included in the coating solution, are converted into silica (SiO 2 ) to ceramicize.
  • silica (SiO 2 ) of the organic-inorganic mixed layer not only heals the interfacial defects of the stress relaxation layer 120 and the barrier layer 130, but also the stress relaxation layer 120 In the case of the inorganic layer, it may penetrate into the inorganic layer to fill voids existing in the inorganic layer.
  • the barrier layer may have a thickness of about 50 to 1,000 nm, for example, about 100 to 500 nm, and may have a coefficient of thermal expansion (CTE) of about 5 to 30 ppm / ° C. Crack generation can be minimized in the above range, and the effect of gas barrier properties is excellent.
  • CTE coefficient of thermal expansion
  • the UV blocking layer 140 may be further formed on the barrier layer 120.
  • the UV blocking layer 140 protects the barrier layer from ultraviolet rays, thereby increasing weather resistance and improving barrier properties.
  • the ultraviolet blocking layer 140 includes a material absorbing light having a wavelength of about 200 to 340 nm, which is an ultraviolet region, as an ultraviolet absorber, thereby preventing deterioration of the barrier film due to ultraviolet rays.
  • Ultraviolet absorbers may include metal oxide fine particles, organic compounds, and the like, and may include metal oxides, for example.
  • the metal oxide used as the ultraviolet absorber is a fine particle having an average particle diameter of about 1 to 100 nm, for example about 5 to 25 nm, one selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, iron oxide and the like. It may contain the above fine particles.
  • the organic compound used as the ultraviolet absorber may include a benzotriazole, triazine, or the like.
  • the ultraviolet absorber may include a HALS agent having an antioxidant function, for example, a hindered amine compound may be used as the HALS agent.
  • an acrylate monomer, an acrylate oligomer, a siloxane monomer, a siloxane polymer, a silicone monomer, a silicone polymer, an acrylic resin, or a uritan resin may be used.
  • the UV absorber may be included in about 1 to 45% by weight of the UV blocking layer, the binder resin may be included in about 55 to 99% by weight of the UV blocking layer.
  • the coating liquid for forming a barrier layer containing silica may be hydride polysiloxane, hydride polysilazane or a mixture thereof; And solvents. Referring to each component constituting the coating solution is as follows.
  • the coating solution of the present invention may include a hydrogenated polysiloxane, hydrogenated polysilazane or a mixture thereof as a composition for forming a silica layer.
  • the hydrogenated polysiloxane or hydrogenated polysilazane may be used for insulating films, separators, hard coatings, etc. in that it has a feature of converting into a dense silica glass material by heating and oxidation reactions.
  • the hydrogenated polysiloxane may include silicon-oxygen-silicon (Si-O-Si) bonding units in addition to silicon-nitrogen (Si-N) bonding units in the structure.
  • silicon-oxygen-silicon (Si-O-Si) bonding units can alleviate stress upon curing to reduce shrinkage.
  • Hydrogenated polysilazanes have a basic backbone in the structure including silicon-hydrogen (Si-H), nitrogen-hydrogen (N-H) coupling units in addition to silicon-nitrogen (Si-N) coupling units.
  • the (Si-N) bond may be substituted with a (Si-O) bond.
  • the hydrogenated polysiloxane may have a unit represented by Formula 1, a unit represented by Formula 2, and a terminal portion represented by Formula 3 below:
  • R1 to R7 are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 aryl group , Substituted or unsubstituted C3 to C30 arylalkyl group, substituted or unsubstituted C3 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 heterocyclic alkyl group, substituted or unsubstituted C3 to C30 alkenyl group, Substituted or unsubstituted alkoxy group, substituted or unsubstituted carbonyl group, hydroxy group or a combination thereof.
  • substituted means hydrogen, halogen atom, hydroxyl group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, carbonyl group, carbamyl group, thiol group, ester group, Carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphate groups or salts thereof, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and carbon atoms
  • An aryl group having -30, an aryloxy group having 6-30 carbon atoms, a cycloalkyl group having 3-30 carbon atoms, a cycloalkenyl group having 3-30 carbon atoms, a cycloalkynyl group having 3-30 carbon atoms, or a combination thereof is meant.
  • the hydrogenated polysiloxane or hydrogenated polysilazane may have an oxygen content of about 0.2% to 3% by weight. When it is contained in the above range, the stress relaxation by the silicon-oxygen-silicon (Si-O-Si) bond in the structure is sufficient to prevent shrinkage during heat treatment, thereby preventing cracks in the formed gas barrier layer. Can be.
  • the oxygen content of the hydrogenated polysiloxane or hydrogenated polysilazane may be about 0.2 to 3% by weight, more specifically 0.5 to 2% by weight.
  • the hydrogenated polysiloxane or polysilazane has a structure in which the terminal portion is capped with hydrogen, and the terminal group represented by Formula 3 is about 15 with respect to the total content of Si—H bonds in the hydrogenated polysiloxaneoxane or hydrogenated polysilazane structure. To 35% by weight.
  • the SiH 3 part becomes SiH 4 during curing to prevent scattering to prevent shrinkage and the gas barrier layer formed therefrom may prevent cracking.
  • the terminal group of Chemical Formula 3 may be included in an amount of about 20 to 30 wt% based on the total content of Si—H bonds in the hydrogenated polysiloxane or hydrogenated polysilazane structure.
  • the hydrogenated polysiloxane or hydrogenated polysilazane of the present invention may have a weight average molecular weight (Mw) of about 1,000 to 5,000 g / mol. In the above range, it is possible to form a dense organic-inorganic mixed layer with a thin film coating while reducing components to evaporate during heat treatment.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) may be about 1,500 to 3,500 g / mol.
  • the hydrogenated polysiloxane, hydrogenated polysilazane or a mixture thereof may be included in an amount of about 0.1 to 50 wt% based on the total content of the coating solution. If included in the above range can maintain a suitable viscosity and can be formed flat and evenly without bubbles and voids (Void).
  • the solvent may be used as long as it is a solvent which can dissolve them without being reactive with hydrogenated polysiloxane or hydrogenated polysilazane.
  • a solvent containing no -OH group may be used because it is reactive with the siloxane compound.
  • ethers such as hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used.
  • hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, sorbetso, and taben
  • halogen hydrocarbons such as methylene chloride and tricholoethane, dibutyl ether, dioxane, tetra hybrido furan and the like Ryu.
  • the solubility of the siloxane compound or the evaporation rate of the solvent may be selected as appropriate, and a plurality of solvents may be mixed.
  • the coating liquid of the present invention may further include a thermal acid generator (TAG).
  • TAG thermal acid generator
  • the thermal acid generator is an additive for improving the developability of the hydride polysiloxane and the contamination by uncuring, so that the hydride polysiloxane may be developed at a relatively low temperature.
  • the thermal acid generator is not particularly limited as long as it is a compound capable of generating acid (H +) by heat, but may be selected to have low volatility by being activated at about 90 ° C. or higher to generate sufficient acid.
  • Such thermal acid generators can be selected, for example, from nitrobenzyl tosylate, nitrobenzyl benzenesulfonate, phenol sulfonate and combinations thereof.
  • the thermal acid generator may be included in about 25% by weight or less, for example about 0.01 to 20% by weight based on the total content of the coating liquid.
  • the siloxane compound When included in the above range, the siloxane compound may be developed at a relatively low temperature. However, in order to have better gas barrier properties, organic components may not be included.
  • the coating liquid of the present invention may further include a surfactant.
  • the said surfactant is not specifically limited, For example, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ether, polyoxyethylene rail ether, polyoxyethylene nonyl phenol ether, etc.
  • Polyoxyethylene sorbitan such as polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate
  • Nonionic surfactants such as fatty acid esters, F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megapack F171, F173 (manufactured by Dainippon Ink, Inc.).
  • Fluorine-based surfactants such as Prorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) Kano siloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), etc., etc. are mentioned.
  • the surfactant may be included in about 10% by weight or less, for example, about 0.001 to 5% by weight based on the total content of the coating liquid. In order to have better gas barrier properties, the organic component may not be included.
  • the gas barrier film manufacturing method of the present invention comprises the steps of forming a stress relaxation layer by physical or chemical vapor deposition on one surface of the (S1) substrate; (S2) forming a barrier layer by applying and curing a coating solution including a hydrogenated polysilazane or a hydrogenated polysiloxazane on the stress relaxation layer; (S3) forming a UV blocking layer including metal oxide fine particles on the barrier layer.
  • a deposition method When the stress relaxation layer is formed of an inorganic layer, all methods such as a deposition method and a coating method can be used, but a vapor deposition method may be used to sufficiently secure a gas barrier property and obtain a uniform thin film.
  • a deposition method may include all methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), and the like, such as vacuum deposition, ion plating, and sputtering.
  • a coating liquid containing silica nanoparticles, siloxane, silazane or siloxanexazan, etc. may be roll coated, spin coated, dip coated, The coating liquid may be applied using a flow coating, spray coating, or the like, and then cured by UV irradiation, plasma treatment, heat treatment, or a combination thereof to form an organic-inorganic mixed layer.
  • the barrier layer is coated with the above-described barrier layer coating liquid on the stress relaxation layer using a roll coating, spin coating, dip coating, flow coating, spray coating, or the like. It may be formed through a curing process by ultraviolet irradiation, plasma treatment and heat treatment or a combination thereof.
  • curing refers to a process of converting a siloxane compound, such as hydrogenated polysiloxane or hydrogenated polysilazane, into silica to ceramicize.
  • the curing process may be performed by heat treatment at a temperature of about 150 ° C. or less, but may further perform ultraviolet irradiation, plasma treatment, and high humidity drying to increase the conversion to silica.
  • the conversion to silica can be increased by heat treatment for about 5 to 20 minutes at low temperature, high humidity, for example, at about 50 to 100 °C and relative humidity of about 50 to 80%.
  • the ultraviolet irradiation may be performed using a vacuum ultraviolet. Specifically, about 100 to 200 nm vacuum ultraviolet light may be used. Irradiation intensity and irradiation amount of vacuum ultraviolet ray can be set suitably.
  • the vacuum ultraviolet ray may be irradiated at about 0.1 to 5 minutes, at an irradiation intensity of about 10 to 200 mW / cm 2, and at an irradiation amount of about 100 to 6000 mJ / cm 2, specifically about 1,000 to 5,000 mJ / cm 2.
  • the UV blocking layer may be formed by applying a UV coating layer coating liquid containing metal oxide fine particles to the barrier layer using a roll coating, spin coating, dip coating, flow coating, spray coating, or the like. After coating by using, it may be formed through a curing process by ultraviolet irradiation, plasma treatment and heat treatment or a combination thereof. Alternatively, the coating may be left to stand at room temperature for about 5 hours or more to naturally cure.
  • the curing method is not limited thereto and may be appropriately selected by those skilled in the art.
  • the vacuum ultraviolet ray is a vacuum ultraviolet ray of about 100 to 200 nm. Irradiation intensity and irradiation amount of vacuum ultraviolet ray can be set suitably. In one embodiment, the vacuum ultraviolet process may be performed for about 0.1 to 5 minutes, the irradiation intensity is about 10 to 200mW / cm2, the irradiation amount can be irradiated at about 100 to 6,000mJ / cm2, for example 1,000 to 5,000 mJ / cm2 have.
  • Flexible display device and solar cell module including gas barrier film
  • the above-described gas barrier film may be suitably used in the flexible display device as one embodiment.
  • the flexible substrate is thinner, lighter, flexible, and can be processed into various forms than glass.
  • plastic substrates developed to date show inferior physical properties to glass in terms of heat resistance, moisture and / or oxygen barrier properties, and fairness.
  • the flexible substrate is a plastic substrate, a gas barrier film for imparting oxygen and moisture barrier properties, and due to the difference in physical properties of the substrate and the gas barrier film to prevent cracks in the flexible substrate and to improve the flatness of the substrate
  • the buffer layer may include a flat layer.
  • the gas barrier film may be used as a back protective sheet of the solar cell module. Since the solar cell is mainly used outdoors, the members constituting the solar cell module require sufficient durability and weather resistance.
  • the back protective sheet protects the solar cell element from mechanical shock and pressure from the outside and prevents the penetration of moisture to prevent deterioration.
  • the back protective sheet is excellent in durability and weather resistance and barrier against moisture or gas.
  • the solar cell module of the present invention may include a transparent front substrate on which solar light is incident, a solar cell element, an EVA filler filling the solar cell element, and the gas barrier film.
  • the inside of the 2L reactor equipped with the stirrer and the temperature controller was replaced with dry nitrogen, and 2.0 g of pure water was injected into 1,500 g of dry pyramid, mixed well, and the mixture was kept in a reactor at 5 ° C.
  • 100 g of dichlorosilane was slowly injected over 1 hour, and then 70 g of ammonia was slowly injected over 3 hours with stirring.
  • dry nitrogen was injected for 30 minutes and the ammonia remaining in the reactor was removed.
  • the product on the obtained white slurry was filtered using a 1 ⁇ m Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtrate.
  • Barrier layer coating solution I was prepared by filtration with a 0.03 ⁇ m filter made of Teflon.
  • the oxygen content of the obtained hydrogenated polysiloxazane is 0.5%, SiH 3 / SiH ( total) is 0.20, a weight average molecular weight of 2,000g / mol.
  • the inside of the 2L reactor equipped with the stirrer and the temperature controller was replaced with dry nitrogen, and 1.1 g of pure water was injected into 1,500 g of dry pyramid, and the mixture was sufficiently mixed.
  • 100 g of dichlorosilane was slowly injected over 1 hour, and then 70 g of ammonia was slowly injected over 3 hours with stirring.
  • dry nitrogen was injected for 30 minutes and the ammonia remaining in the reactor was removed.
  • the product on the obtained white slurry was filtered using a 1 ⁇ m Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtrate.
  • a barrier layer coating solution II was prepared by filtration through a 0.03 ⁇ m filter made of Teflon.
  • the hydrogenated polysiloxane obtained had an oxygen content of 2.1%, a SiH 3 / SiH (total) of 0.19 and a weight average molecular weight of 2,700 g / mol.
  • the inside of the 2L reactor equipped with the stirrer and the temperature controller was replaced with dry nitrogen, 0.3 g of pure water was injected into 1,500 g of dry pyridine, mixed well, and the mixture was placed in a reactor and warmed to 20 ° C.
  • 100 g of dichlorosilane was slowly injected over 1 hour, and then 70 g of ammonia was slowly injected over 3 hours with stirring.
  • dry nitrogen was injected for 30 minutes, and the ammonia remaining in the reactor was removed.
  • the product on the obtained white slurry was filtered using a 1 ⁇ m Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtrate.
  • a barrier layer coating solution III was prepared by filtration through a 0.03 ⁇ m filter made of Teflon.
  • the oxygen content of the obtained hydrogenated polysiloxazane is 0.4%, SiH 3 / SiH ( total) is 0.30, a weight average molecular weight of 2,600g / mol.
  • tetraethyl silicate TEOS, Sigma-Aldrich Co., Ltd.
  • MTMS methyltrimethoxysilane
  • MTMS Shin Etsu KBM503
  • a binder composition was prepared by mixing 5 g of a titanium curing catalyst (D-20 of Shin-Etsu Chemical Co., D-20) and 100 g of butanol with 100 g of an alkoxysilicone oligomer (X-40-9250, Shin-Etsu Chemical Co., Ltd.) as a siloxane-based binder, followed by stirring at 1000 rpm for 10 minutes. It was.
  • core-shell zinc oxide particles Naanofine Co., Ltd., Sakai Chemical Co., Ltd.
  • butanol 100 g
  • butanol 100 g
  • alkoxy silicon oligomer X-40-9250
  • a core-shell zinc oxide particle-containing butanol dispersion was added to the binder composition so that the content of the core-shell zinc oxide particles in the dispersion was 20wt%, followed by stirring to prepare a UV barrier coating liquid.
  • a 50 nm-thick AlOx film (stress relief layer I) was formed on one surface of a 100 ⁇ m PET film (KEL86W by Teijin-Dupont Co., Ltd.) by reactive sputtering. Specifically, the Al target was mounted and formed while injecting O 2 gas under conditions of vacuum degree of 1.8 mTorr, PEM (Plasma Emittion Monitoring) Set Point 2.5, and Power 5kw. On the AlOx film, spin coating was performed with barrier layer coating solution I.
  • the coating solution was diluted to a solid content of 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,500rpm for 20 seconds, dried for 3 minutes in an 80 °C convection oven, 2,000 mJ in a UV irradiator UV irradiation at 180 cm / cm 2, and then cured for 10 minutes in an 85 ° C., 85% constant temperature and humidity chamber to form a barrier layer having a thickness of 200 nm. After spin-coating (1,000 rpm, 20 seconds) with the UV barrier coating solution on the barrier layer, and left for 6 hours at room temperature to form a UV barrier layer having a thickness of 5 ⁇ m to prepare a barrier film.
  • Table 1 The measured values after measuring the physical properties of the barrier film are shown in Table 1 below.
  • the urethane-based hybrid polysilazane solution (Clariant HSU200s) was spin coated (1,000 rpm, 20 seconds) on one surface of 100 ⁇ m PET film (KEL86W of Teijin-Dupont Co., Ltd.) and cured for 30 minutes in a 120 °C convection oven for a stress of 800 nm. Mitigating Layer II was formed. Spin coating was performed on the stress relaxation layer II with a barrier coating liquid I.
  • the coating solution was diluted to a solid content of 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,500rpm for 20 seconds, dried for 3 minutes at 80 °C convection oven, 2,000mJ / UV irradiation in cm 2 for 135 seconds, and then cured for 10 minutes in an 85 ° C., 85% constant temperature and humidity chamber to form a barrier layer having a thickness of 200 nm.
  • the resultant was left at room temperature for 6 hours to form a UV barrier layer having a thickness of 5 ⁇ m to prepare a barrier film.
  • Table 1 The measured values after measuring the physical properties of the barrier film are shown in Table 1 below.
  • the coating solution was diluted to a solid content of 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,500rpm for 20 seconds, dried for 3 minutes in an 80 °C convection oven, 2,000mJ in a UV irradiator UV irradiation at / cm 2 for 180 seconds, then cured for 10 minutes in a 85 °C, 85% constant temperature and humidity chamber to form a barrier layer of 200nm thickness. After spin-coating (1,000 rpm, 20 seconds) with the UV barrier coating solution on the barrier layer, the resultant was left at room temperature for 6 hours to form a UV barrier layer having a thickness of 5 ⁇ m to prepare a barrier film.
  • Table 1 The measured values after measuring the physical properties of the barrier film are shown in Table 1 below.
  • An AlOx film (stress relaxation layer I) having a thickness of 50 nm was formed on one surface of a 100 ⁇ m PET film (KEL86W manufactured by Teijin-Dupont). Specifically, the Al target was mounted and formed while injecting O 2 gas under a vacuum degree of 1.8 mTorr, PEM (Plasma Emittion Monitoring) Set Point 2.5, and Power 5 kw. On the AlOx film, spin coating was performed with barrier layer coating solution II.
  • the coating solution was diluted to a solid content of 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,500rpm for 20 seconds, dried for 3 minutes in an 80 °C convection oven, 2,000mJ in a UV irradiator UV irradiation at / cm 2 for 180 seconds, then cured for 10 minutes in a 85 °C, 85% constant temperature and humidity chamber to form a barrier layer of 200nm thickness. After spin-coating (1,000 rpm, 20 seconds) with the UV barrier coating solution on the barrier layer, the resultant was left at room temperature for 6 hours to form a UV barrier layer having a thickness of 5 ⁇ m to prepare a barrier film.
  • DBE dibuthyl ether
  • a barrier film was prepared in the same manner as in Example 4, except that barrier layer coating solution III was used.
  • a barrier film was prepared in the same manner as in Example 1 except that the stress relaxation layer thickness was coated at 100 nm and the barrier layer coating solution IV was used.
  • a barrier film was prepared in the same manner as in Example 2, except that barrier layer coating solution II was used.
  • a barrier film was prepared in the same manner as in Example 3, except that barrier layer coating solution II was used.
  • One side of the 100 ⁇ m PET film (Teijin-Dupont Co., Ltd. KEL86W) was spin coated with a barrier layer coating solution I.
  • the coating solution was diluted to a solid content of 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,500rpm for 20 seconds, dried for 3 minutes in an 80 °C convection oven, 2,000mJ in a UV irradiator UV irradiation at / cm 2 for 180 seconds, then cured for 10 minutes in a 85 °C, 85% constant temperature and humidity chamber to form a barrier layer of 200nm thickness.
  • the resultant was left at room temperature for 6 hours to form a UV barrier layer having a thickness of 5 ⁇ m to prepare a barrier film.
  • a 50 nm AlOx film (stress relief layer I) was formed on one surface of a 100 ⁇ m PET film (KEL86W from Teijin-Dupont). Specifically, the Al Target was mounted and formed while injecting O 2 gas under conditions of vacuum degree of 1.8 mTorr, PEM (Plasma Emittion Monitoring) Set Point 2.5, and Power 5kw. The AlOx layer was spin coated with a barrier layer coating solution IV.
  • the coating solution was diluted to a solid content of 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,500rpm for 20 seconds, dried for 3 minutes at 80 °C convection oven, 2,000mJ / After 180 seconds of UV irradiation in cm 2 , it was cured for 10 minutes in 85 °C, 85% constant temperature and humidity chamber to form a barrier layer of 200nm thickness. After spin-coating (1,000 rpm, 20 seconds) with the UV barrier coating solution on the barrier layer, the resultant was left at room temperature for 6 hours to form a UV barrier layer having a thickness of 5 ⁇ m to prepare a barrier film.
  • DBE dibuthyl ether
  • a barrier film was prepared in the same manner as in Comparative Example 1, except that barrier layer coating solution IV was used.
  • a 50 nm AlOx film (stress relief layer I) was formed on one surface of a 100 ⁇ m PET film (KEL86W from Teijin-Dupont). Specifically, the Al Target was mounted and formed while injecting O 2 gas under a vacuum degree of 1.8 mTorr, PEM (Plasma Emittion Monitoring) Set Point 2.5, and Power 5kw. On the AlOx film, spin coating was performed with barrier layer coating solution I.
  • the coating solution was diluted to a solid content of 9.5% with DBE (dibuthyl ether), spin coating was coated for 20 seconds at 1,500rpm, dried for 3 minutes at 80 °C convection oven, 85 °C, 85% Curing in a constant temperature and humidity chamber for 10 minutes to form a barrier layer of 200nm thickness.
  • DBE dibuthyl ether
  • One side of a 100 ⁇ m PET film (KEL86W from Teijin-Dupont Co., Ltd.) was spin coated with a barrier layer coating solution II.
  • the coating solution was diluted to a solid content of 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,500rpm for 20 seconds, dried for 3 minutes in an 80 °C convection oven, 2,000mJ in a UV irradiator UV irradiation at 180 cm / cm 2 , followed by curing in 85 ° C., 85% constant temperature and humidity chamber for 10 minutes to form a barrier layer 200 nm thick.
  • the resultant was left at room temperature for 6 hours to form a UV barrier layer having a thickness of 5 ⁇ m to prepare a barrier film.
  • a barrier film was prepared in the same manner as in Comparative Example 5, except that barrier layer coating solution III was used.
  • a barrier film was prepared in the same manner as in Comparative Example 4, except that barrier layer coating solution IV was used.
  • Moisture Permeability (g / m 2 / day) : Measured according to ASTM F-1249 standard using Aquatran Model1 (Mocon). Specimen size is 100 * 100mm.
  • Yellowness Index (YI) : Using a Lambda 950 (Perkin Elma, Inc.), YI values were measured based on a D65 light source using a color coordinate calculation program for a transmission spectrum of 300 nm to 1100 nm.
  • Coefficient of thermal expansion Using TA Instruments Q400, the coefficient of thermal expansion was set to 0.05 N, and the coefficient of thermal expansion of each layer was measured at 25 to 100 ° C (raising rate of 5 ° C / min).
  • Example 8 Stress Relieving Layer (Thickness) I 50 nm - - 50 nm 50 nm 100 nm - - II - 800 nm - - - - 800 nm - III - - 800 nm - - - 800 nm Barrier layer (thickness) Coating solution I 200 nm 200 nm 200 nm - - - - - Coating solution II - - - 200 nm - - 200 nm 200 nm Coating solution III - - - - 200 nm - - - Coating solution IV - - - - - 200 nm - - UV protection layer (thickness) 5 ⁇ m 5 ⁇ m 5 ⁇ m 5 ⁇ m 5 ⁇ m 5 ⁇ m 5 ⁇ m 5 ⁇ m 5 ⁇ m 5 ⁇ m 5 ⁇ m WVTR (g / m 2 / day) ⁇

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Abstract

La présente invention concerne un film barrière à gaz avec lequel une couche de soulagement des contraintes, une couche de barrière et une couche de blocage des UV sont formées séquentiellement sur un substrat, la couche de barrière comprend du dioxyde de silicium (SiO2, 1,5≤x≤2,5), la couche de soulagement des contraintes est une couche inorganique ou une couche mélangée organique-inorganique, la couche de blocage des UV comprend des microparticules d'oxyde métallique et la perméabilité à l'eau mesurée selon ASTM F-1249 est approximativement inférieure ou égale à (5×10-4)g/(m2ㆍjour). Le film barrière à gaz possède des propriétés de barrière à gaz remarquables, permet un revêtement humide hors vide et, par conséquent, offre un temps de préparation court et d'excellentes propriétés de flexibilité, de transparence et d'absorption des UV tout en prévenant très efficacement les fissures.
PCT/KR2014/004874 2013-05-31 2014-05-30 Film barrière à gaz et son procédé de préparation WO2014193199A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112087897A (zh) * 2020-09-11 2020-12-15 Oppo广东移动通信有限公司 壳体组件及其制备方法和电子设备

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101864878B1 (ko) * 2014-12-30 2018-07-16 도레이첨단소재 주식회사 투명 배리어 필름
WO2016108629A1 (fr) * 2014-12-31 2016-07-07 코오롱인더스트리 주식회사 Substrat de polyimide et module de substrat d'affichage comportant un tel substrat
KR101880210B1 (ko) * 2015-04-10 2018-07-20 주식회사 엘지화학 배리어 필름

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006297737A (ja) * 2005-04-20 2006-11-02 Fuji Photo Film Co Ltd ガスバリアフィルム
KR20080012552A (ko) * 2006-08-03 2008-02-12 주식회사 엘지화학 다층 플라스틱 기판 및 그 제조 방법
JP2011218586A (ja) * 2010-04-06 2011-11-04 Gunze Ltd 透明ガスバリアフィルム
JP2011238355A (ja) * 2010-05-06 2011-11-24 Konica Minolta Holdings Inc ガスバリア性フィルム、及び有機光電変換素子、有機エレクトロルミネッセンス素子
JP2013086445A (ja) * 2011-10-21 2013-05-13 Konica Minolta Advanced Layers Inc ガスバリア性フィルム、ガスバリア性フィルムの製造方法、及びガスバリア性フィルムを有する電子デバイス

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006297737A (ja) * 2005-04-20 2006-11-02 Fuji Photo Film Co Ltd ガスバリアフィルム
KR20080012552A (ko) * 2006-08-03 2008-02-12 주식회사 엘지화학 다층 플라스틱 기판 및 그 제조 방법
JP2011218586A (ja) * 2010-04-06 2011-11-04 Gunze Ltd 透明ガスバリアフィルム
JP2011238355A (ja) * 2010-05-06 2011-11-24 Konica Minolta Holdings Inc ガスバリア性フィルム、及び有機光電変換素子、有機エレクトロルミネッセンス素子
JP2013086445A (ja) * 2011-10-21 2013-05-13 Konica Minolta Advanced Layers Inc ガスバリア性フィルム、ガスバリア性フィルムの製造方法、及びガスバリア性フィルムを有する電子デバイス

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112087897A (zh) * 2020-09-11 2020-12-15 Oppo广东移动通信有限公司 壳体组件及其制备方法和电子设备
CN112087897B (zh) * 2020-09-11 2022-05-31 Oppo广东移动通信有限公司 壳体组件及其制备方法和电子设备

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