WO2018110272A1 - Film barrière aux gaz et dispositif électroluminescent organique - Google Patents

Film barrière aux gaz et dispositif électroluminescent organique Download PDF

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Publication number
WO2018110272A1
WO2018110272A1 PCT/JP2017/042580 JP2017042580W WO2018110272A1 WO 2018110272 A1 WO2018110272 A1 WO 2018110272A1 JP 2017042580 W JP2017042580 W JP 2017042580W WO 2018110272 A1 WO2018110272 A1 WO 2018110272A1
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Prior art keywords
film
gas barrier
cyclic olefin
barrier film
layer
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PCT/JP2017/042580
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English (en)
Japanese (ja)
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吉岡忠司
佐竹光
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東レフィルム加工株式会社
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Priority to JP2017563274A priority Critical patent/JPWO2018110272A1/ja
Publication of WO2018110272A1 publication Critical patent/WO2018110272A1/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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/842—Containers
    • H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

  • the present invention relates to a gas barrier film suitably used for electronic members such as foods, pharmaceutical packaging applications, solar cells, electronic paper, and organic electroluminescence (EL) devices, which require gas barrier properties.
  • the present invention relates to an organic EL device using.
  • the gas barrier film usually has a structure in which a gas barrier layer is laminated on a base film.
  • vapor deposition films of inorganic oxides such as aluminum oxide, silicon oxide, and magnesium oxide are generally known.
  • plastic films for example, plastic films made of polyolefin, polyester, polyamide, polycarbonate, polystyrene, polyvinyl alcohol, saponified ethylene vinyl acetate copolymer, polyacrylonitrile, polyacetal, and the like are known. Yes.
  • a gas barrier film for electronic devices such as organic electroluminescence (EL) and liquid crystal
  • a gas barrier film using a cyclic olefin resin film having low retardation (low birefringence) and high transparency as a base film is used.
  • Patent Documents 3 and 4 it has been proposed to dispose a hard coat layer between the base film and the gas barrier layer in order to improve the adhesion between the base film and the gas barrier layer.
  • gas barrier films have been required to be developed into flexible electronic devices such as flexible solar cell devices, organic electroluminescence (EL) devices, and liquid crystal display devices. That is, the gas barrier film is required to have flexibility that can withstand bending, bending, or a complicated planar shape.
  • a gas barrier film in which a cyclic olefin resin film is used as a base film and an inorganic film such as silicon dioxide is laminated as a gas barrier layer has flexibility. There is a problem that it is low.
  • the gas barrier film in which the hard coat layer is disposed between the base film and the gas barrier layer also has a problem of low flexibility.
  • an object of the present invention is to provide a gas barrier film having low retardation, high transparency, and good flexibility in view of the above-mentioned problems.
  • Another object of the present invention is to provide an organic EL device provided with the gas barrier film of the present invention.
  • Zn atom concentration measured by X-ray photoelectron spectroscopy (XPS method) of the inorganic film is 20 to 40 atom%, Si atom concentration is 5 to 20 atom%, Al atom concentration is 0.5 to 5 atom%, The gas barrier film according to [1], wherein the O atom concentration is 35 to 70 atom%.
  • the cured resin layer contains particles, and the ratio (r / d) of the average particle diameter (r: ⁇ m) of the particles to the thickness (d: ⁇ m) of the cured resin layer is 0.7 or less.
  • the gas barrier film according to [8]. [10] The gas barrier film according to [8] or [9], wherein the cured resin layer has a surface roughness (Ra) measured by an atomic force microscope of 2.0 nm or more and 10.0 nm or less.
  • An organic EL device comprising the gas barrier film according to any one of [1] to [10].
  • a gas barrier film having low retardation, high transparency, and good flexibility can be provided.
  • the gas barrier film of the present invention is suitable for an organic EL device.
  • the gas barrier film of the present invention has a gas barrier layer made of a single inorganic film directly on at least one surface of the cyclic olefin resin film.
  • Such an inorganic film contains at least zinc oxide, silicon dioxide, and aluminum oxide.
  • the inorganic film containing at least zinc oxide, silicon dioxide and aluminum oxide may be referred to as “inorganic film of the film of the present invention”.
  • the gas barrier layer in the present invention is composed of only a single inorganic film containing at least zinc oxide, silicon dioxide and aluminum oxide.
  • an inorganic film containing at least zinc oxide, silicon dioxide, and aluminum oxide for example, a single film in which two or more inorganic films having different composition ratios of zinc oxide, silicon dioxide, and aluminum oxide are laminated. It is defined as an inorganic film. That is, a film in which two or more inorganic films corresponding to the “inorganic film of the film of the present invention” are laminated is defined as a single inorganic film.
  • the gas barrier layer in the present invention does not include other inorganic films other than the inorganic film of the film of the present invention as described below.
  • an inorganic film made only of a silicon compound for example, silicon oxide, silicon nitride, silicon nitride oxide
  • an inorganic film made only of an aluminum compound for example, aluminum oxide
  • a zinc compound for example, zinc oxide, zinc sulfide
  • the gas barrier layer in the present invention does not include a gas barrier organic film, for example, an organic film made of an organosilicon compound.
  • a gas barrier organic film for example, an organic film made of an organosilicon compound.
  • the organic film made of an organosilicon compound include an organic film made of a silicon compound having a polysilazane skeleton, or a plasma CVD film using hexamethyldisiloxane (HMDSO) gas.
  • HMDSO hexamethyldisiloxane
  • the flexibility and transparency of the gas barrier film may be lowered.
  • the gas barrier film of the present invention has the inorganic film of the film of the present invention directly on at least one surface of the cyclic olefin resin film. That is, in the gas barrier film of the present invention, an undercoat layer such as a hard coat layer is not interposed between the cyclic olefin resin film and the inorganic film of the film of the present invention.
  • the flexibility of the gas barrier film may be lowered.
  • microcracks may be generated in the hard coat layer when the gas barrier film is cut into a predetermined size.
  • a microcrack occurs in the hard coat layer, it may be transmitted to the gas barrier layer laminated on the hard coat layer, and the microcrack may also occur in the gas barrier layer.
  • the gas barrier property may be lowered when the gas barrier film is applied to a flexible organic EL device and is folded or folded. Details will be described later.
  • the gas barrier layer in the present invention comprises a single layer of an inorganic film (inorganic film of the film of the present invention) containing at least zinc oxide, silicon dioxide and aluminum oxide.
  • the Zn atom concentration is 20 to 40 atom%
  • the Si atom concentration is 5 to 20 atom%
  • the Al atom concentration is 0.1 as measured by X-ray photoelectron spectroscopy (XPS method).
  • 5 to 5 atom% and the O atom concentration are preferably 35 to 70 atom%.
  • the oxide that suppresses the crystal growth of zinc oxide tends to be insufficient. Sexuality may not be obtained.
  • the Zn atom concentration is lower than 20 atom% or the Si atom concentration is higher than 20 atom%, the amorphous component of silicon dioxide inside the inorganic film tends to increase, and the flexibility of the inorganic film may be reduced.
  • the affinity between zinc oxide and silicon dioxide tends to be excessively high, so the hardness of the inorganic film is likely to increase, and cracks are likely to occur against heat and external stress. There is a case.
  • the Al atom concentration is less than 0.5 atom%, the affinity between zinc oxide and silicon dioxide becomes insufficient, and the bonding force between the particles forming the inorganic film becomes difficult to increase, so the flexibility may be lowered.
  • the O atom concentration When the O atom concentration is higher than 70 atom%, the amount of defects inside the inorganic film tends to increase, so that high gas barrier properties may not be obtained. If the O atom concentration is less than 35 atom%, the oxidation state of zinc, silicon, and aluminum tends to be insufficient, crystal growth cannot be suppressed, and the particle diameter tends to increase, which may deteriorate the gas barrier properties.
  • the Zn atom concentration is 25 to 35 atom%
  • the Si atom concentration is 10 to 15 atom%
  • the Al atom concentration is 1 to 3 atom%
  • the O atom concentration is 50 to 64 atom%.
  • the above composition is formed with the same composition as the mixed sintered material used when forming the inorganic film, it should be adjusted by using a mixed sintered material having a composition that matches the composition of the target inorganic film. Can do.
  • the method for forming the inorganic film of the film of the present invention is not particularly limited, and it is formed by using a mixed sintered material of zinc oxide, silicon dioxide, and aluminum oxide by a vacuum deposition method, a sputtering method, an ion plating method, or the like. be able to.
  • a single material of zinc oxide, silicon dioxide, and aluminum oxide form a film of zinc oxide, silicon dioxide, and aluminum oxide simultaneously from separate vapor deposition sources or sputter electrodes, and mix them to the desired composition.
  • a sputtering method using a mixed sintered material is more preferable from the viewpoint of composition reproducibility of the inorganic film.
  • a heat-resistant protective film such as a polyethylene terephthalate (PET) film is provided on the surface opposite to the surface on which the inorganic film of the cyclic olefin resin film is formed.
  • PET polyethylene terephthalate
  • the obtained PET protective film is preferably laminated in advance.
  • the inorganic film of the film of the present invention is made of other metals such as titanium, tin, copper, indium, gallium, zirconium, niobium, molybdenum and tantalum, or oxides, nitrides and sulfides of these metals. Can be included as long as the effects (gas barrier properties, flexibility, transparency) of the present invention are not impaired.
  • the thickness of the inorganic film of the film of the present invention is preferably 10 nm or more, more preferably 20 nm or more, and particularly preferably 30 nm or more from the viewpoint of obtaining good gas barrier properties.
  • the upper limit of the thickness is preferably 500 nm or less, more preferably 300 nm or less, and particularly preferably 200 nm or less from the viewpoint of suppressing curling of the gas barrier film.
  • the thickness of the inorganic film of the film of the present invention is 30 to 60 nm from the viewpoint of obtaining high transparency (high total light transmittance). Or in the range of 120 to 170 nm.
  • the cyclic olefin resin film of the present invention From the relationship between the refractive index of visible light (around 1.70) of the inorganic film of the film of the present invention and the refractive index of visible light (around 1.53) of the cyclic olefin resin film, the cyclic olefin resin film of the present invention
  • the transmittance when the inorganic film is laminated is relatively high in the above-mentioned two ranges (inorganic film thickness of 30 to 60 nm, or 120 to 170 nm).
  • the inorganic film of the film of the present invention has a feature that no cracks are generated at the time of cutting or that the cracks are extremely small. This feature is that the cut sheet obtained by cutting the gas barrier film of the present invention into a predetermined size is applied to a flexible organic EL device, and the effect of suppressing the gas barrier property from being lowered even when folded or folded. There is. Details will be described later.
  • the thickness of the inorganic film is small. From this viewpoint, the thickness of the inorganic film is more preferably in the range of 30 to 60 nm.
  • the cyclic olefin resin film in the present invention is a resin film mainly composed of a cyclic olefin resin (COP) or a cyclic olefin copolymer resin (COC).
  • the main component means that the constituent ratio of COP or COC among the resin components constituting the resin film is 50% by mass or more, preferably 60% by mass or more.
  • it is 80 mass% or more, More preferably, it is 90 mass% or more, Most preferably, it is 95 mass% or more.
  • the cyclic olefin resin film has relatively low moisture permeability and high transparency as compared with a polyester film, particularly a polyethylene terephthalate film, which has been widely used conventionally, and when used in an organic EL device, There is a feature that luminous efficiency is improved. Furthermore, it has the advantage that when it is used for an organic EL device with low retardation (low birefringence), the viewing angle dependency of color is small.
  • Cyclic olefin resin means a resin made of a homopolymer of cyclic olefin.
  • the cyclic olefin copolymer resin means a resin composed of a copolymer of a cyclic olefin and another monomer other than the cyclic olefin.
  • Examples of monomers other than the cyclic olefin that can be used for obtaining the cyclic olefin copolymer resin (COC) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-1- Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl- 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc. It is done.
  • the cyclic olefin resin film according to the present invention can also be obtained as a commercial product.
  • Commercially available products include, for example, “Zeonex (registered trademark)”, “ZEONOR (registered trademark)” manufactured by Nippon Zeon Co., Ltd., “Essina (registered trademark)” of Sekisui Chemical Co., Ltd., JSR Corporation "Arton (registered trademark)”, Hitachi Chemical's "Optretz”, Mitsui Chemicals' "Apel (registered trademark)”.
  • the thickness of the cyclic olefin resin film is not particularly limited, but it is preferably smaller from the viewpoint of ensuring high flexibility. Specifically, the thickness is preferably less than 100 ⁇ m, more preferably less than 80 ⁇ m, and particularly preferably less than 50 ⁇ m.
  • the lower limit thickness is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and particularly preferably 20 ⁇ m or more from the viewpoint of securing strength against tension or impact.
  • the thickness of the gas barrier film of the present invention is preferably small from the viewpoint of reducing the thickness of the organic EL device.
  • the thickness of the cyclic olefin resin film is preferably less than 50 ⁇ m, more preferably less than 40 ⁇ m, and particularly preferably less than 35 ⁇ m.
  • the lower limit thickness is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more.
  • a gas barrier film in which an inorganic film of the film of the present invention is laminated on only one side on a cyclic olefin resin film having a thickness of less than 50 ⁇ m is likely to curl.
  • the thickness of the inorganic film of the film of the present invention is preferably in the range of 30 to 60 nm, more preferably in the range of 40 to 55 nm. That is, in the gas barrier film of the present invention, the thickness of the cyclic olefin resin film is preferably less than 50 ⁇ m, the thickness of the inorganic film is preferably in the range of 30 to 60 nm, and the thickness of the cyclic olefin resin film is 50 ⁇ m.
  • the thickness of the inorganic film is in the range of 40 to 55 nm.
  • the inorganic film of the film of the present invention having a thickness of 30 to 60 nm, preferably 40 to 55 nm, on a cyclic olefin resin film having a thickness of less than 50 ⁇ m, high transparency while maintaining good gas barrier properties ( High total light transmittance) can be easily obtained.
  • the cyclic olefin resin film in the present invention preferably has a low retardation.
  • the in-plane retardation (Re550) with respect to light having a wavelength of 550 nm is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 300 nm or less.
  • the lower limit is 0 nm.
  • the retardation Re550 of the cyclic olefin resin film is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 10 nm or less.
  • a gas barrier film using such a low-retardation cyclic olefin resin film has the advantage that the viewing angle dependence of the luminescent color of the organic EL element is reduced.
  • the gas barrier film of the present invention can also serve as a retardation film ( ⁇ / 4 plate) constituting a circularly polarizing plate of an organic EL display device (organic EL display).
  • the cyclic olefin resin film has a function as a retardation film ( ⁇ / 4 plate).
  • “the cyclic olefin resin film has a function as a retardation film” means that the retardation Re550 of the cyclic olefin resin film is in the range of 110 to 170 nm.
  • the retardation Re550 is more preferably in the range of 120 to 150 nm, and particularly preferably in the range of 130 to 145 nm.
  • the retardation (Re550) in the in-plane direction with respect to light having a wavelength of 550 nm of the cyclic olefin resin film is a value represented by the following formula.
  • nx represents the refractive index in the slow axis direction in the plane of the cyclic olefin resin film
  • ny represents the refractive index in the fast axis direction in the plane of the cyclic olefin resin film
  • d represents the film thickness (nm )
  • the in-plane refers to the in-plane of the cyclic olefin resin film and the in-plane perpendicular to the thickness direction of the film. Retardation can be measured by the parallel Nicol rotation method using a birefringence meter as used in the examples.
  • the retardation of the cyclic olefin resin film can be controlled, for example, by adjusting a stretching direction and a stretching ratio at the time of production (film formation). Moreover, it can select from the commercial item mentioned above suitably, and can use it.
  • the gas barrier film of the present invention has a gas barrier layer on at least one surface of the cyclic olefin resin film.
  • the gas barrier layer may be provided only on one side of the cyclic olefin resin film or may be provided on both sides, but is preferably provided only on one side.
  • the cured resin layer is provided on the side opposite to the side on which the gas barrier layer of the cyclic olefin resin film is provided (hereinafter sometimes referred to as “back side”). Is preferably provided. Details of the cured resin layer will be described later.
  • the gas barrier film of the present invention preferably has high flexibility. That is, it is preferable that the bendability is good.
  • the cylindrical mandrel method JIS K5600-5-1: 1999 is used as an index for evaluating the flexibility.
  • the cylindrical mandrel method is a method for observing and evaluating the occurrence of cracks and the like when a gas barrier film is wound around a cylindrical mandrel (column) having a diameter of 2 mm to several tens of mm.
  • a gas barrier film is wound around a cylindrical mandrel having a diameter of 2 mm so that the gas barrier layer is on the outer side, It is preferable that no cracks occur in the gas barrier layer.
  • the gas barrier property of the gas barrier film of the present invention is evaluated by the water vapor transmission rate.
  • the water vapor permeability of the gas barrier film of the present invention is preferably less than 5.0 ⁇ 10 ⁇ 3 g / m 2 / day, and preferably less than 3.0 ⁇ 10 ⁇ 3 g / m 2 / day. More preferably, it is particularly preferably less than 1.0 ⁇ 10 ⁇ 3 g / m 2 / day.
  • the gas barrier film of the present invention preferably has high transparency. Specifically, the gas barrier film of the present invention preferably has a total light transmittance of 88% or more.
  • the pencil hardness of the cured resin layer is preferably F or more, and more preferably H or more. If the upper limit pencil hardness is too high, the flexibility described later is deteriorated, so 3H or less is preferable, and 2H or less is particularly preferable.
  • the cured resin layer is preferably a thermosetting resin layer or an active energy ray curable resin layer, and particularly preferably an active energy ray curable resin layer.
  • an ultraviolet curable resin layer is preferable.
  • the cured resin layer preferably contains particles. Furthermore, it is preferable that the cured resin layer has fine protrusions due to particles on the surface thereof. This improves the slipperiness and blocking resistance of the gas barrier film.
  • the gas barrier film contains particles whose average particle diameter is sufficiently smaller than the thickness of the cured resin layer.
  • the ratio (r / d) of the average particle diameter (r: ⁇ m) of the particles contained in the cured resin layer to the thickness (d: ⁇ m) of the cured resin layer is preferably 0.7 or less. Is more preferably 0.5 or less, and particularly preferably 0.3 or less.
  • the lower limit ratio is preferably 0.01 or more, more preferably 0.02 or more, and particularly preferably 0.03 or more, because good slipperiness cannot be obtained if the ratio is too small.
  • the gas barrier film laminated with the cured resin layer also conforms to the cylindrical mandrel method (JIS K5600-5-1: 1999) from the viewpoint of ensuring high flexibility, and the cured resin layer is made of the gas barrier film.
  • JIS K5600-5-1: 1999 the cylindrical mandrel method
  • the cured resin layer is made of the gas barrier film.
  • the indentation hardness measured by the nanoindentation method of the cured resin layer is preferably in the range of 200 to 600 N / mm 2 , and is preferably 250 to 550 N. / Mm 2 is more preferable, and a range of 300 to 500 N / mm 2 is particularly preferable.
  • the cured resin layer is preferably an active energy ray curable resin layer containing a urethane resin (urethane (meth) acrylate monomer or oligomer).
  • the urethane resin is preferably a 1 to 5 functional urethane resin, more preferably a 1 to 4 functional urethane resin, and particularly preferably a 1 to 3 functional urethane resin.
  • the thickness of the cured resin layer is preferably less than 4 ⁇ m, more preferably less than 3 ⁇ m, and particularly preferably less than 2 ⁇ m from the viewpoint of securing good flexibility and suppressing curling of the gas barrier film.
  • the lower limit thickness is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, and particularly preferably 0.7 ⁇ m or more from the viewpoint of imparting good slipperiness.
  • the average particle diameter (r) of the particles contained in the cured resin layer is preferably in the range of 0.02 to 0.5 ⁇ m, more preferably in the range of 0.03 to 0.4 ⁇ m, and in the range of 0.04 to 0.2 ⁇ m. Particularly preferred.
  • the average particle size (r) of the particles to be contained in the cured resin layer is less than 0.02 ⁇ m, good slipperiness may not be obtained. On the other hand, if the average particle size (r) is greater than 0.5 ⁇ m, haze is obtained. The value may increase and transparency may decrease.
  • the content of the particles to be contained in the cured resin layer is preferably in the range of 2 to 40% by mass with respect to 100% by mass of the total solid content of the cured resin layer, from the viewpoint of improving slipperiness while ensuring high transparency.
  • the range of 3 to 30% by mass is more preferable, and the range of 5 to 20% by mass is particularly preferable.
  • Examples of the particles to be contained in the cured resin layer include organic particles and inorganic particles.
  • an acrylic resin As the resin constituting the organic particles, an acrylic resin, a styrene resin, a polyester resin, a polyurethane resin, a polycarbonate resin, a polyamide resin, a silicone resin, a fluorine resin, or 2 used for the synthesis of the above resin.
  • examples thereof include copolymer resins of more than one type of monomer.
  • acrylic resin particles are preferably used.
  • Acrylic resin particles include acrylic resin particles, methacrylic resin particles, acrylic monomers or methacrylic monomers and other monomers such as styrene, urethane acrylate, urethane methacrylate, polyester acrylate, polyester methacrylate, silicone acrylate, and silicone methacrylate. Polymerized resin particles may be mentioned.
  • organic particles are preferably synthesized by an emulsion polymerization method.
  • Organic particles having an average particle size of 0.5 ⁇ m or less can be obtained by synthesis by an emulsion polymerization method.
  • the inorganic particles include inorganic particles such as silica, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, and zeolite.
  • silica particles are preferable, and colloidal silica and gas phase method silica (also referred to as dry silica or fumed silica) are particularly preferable.
  • Inorganic particles such as silica particles are preferably modified (surface treatment) with an organic compound.
  • surface-treating the inorganic particles with an organic compound many particles can be localized (floated) on the surface side of the cured resin layer (the side opposite to the cyclic olefin resin film). Thereby, high slipperiness can be imparted with a relatively small particle content.
  • Examples of the organic compound used for the modification (surface treatment) of the inorganic particles include the following general formulas (1) to (3), and these organic compounds can be used alone or in combination.
  • General formula (1) (In general formula (1), n represents an integer of 1 to 10, m represents an integer of 1 to 5.
  • Q represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom.)
  • General formula (2) DR 7 -Rf 2 ...
  • Specific examples of the compound of the general formula (1) include the following compounds. C 4 F 9 CH 2 CH 2 Si (OCH 3) 3 C 6 F 13 CH 2 CH 2 Si (OCH 3 ) 3 C 8 F 17 CH 2 CH 2 Si (OCH 3) 3 C 6 F 13 CH 2 CH 2 CH 2 Si (OCH 3) 3 C 6 F 13 CH 2 CH 2 CH 2 Si (OCH 3) 3 C 6 F 13 CH 2 CH 2 Si (OC 2 H 5) 3 C 8 F 17 CH 2 CH 2 CH 2 Si (OC 2 H 5) 3 C 6 F 13 CH 2 CH 2 CH 2 CH 2 Si (OC 2 H 5 ) 3 C 6 F 13 CH 2 CH 2 SiCl 3 C 6 F 13 CH 2 CH 2 SiBr 3 C 6 F 13 CH 2 CH 2 CH 2 SiCl 3 C 6 F 13 CH 2 CH 2 Si (OCH 3) Cl 2.
  • Specific examples of the general formula (2) include acryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxybutyltrimethoxysilane, acryloxypentyltrimethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyheptyltri Methoxysilane, methacryloxyethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxyhexyltrimethoxysilane, methacryloxyheptyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxy Examples include silane and compounds in which the methoxy group in these compounds is substituted with other alkoxyl groups and hydroxyl groups. .
  • Specific examples of the general formula (3) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluoro Butyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- Perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloc
  • the cured resin layer has a surface roughness (Ra) measured by an atomic force microscope (AFM) on the surface of the cured resin layer of 2.0 nm or more from the viewpoint of improving slipperiness while ensuring high transparency. It is preferably 0 nm or less.
  • the surface roughness (Ra) of the cured resin layer is less than 2.0 nm, the slipperiness may be lowered.
  • surface roughness (Ra) exceeds 10.0 nm, transparency may fall.
  • the surface roughness (Ra) measured with an atomic force microscope (AFM) on the surface of the cured resin layer is preferably 2.5 nm to 7.0 nm, preferably 3.0 nm to 6. Particularly preferably, it is 0 nm or less.
  • the gas barrier film of this invention is bonded to an organic EL element through a sealing adhesive layer. That is, the gas barrier film of the present invention preferably has a sealing adhesive layer laminated on the surface of the gas barrier layer.
  • the sealing adhesive layer is used as a sealing resin such as polyisobutylene, butyl rubber, polyisoprene, styrene-isobutylene modified resin, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene rubber. It is preferable to contain at least one resin selected from the group consisting of polybutadiene rubber, styrene-butadiene rubber, and polybutene. Among these, it is more preferable that polyisobutylene and butyl rubber are included.
  • the sealing adhesive layer preferably further contains a tackifying resin.
  • tackifying resins include alicyclic petroleum resins, alicyclic hydrogenated petroleum resins, aromatic petroleum resins, and rosin resins.
  • alicyclic petroleum resins are preferable, and among alicyclic hydrogenated petroleum resins, hydrogenated terpene resins, hydrogenated ester resins, hydrogenated resins of C5 petroleum resins, C9 A hydrogenated resin of a petroleum petroleum resin is preferred.
  • the mass ratio of the sealing resin to the tackifier resin is preferably 10/90 to 100/0, and more preferably 20/80 to 90/10.
  • the sealing adhesive layer can further contain an ultraviolet absorber, an antioxidant, an antistatic agent, a plasticizer, a filler, a flame retardant, a crosslinking agent, a rust inhibitor, and the like.
  • the thickness of the sealing adhesive layer is preferably in the range of 5 to 150 ⁇ m, more preferably in the range of 10 to 100 ⁇ m, and particularly preferably in the range of 20 to 80 ⁇ m.
  • the sealing adhesive layer preferably has a water vapor transmission rate of 40 g / m 2 / day or less, more preferably 30 g / m 2 / day or less, and 20 g / m 2 / day or less. It is particularly preferred.
  • the sealing pressure-sensitive adhesive layer may be formed by coating on the gas barrier layer of the gas barrier film, or once the sealing pressure-sensitive adhesive layer is applied to the release film, the surface of the sealing pressure-sensitive adhesive layer and the gas barrier The surface of the gas barrier layer of the adhesive film may be bonded.
  • gas barrier film of the present invention can be suitably used for electronic devices such as packaging materials such as pharmaceuticals, organic EL lighting, organic EL devices, and solar cells.
  • the gas barrier film of the present invention since the gas barrier film of the present invention has high flexibility, it is suitable for a flexible (foldable or foldable) organic EL device.
  • the gas barrier film of the present invention is suitable as a retardation film ( ⁇ / 4 plate).
  • Examples of the flexible organic EL device include flexible displays such as a foldable display (foldable display), a bendable display (foldable display), and a rollable display (rollable display).
  • the gas barrier film of the present invention is suitable for the flexible display as described above.
  • the gas barrier film is cut into a predetermined size when applied to an organic EL device or the like. At this time, a micro crack may occur in the cut portion of the gas barrier layer. Even if a microcrack is generated only in the cut portion of the gas barrier layer of the cut sheet of the gas barrier film cut to a predetermined size, the gas barrier performance is not usually a problem. However, when a cut sheet with microcracks in the cut part of the gas barrier layer is applied to a flexible display, when the flexible display is folded or folded, the micro cracks present in the cut part of the gas barrier layer of the cut sheet Gas barrier properties may be reduced.
  • the inorganic film of the gas barrier film of the present invention does not generate cracks at the time of cutting, or is extremely minute or very few even when cracks occur.
  • Such a cut sheet of the gas barrier film of the present invention is applied to a flexible organic EL device, and even if it is folded or folded, a decrease in gas barrier property is suppressed.
  • the cut sheet of the gas barrier film of the present invention is suitable for a flexible organic EL device, for example, a flexible organic EL display. It is particularly suitable for foldable organic EL displays and bendable organic EL displays.
  • the organic EL device of the present invention includes the gas barrier film of the present invention.
  • FIG. 1 is a schematic cross-sectional view of an example of an organic EL device provided with the gas barrier film (cut sheet) of the present invention.
  • the organic EL device 100 includes an organic EL element 102 on a back substrate 101 (polyimide substrate).
  • the organic EL element 102 is covered with a gas barrier film 104 through a sealing adhesive layer 103.
  • An optical film 105 (polarizing film, retardation film, touch panel, etc.) is laminated on the gas barrier film 104, and a surface protective film 106 (hard coat film, antireflection film, etc.) is further laminated thereon.
  • a surface protective film 106 hard coat film, antireflection film, etc.
  • the cut sheet of the gas barrier film of the present invention has a feature that the water vapor transmission rate does not increase even if it is folded or folded.
  • the water vapor transmission rate after the folding test of the cut sheet is preferably less than 5.0 ⁇ 10 ⁇ 3 g / m 2 / day, similar to that before the folding test, and 3.0 ⁇ 10 ⁇ more preferably 3 less than g / m 2 / day, particularly preferably less than 1.0 ⁇ 10 -3 g / m 2 / day. Details of the folding test will be described later.
  • the gas barrier film cut sheet of the present invention preferably has substantially no microcracks at the cut portion of the gas barrier layer. Thereby, the increase in the water vapor transmission rate after the folding test of the cut sheet is suppressed, and the water vapor transmission rate after the folding test of the cut sheet can be within the above range.
  • the micro crack refers to a crack having a length of 30 ⁇ m or more.
  • the fact that microcracks are not substantially present in the cut portion of the gas barrier layer means that the cut portion of the cut sheet (at a magnification of 200 times using a digital microscope (“VHX-1000” manufactured by Keyence Corporation)) ( For example, when the cut sheet is rectangular, its four sides) are observed at approximately 10 mm intervals, which means that the number of microcracks per 200 mm length of the cut portion is less than 50.
  • the number of microcracks in the microcrack measurement method is preferably less than 30 (pieces / cut portion length 200 mm), more preferably less than 10 (pieces / cut portion length 200 mm), and 0 (pieces / cut portion length 200 mm). Particularly preferred.
  • the gas barrier film of the present invention that is, the structure having a gas barrier layer composed of a single inorganic film containing zinc oxide, silicon dioxide and aluminum oxide directly on the cyclic olefin resin film, Generation of cracks is suppressed.
  • Measurement mode Load-unloading test ⁇ Maximum load: 100 mN -Holding time when maximum load is reached: 1 second-Loading speed, unloading speed: 10 mN / sec Indentation depth: 1/10 of the film thickness.
  • Composition analysis of gas barrier layer is determined by X-ray photoelectron spectroscopy (XPS). Method). That is, after removing the outermost layer by etching about 5 nm by sputter etching using argon ions, the content ratio of each element was measured.
  • the measurement conditions of the XPS method are as follows.
  • the gas barrier film was cut to prepare two sheet pieces (20 cm ⁇ 15 cm).
  • the two sheet pieces are slightly shifted and overlapped so that the gas barrier layer surface of the two sheet pieces and the cured resin layer face each other and placed on a smooth table, and the lower sheet piece is fixed on the table with fingers,
  • the quality of the slipperiness was determined by sliding the upper sheet piece by hand.
  • the measurement environment is 23 ° C. and 55% RH.
  • B The upper sheet piece does not slip.
  • Retardation of substrate film Retardation in the in-plane direction with respect to light (Re550) at a wavelength of 550 nm of the substrate film was parallel using a birefringence meter KOBRA-WR manufactured by Oji Scientific Instruments. It was measured by the Nicol rotation method.
  • Number per cutting part 200 mm total number / (200 mm / total length of cutting part) Formula 1 (In addition, the total length of the cutting part in a present Example is 640 mm)
  • D The number of fine cracks per 200 mm cut portion is 50 or more and less than 100.
  • E The number of fine cracks per 200 mm cut portion is 100 or more.
  • a sputter target which is a mixed sintered material formed of zinc oxide, silicon dioxide, and aluminum oxide, is placed on the sputter electrode 12 using the winding type sputtering / CVD apparatus 1 having the structure shown in FIG. Sputtering with gas was performed, and an inorganic film was laminated on one surface of the cyclic olefin resin film to obtain a gas barrier film 4.
  • the specific operation is as follows. First, in the winding chamber 6 of the winding type sputtering / CVD apparatus 1 in which a sputtering target sintered with a composition ratio of zinc oxide / silicon dioxide / aluminum oxide of 77/20/3 is installed on the sputtering electrode 12. Then, the surface of the unwinding shaft 7 on which the inorganic film of the cyclic olefin resin film is provided is set so as to face the sputter electrode 12, and the unwinding and unwinding side guide rolls 8, 9, 10 are passed through the cooling drum.
  • Argon gas and oxygen gas were introduced at an oxygen gas partial pressure of 10% so that the degree of decompression was 2 ⁇ 10 ⁇ 1 Pa, and an argon / oxygen gas plasma was generated by applying an applied power of 4000 W from a DC power source. A film was formed. The thickness was adjusted by the film transport speed. Then, it wound around the winding shaft 16 via the winding side guide rolls 13, 14, 15.
  • composition of this inorganic film was such that the Zn atom concentration was 27.5 atom%, the Si atom concentration was 13.1 atom%, the Al atom concentration was 2.3 atom%, and the O atom concentration was 57.1 atom%.
  • a gas barrier film was produced in the same manner as in Example 1 except that was changed to 50 nm.
  • Example 3 a gas barrier film having a function as a retardation film ( ⁇ / 4 plate) was produced. That is, a protective film of a cyclic olefin resin film (“Zeonor Film (registered trademark)” ZM14-140 of Nippon Zeon Co., Ltd .: a PET protective film previously laminated on one side) having a thickness of 28 ⁇ m and a retardation Re550 of 140 nm is laminated.
  • a gas barrier film was prepared by laminating an inorganic film on the non-coated surface in the same manner as in Example 1. However, the thickness of the inorganic film was adjusted to 50 nm.
  • UV-1700B urethane acrylate oligomer
  • MEK organic solvent
  • Example 3 A gas barrier film was produced in the same manner as in Example 1 except that the base film was changed to a polyethylene terephthalate film having a thickness of 50 ⁇ m (“Lumirror (registered trademark) U48” manufactured by Toray Industries, Inc.).
  • Comparative Example 4 In Comparative Example 1, a gas barrier film was produced in the same manner as in Comparative Example 1, except that the base film was changed to a polyethylene terephthalate film (“Lumirror (registered trademark)” U48 manufactured by Toray Industries, Inc.) having a thickness of 50 ⁇ m. .
  • a polyethylene terephthalate film (“Lumirror (registered trademark)” U48 manufactured by Toray Industries, Inc.) having a thickness of 50 ⁇ m. .
  • a roll-up type sputtering / CVD apparatus 1 having a structure shown in FIG. 2 was used, and a silicon dioxide film (SiO 2 film) having a thickness of 200 nm was laminated.
  • a roll-up type sputtering / CVD apparatus 1 having the structure shown in FIG. 2 was used to laminate a silicon nitride film (SiN film) having a thickness of 200 nm on the surface.
  • the silicon nitride film was formed by generating plasma in a mixed gas composed of SiH 4 , NH 3 , and N 2 .
  • COP represents a cyclic olefin resin film
  • PET represents a polyethylene terephthalate film
  • HC represents a hard coat layer.
  • Examples 1 to 3 are excellent in water vapor transmission rate, gas barrier property, and total light transmittance.
  • Comparative Example 1 since the undercoat layer (hard coat layer) is disposed between the cyclic olefin resin film and the gas barrier layer, the flexibility (A) of the gas barrier layer is lowered.
  • the inorganic film of the film of the present invention is directly laminated on a polyethylene terephthalate film (PET film), but the gas barrier property (water vapor permeability) is inferior.
  • PET film polyethylene terephthalate film
  • the gas barrier property water vapor permeability
  • the PET film is affected by inferior smoothness compared to the cyclic olefin resin film.
  • the total light transmittance is reduced.
  • a gas barrier layer (inorganic film of the film of the present invention) is laminated on a polyethylene terephthalate film (PET film) via an undercoat layer (hard coat layer), and the gas barrier property (water vapor permeability) is Although it is good, the flexibility (A) of the gas barrier layer is lowered, and the total light transmittance is also lowered.
  • Comparative Examples 5 and 6 are gas barrier films provided with a silicon dioxide film (SiO 2 film) or a silicon nitride film (SiN film) instead of the inorganic film of the film of the present invention. Light transmittance is inferior.
  • the cut sheets of the gas barrier films of Examples 1 to 3 are substantially free from microcracks at the cut portions of the gas barrier layer, and the increase in water vapor permeability after the folding test is suppressed.
  • Comparative Examples 1 and 4 provided with an undercoat layer (hard coat layer), Comparative Example 2 in which an inorganic film of the film of the present invention and another film (SiO 2 film) were laminated, and an inorganic film of the film of the present invention
  • the cut sheets of the gas barrier films of Comparative Examples 5 and 6 provided with a silicon dioxide film (SiO 2 film) or a silicon nitride film (SiN film) both have microcracks at the cut portion of the gas barrier layer. The water vapor transmission rate after the folding test is greatly increased.
  • Example 11 Prior to producing the gas barrier film of Example 1, the protective film of the cyclic olefin resin film was peeled off, and the following cured resin layer coating solution a1 was applied to the peeled surface with a gravure coater and dried at 90 ° C. The cured resin layer was formed by irradiating with UV rays of 400 mJ / cm 2 and curing.
  • the thickness of the cured resin layer is 1.5 ⁇ m, the average particle diameter of the particles is 0.08 ⁇ m, and the ratio (r / d) between the average particle diameter of the particles (r: ⁇ m) and the thickness of the cured resin layer (d: ⁇ m). was 0.05. Moreover, the pencil hardness of this cured resin layer was F.
  • ⁇ Coating liquid a1 for cured resin layer The silica particle dispersion b1 shown below was added to an ultraviolet curable coating agent “Aika Itron (registered trademark)” Z-850-3 manufactured by Aika Kogyo Co., Ltd., in an amount of 10 mass based on the total solid content of the coating solution. % And diluted with an organic solvent (MEK) to prepare a coating solution having a solid content concentration of 20% by mass.
  • an ultraviolet curable coating agent “Aika Itron (registered trademark)” Z-850-3 manufactured by Aika Kogyo Co., Ltd.
  • a gas barrier layer (inorganic film) was laminated on the surface opposite to the surface of the cured resin layer of the cyclic olefin resin film on which the cured resin layer was laminated in the same manner as in Example 1 to produce a gas barrier film.
  • Example 12 Prior to producing the gas barrier film of Example 2, the protective film of the cyclic olefin resin film was peeled off, and a cured resin layer was laminated on the peeled surface in the same manner as in Example 11. Next, a gas barrier layer (inorganic film) was laminated on the surface opposite to the surface of the cured resin layer of the cyclic olefin resin film on which the cured resin layer was laminated in the same manner as in Example 2 to produce a gas barrier film.
  • a gas barrier layer inorganic film
  • Example 13 Prior to producing the gas barrier film of Example 3, the protective film of the cyclic olefin resin film was peeled off, and a cured resin layer was laminated on the peeled surface in the same manner as in Example 11. Next, a gas barrier film in which a gas barrier layer (inorganic film) was laminated on the surface opposite to the surface of the cured resin layer of the cyclic olefin resin film on which the cured resin layer was laminated was produced in the same manner as in Example 3.
  • a gas barrier layer inorganic film
  • the thickness of the cured resin layer is 1.5 ⁇ m, the average particle diameter of the particles is 0.08 ⁇ m, and the ratio (r / d) between the average particle diameter of the particles (r: ⁇ m) and the thickness of the cured resin layer (d: ⁇ m).
  • the pencil hardness of this cured resin layer was H.
  • a hard coat layer and a gas barrier layer are sequentially laminated on the surface opposite to the surface of the cured resin layer of the cyclic olefin resin film on which the cured resin layer is laminated in the same manner as in Comparative Example 1 to provide gas barrier properties.
  • a film was prepared.
  • ⁇ Coating liquid a2 for cured resin layer> In a UV curable resin coating solution containing urethane acrylate oligomer (“UV-1700B” of Nippon Synthetic Chemical Co., Ltd.), the silica particle dispersion b1 is 8 masses in terms of solid content with respect to the total solid content of the coating solution. % And diluted with an organic solvent (MEK) to prepare a coating solution having a solid content concentration of 20% by mass.
  • MEK organic solvent
  • the thickness of this cured resin layer was 1.5 ⁇ m.
  • the pencil hardness of this cured resin layer was H.
  • a hard coat layer and a gas barrier layer are sequentially laminated in the same manner as in Comparative Example 2 on the surface opposite to the surface of the cured resin layer of the cyclic olefin resin film on which the cured resin layer is laminated.
  • a film was prepared.
  • ⁇ Coating liquid a3 for cured resin layer An ultraviolet curable resin coating solution containing urethane acrylate oligomer (“UV-1700B” from Nippon Synthetic Chemical Co., Ltd.) was diluted with an organic solvent (MEK) to prepare a coating solution having a solid content concentration of 20% by mass.
  • UV-1700B ultraviolet curable resin coating solution containing urethane acrylate oligomer
  • MEK organic solvent
  • COP represents a cyclic olefin resin film.
  • HC represents a hard coat layer.

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  • Mechanical Engineering (AREA)
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Abstract

Le but de la présente invention est de fournir un film barrière aux gaz qui possède un faible retard optique et une flexibilité favorable, tout en étant extrêmement transparent. Afin d'atteindre cet objectif, la présente invention présente la configuration suivante. Plus précisément, l'invention concerne un film barrière aux gaz ayant une couche barrière aux gaz composée d'une seule membrane inorganique directement sur au moins une surface d'un film de résine d'oléfine cyclique, la membrane inorganique comportant au moins de l'oxyde de zinc, du dioxyde de silicium et de l'oxyde d'aluminium.
PCT/JP2017/042580 2016-12-15 2017-11-28 Film barrière aux gaz et dispositif électroluminescent organique WO2018110272A1 (fr)

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KR102326010B1 (ko) * 2021-01-13 2021-11-11 코오롱인더스트리 주식회사 수분 및 산소 배리어성 적층체

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JP2014043094A (ja) * 2012-08-01 2014-03-13 Toray Ind Inc ガスバリア性フィルム
WO2014097997A1 (fr) * 2012-12-19 2014-06-26 コニカミノルタ株式会社 Dispositif électronique
JP2015189047A (ja) * 2014-03-27 2015-11-02 富士フイルム株式会社 機能性フィルムおよび機能性フィルムの製造方法
JP2016064650A (ja) * 2014-09-16 2016-04-28 東レ株式会社 ガスバリア性フィルム
JP2016095974A (ja) * 2014-11-13 2016-05-26 日本ゼオン株式会社 基材フィルム、バリア積層体及び有機エレクトロルミネッセンス表示装置
JP2016175223A (ja) * 2015-03-19 2016-10-06 凸版印刷株式会社 ガスバリア性積層体、及びそれを用いた太陽電池モジュール並びに画像表示素子
WO2017131202A1 (fr) * 2016-01-29 2017-08-03 日東電工株式会社 Film stratifié conducteur

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JP2013189657A (ja) * 2011-02-25 2013-09-26 Mitsubishi Materials Corp 透明酸化物膜およびその製造方法
JP2014043094A (ja) * 2012-08-01 2014-03-13 Toray Ind Inc ガスバリア性フィルム
WO2014097997A1 (fr) * 2012-12-19 2014-06-26 コニカミノルタ株式会社 Dispositif électronique
JP2015189047A (ja) * 2014-03-27 2015-11-02 富士フイルム株式会社 機能性フィルムおよび機能性フィルムの製造方法
JP2016064650A (ja) * 2014-09-16 2016-04-28 東レ株式会社 ガスバリア性フィルム
JP2016095974A (ja) * 2014-11-13 2016-05-26 日本ゼオン株式会社 基材フィルム、バリア積層体及び有機エレクトロルミネッセンス表示装置
JP2016175223A (ja) * 2015-03-19 2016-10-06 凸版印刷株式会社 ガスバリア性積層体、及びそれを用いた太陽電池モジュール並びに画像表示素子
WO2017131202A1 (fr) * 2016-01-29 2017-08-03 日東電工株式会社 Film stratifié conducteur

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102326010B1 (ko) * 2021-01-13 2021-11-11 코오롱인더스트리 주식회사 수분 및 산소 배리어성 적층체
WO2022154305A1 (fr) * 2021-01-13 2022-07-21 코오롱인더스트리 주식회사 Stratifié barrière à l'humidité et à l'oxygène

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