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WO2018088352A1 - Film barrière au gaz, et dispositif contenant celui-ci - Google Patents

Film barrière au gaz, et dispositif contenant celui-ci Download PDF

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Publication number
WO2018088352A1
WO2018088352A1 PCT/JP2017/039903 JP2017039903W WO2018088352A1 WO 2018088352 A1 WO2018088352 A1 WO 2018088352A1 JP 2017039903 W JP2017039903 W JP 2017039903W WO 2018088352 A1 WO2018088352 A1 WO 2018088352A1
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Prior art keywords
layer
thin film
inorganic thin
gas barrier
film layer
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PCT/JP2017/039903
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English (en)
Japanese (ja)
Inventor
美保 大関
山下　恭弘
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to KR1020197016473A priority Critical patent/KR102446746B1/ko
Priority to CN201780065240.1A priority patent/CN109890607A/zh
Publication of WO2018088352A1 publication Critical patent/WO2018088352A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • 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
    • C08J7/048—Forming gas barrier coatings
    • 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
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates

Definitions

  • the present invention relates to a gas barrier film and a device including the same.
  • the present invention provides light resistance to a moisture barrier gas barrier film used in a device such as a flexible display, suppresses UV deterioration inside the device below the gas barrier film, and / or suppresses UV deterioration of the gas barrier film itself. Plan.
  • the inventors of the present invention have studied the gas barrier film in detail to solve the previous problem, and have completed the present invention.
  • a gas barrier film having a base material layer including at least a flexible base material, an inorganic thin film layer, and an organic layer containing an ultraviolet absorber in this order,
  • the inorganic thin film layer contains silicon atoms, oxygen atoms and carbon atoms,
  • the gas barrier film according to [1] which has a further inorganic thin film layer on the surface of the base material layer opposite to the ultraviolet absorber-containing organic layer side.
  • the ratio of the number of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer continuously changes in the thickness direction of the inorganic thin film layer.
  • the inorganic thin film layer is any one of [1] to [5], wherein an average atomic ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is in the range of the formula (1).
  • the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition represented by Formula (5) in a region of 90% or more in the film thickness direction of the inorganic thin film layer.
  • the carbon distribution curve has at least one extreme value.
  • the peak intensity (I 1 ) existing at 950 to 1050 cm ⁇ 1 and the peak intensity (I 1 ) existing at 1240 to 1290 cm ⁇ 1 is in the range of formula (2), gas barrier properties according to any one of [1] to [7] film.
  • the gas barrier film of the present invention has sufficient light resistance and flexibility, it can be suitably used for a device.
  • the gas barrier film of the present invention has a base material layer having at least a flexible base material, an inorganic thin film layer, and a coating layer containing an ultraviolet absorber in this order, and the inorganic thin film layer includes silicon atoms, oxygen atoms, and carbon atoms.
  • the gas barrier film has a light transmittance at 380 nm of 20% or less.
  • the base material layer has at least a flexible base material.
  • the base material layer may be a single layer or a plurality of layers.
  • the base material layer is comprised with the flexible base material.
  • the base material layer is a plurality of layers, the base material layer preferably has at least a flexible base material, and the base material layer preferably exhibits flexibility. It is more preferable that the surface is a flexible substrate, and it is more preferable that each of the plurality of layers is composed of a flexible substrate.
  • a resin film containing at least one resin as a resin component can be used, and a colorless and transparent resin film is preferable.
  • resins that can be used for the resin film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin; polyamide resins; polycarbonate resins; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin; Polyether sulfide (PES). It can also be used.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin
  • polyamide resins polycarbonate resins
  • Polystyrene resin Polyvin
  • the flexible substrate may be an unstretched resin film, and the unstretched resin substrate is uniaxially stretched, tenter-type sequential biaxial stretch, tenter-type simultaneous biaxial stretch, tubular-type simultaneous biaxial stretch, etc.
  • the resin film may be stretched in the flow direction of the resin base material (MD direction) and / or the direction perpendicular to the flow direction of the resin base material (TD direction) by the known method.
  • the thickness of the flexible substrate can be appropriately set in consideration of the production of a stable gas barrier film.
  • the thickness is preferably 5 to 500 ⁇ m, more preferably 10 to 200 ⁇ m, and still more preferably 50 to 100 ⁇ m.
  • the thickness of the base material layer is preferably 5 to 500 ⁇ m, more preferably 10 to 200 ⁇ m, and still more preferably 50 to 100 ⁇ m.
  • the substrate layer is a plurality of layers, the total thickness of all the layers constituting the substrate layer including the flexible substrate is preferably 5 to 500 ⁇ m, more preferably 10 to 200 ⁇ m, The thickness is preferably 50 to 100 ⁇ m.
  • the layer constituting the flexible substrate may be a retardation film having different in-plane two-component refractive indexes such as a ⁇ / 4 retardation film and a ⁇ / 2 retardation film.
  • cellulose resin, polycarbonate resin, polyarylate resin, polyester resin, acrylic resin, polysulfone resin, polyethersulfone resin, cyclic olefin resin, alignment solidification of liquid crystal compound A layer etc. can be illustrated.
  • polycarbonate resin films are preferably used because they are inexpensive and uniform.
  • a film forming method a solvent casting method or a precision extrusion method capable of reducing the residual stress of the film can be used, but the solvent casting method is preferably used in terms of uniformity.
  • the stretching method is not particularly limited, and can be applied such as longitudinal uniaxial between rolls and tenter transverse uniaxial stretching that can obtain uniform optical characteristics.
  • the in-plane retardation Re (550) at a wavelength of 550 nm is preferably 100 to 180 nm, more preferably 110 to 170 nm. More preferably, it is 120 to 160 nm.
  • the in-plane retardation Re (550) at a wavelength of 550 nm is preferably 220 to 320 nm, more preferably 240 to 300 nm. More preferably, it is 250 to 280 nm.
  • the flexible substrate When the flexible substrate is a retardation film, it may exhibit reverse wavelength dispersion in which the retardation value increases according to the wavelength of the measurement light, and the retardation value decreases according to the wavelength of the measurement light.
  • a positive chromatic dispersion characteristic may be exhibited, or a flat chromatic dispersion characteristic in which the retardation value hardly changes depending on the wavelength of the measurement light may be exhibited.
  • the flexible substrate is a retardation film exhibiting reverse wavelength dispersion
  • the retardation at the wavelength ⁇ of the flexible substrate is expressed as Re ( ⁇ )
  • the flexible substrate 10 is Re (450) / Re (550) ⁇ 1 and Re (650) / Re (550)> 1 can be satisfied.
  • the flexible base material is preferably colorless and transparent from the viewpoint that light can be transmitted and absorbed. More specifically, the total light transmittance is preferably 80% or more, and more preferably 85% or more. Further, the haze is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less.
  • the flexible substrate can be used as a substrate of an organic device or an energy device
  • the flexible substrate is preferably insulative and preferably has an electric resistivity of 10 6 ⁇ cm or more.
  • the surface of the flexible substrate may be subjected to surface activation treatment from the viewpoint of adhesion with an inorganic thin film layer or the like.
  • Examples of the surface activation treatment include corona treatment, plasma treatment, flame treatment, and liquid cleaning treatment.
  • the base material layer may include the same or different kinds of organic layers A on at least one surface of the flexible base material for the purpose of improving the adhesion and / or flatness with the inorganic thin film layer. .
  • the same or different types of organic layers A may be included on at least one surface of the flexible substrate constituting the substrate layer.
  • the surface of the substrate layer on which the inorganic thin film layer can be laminated (that is, at least one surface of the surfaces of the substrate layer) is a flexible substrate, and the flexible substrate Embodiments having the organic layer A on at least one of the surfaces, more preferably on the surface on which the inorganic thin film layer is laminated, are mentioned.
  • both sides of the base material layer are flexible base materials, and on at least one surface of the flexible base material, more preferably on the surface on which the inorganic thin film layer is laminated.
  • An embodiment having an organic layer A is mentioned.
  • the thickness of the organic layer is preferably 0.5 to 10 ⁇ m, more preferably 0.8 to 5 ⁇ m, and still more preferably 1 to 3 ⁇ m.
  • Examples of the organic layer A include a planarization layer, an easy slip layer, and an anti-blocking layer.
  • the base material layer When the base material layer includes the organic layer A, the base material layer has an organic layer only on one surface of the flexible base material, or different types of the base material layer on both surfaces of the flexible base material. It may have an organic layer, for example, a flat layer on one surface and a slippery layer on the other surface.
  • a resin composition containing a monomer and / or oligomer of a photocurable resin such as an ultraviolet ray or an electron beam curable resin is usually applied on a flexible substrate, and if necessary, dried. It can be formed by being cured by irradiation with ultraviolet rays or electron beams.
  • the resin composition may contain additives such as a solvent, a photopolymerization initiator, a thermal polymerization initiator, an antioxidant, an ultraviolet absorber, and a plasticizer as necessary.
  • Examples of methods by coating include various conventionally used coating methods such as spray coating, spin coating, bar coating, curtain coating, dipping method, air knife method, slide coating, hopper coating, reverse roll coating, gravure coating, Examples of the method include extrusion coating.
  • the flattening layer is formed by applying a UV curable resin on a substrate and UV curing.
  • a UV curable resin examples thereof include a UV curable urethane acrylate resin, a UV curable epoxy acrylate resin, a UV curable polyester acrylate resin, a UV curable epoxy resin, and a UV curable polyol acrylate resin.
  • the flattening layer when the temperature change of the elastic modulus of the flattening layer surface is evaluated by a rigid pendulum type physical property tester (for example, RPT-3000W manufactured by A & D Co., Ltd.), the flattening layer surface It is preferable that the temperature at which the elastic modulus is reduced by 50% or more is 150 ° C. or more.
  • the easy-sliding layer is formed, for example, by applying a UV curable resin containing inorganic particles on a substrate and UV curing.
  • the UV curable resin include a UV curable urethane acrylate resin, a UV curable epoxy acrylate resin, a UV curable polyester acrylate resin, a UV curable epoxy resin, and a UV curable polyol acrylate resin.
  • the inorganic particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, and zirconium oxide.
  • the inorganic thin film layer has at least a silicon atom (Si), an oxygen atom (O), and a viewpoint that can exhibit a higher level of water vapor permeation prevention performance, and a viewpoint of bending resistance, ease of manufacturing, and low manufacturing cost.
  • As the inorganic thin film layer a known inorganic material layer having gas barrier properties can be appropriately used.
  • the inorganic thin film layer may be a single layer or a plurality of layers. Further, the step of forming the inorganic thin film layer may be performed once or may be performed a plurality of times. When performed several times, it may be performed under the same conditions or may be performed under different conditions.
  • inorganic materials are metal oxides, metal nitrides, metal oxynitrides, metal oxycarbides, and mixtures containing at least two of these.
  • the inorganic material layer a multilayer film in which two or more inorganic thin film layers described above are stacked may be used.
  • an inorganic thin film layer can be provided in the surface of one or both of a base material layer.
  • the inorganic thin film layer has a general formula of SiO ⁇ C ⁇ [wherein ⁇ and ⁇ each independently represents a positive number less than 2. ] Can be the main component.
  • the main component means that the content of the component is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more with respect to the mass of all components constituting the inorganic thin film layer. It means that.
  • Inorganic thin layer may contain one kind of compound represented by the general formula SiO ⁇ C ⁇ , may contain a general formula SiO alpha C beta in two or more compounds represented.
  • One or more of ⁇ and ⁇ in the general formula may be a constant value or may vary in the thickness direction of the inorganic thin film layer.
  • the inorganic thin film layer contains an element other than silicon atom, oxygen atom and carbon atom such as hydrogen atom, nitrogen atom, boron atom, aluminum atom, phosphorus atom, sulfur atom, fluorine atom and chlorine atom. You may contain.
  • the inorganic thin film layer contains a hydrogen atom in addition to a silicon atom, an oxygen atom and a carbon atom
  • the general formula is SiO ⁇ C ⁇ H ⁇ [wherein ⁇ and ⁇ are as defined above, and ⁇ is less than 6.
  • the compound represented by [denotes a positive number of] is a main component.
  • the main component means that the content of the component is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more with respect to the mass of all components constituting the inorganic thin film layer. It means that.
  • Inorganic thin layer may contain one kind of compound represented by the general formula SiO ⁇ C ⁇ H ⁇ , also contain the general formula SiO ⁇ C ⁇ H 2 or more compounds represented by the gamma Good.
  • One or more of ⁇ , ⁇ , and ⁇ in the general formula may be a constant value or may vary in the thickness direction of the thin film layer.
  • the inorganic thin film layer has a high density when the average atomic ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is expressed by C / Si, and defects such as fine voids and cracks
  • the range of C / Si preferably satisfies the formula (1). 0.10 ⁇ C / Si ⁇ 0.50 (1) Further, it is more preferably in the range of 0.15 ⁇ C / Si ⁇ 0.45, more preferably in the range of 0.20 ⁇ C / Si ⁇ 0.40, and 0.25 ⁇ C / Si ⁇ 0. A range of 35 is particularly preferred.
  • the inorganic thin film layer has a high density when the average atomic ratio of oxygen atoms (O) to silicon atoms (Si) in the inorganic thin film layer is expressed by O / Si, and fine voids, cracks, etc.
  • O oxygen atoms
  • Si silicon atoms
  • it is preferably in the range of 1.50 ⁇ O / Si ⁇ 1.90, more preferably in the range of 1.55 ⁇ O / Si ⁇ 1.85, and 1.60 ⁇ O. /Si ⁇ 1.80 is more preferable, and 1.65 ⁇ O / Si ⁇ 1.75 is particularly preferable.
  • the average atomic number ratios C / Si and O / Si are measured by XPS depth profile under the following conditions. From the obtained distribution curves of silicon atoms, oxygen atoms and carbon atoms, the averages in the thickness direction of the respective atoms. After obtaining the atomic concentration, the average atomic ratio C / Si and O / Si can be calculated.
  • the inorganic thin film layer has a peak intensity (I 1 ) existing at 950 to 1050 cm ⁇ 1 and a peak existing at 1240 to 1290 cm ⁇ 1 when infrared spectroscopic measurement (ATR method) is performed on the surface of the inorganic thin film layer.
  • the intensity ratio with the intensity (I 2 ) may be in a range satisfying the expression (2). 0.01 ⁇ I 2 / I 1 ⁇ 0.05 (2)
  • the peak intensity ratio I 2 / I 1 calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si—CH 3 to Si—O—Si in the inorganic thin film layer.
  • the inorganic thin film layer satisfying the relationship represented by the formula (2) has high denseness and has fewer defects such as fine voids and cracks. Therefore, the inorganic thin film layer is considered to have excellent gas barrier properties and excellent impact resistance. It is done.
  • the range of the peak intensity ratio I 2 / I 1, from the viewpoint of maintaining a high density of the inorganic thin layer preferably in the range of 0.02 ⁇ I 2 / I 1 ⁇ 0.04.
  • Infrared spectroscopic measurement of the surface of the inorganic thin film layer is a Fourier transform infrared spectrophotometer equipped with an ATR attachment (PIKE MIRacle) using a germanium crystal as a prism (manufactured by JASCO Corporation, FT / IR-460Plus) Can be measured.
  • PIKE MIRacle an ATR attachment
  • germanium crystal as a prism
  • the inorganic thin film layer has a peak intensity (I 1 ) existing at 950 to 1050 cm ⁇ 1 and a peak existing at 770 to 830 cm ⁇ 1 when infrared spectroscopic measurement (ATR method) is performed on the surface of the inorganic thin film layer.
  • the intensity ratio with the intensity (I 3 ) may be in the range of the formula (3). 0.25 ⁇ I 3 / I 1 ⁇ 0.50 (3)
  • the peak intensity ratio I 3 / I 1 calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si—C, Si—O, etc. to Si—O—Si in the inorganic thin film layer. .
  • the inorganic thin film layer satisfying the relationship represented by the formula (3) is considered to have excellent flex resistance and excellent impact resistance since carbon is introduced while maintaining high density.
  • the range of the peak intensity ratio I 3 / I 1 the range of 0.25 ⁇ I 3 / I 1 ⁇ 0.50 is preferable from the viewpoint of maintaining a balance between the denseness and the bending resistance of the inorganic thin film layer, and 0.30
  • the range of ⁇ I 3 / I 1 ⁇ 0.45 is more preferable.
  • Inorganic thin layer when performing infrared spectroscopy measurement of (ATR method) of the inorganic thin film layer surface, a peak exists in the 770 ⁇ 830 cm -1 intensity (I 3), peaks at 870 ⁇ 910 cm -1
  • the intensity ratio with the intensity (I 4 ) may be in the range of the formula (4). 0.70 ⁇ I 4 / I 3 ⁇ 1.00 (4)
  • the peak intensity ratio I 4 / I 3 calculated from the infrared spectroscopic measurement (ATR method) is considered to represent the ratio between peaks related to Si—C in the inorganic thin film layer.
  • the inorganic thin film layer satisfying the relationship represented by the formula (4) is considered to have excellent flex resistance and excellent impact resistance since carbon is introduced while maintaining high density.
  • the range of the peak intensity ratio I 4 / I 3 the range of 0.70 ⁇ I 4 / I 3 ⁇ 1.00 is preferable from the viewpoint of maintaining the balance between the denseness and the bending resistance of the inorganic thin film layer, and 0.80
  • the range of ⁇ I 4 / I 3 ⁇ 0.95 is more preferable.
  • the thickness of the inorganic thin film layer is preferably 5 to 3000 nm from the viewpoint of making it difficult to break when the inorganic thin film layer is bent. Further, when the inorganic thin film layer is formed by plasma CVD using glow discharge plasma, the inorganic thin film layer is formed while discharging through the substrate. More preferably, it is ⁇ 1000 nm.
  • the inorganic thin film layer may have an average density of 1.8 g / cm 3 or more.
  • the “average density” of the inorganic thin film layer is the number of silicon atoms, the number of carbon atoms, the number of oxygen atoms, and the hydrogen forward scattering method (Hydrogen Forward Scattering Method) obtained by Rutherford Backscattering Spectrometry (RBS).
  • HSS hydrogen forward scattering method
  • RBS Rutherford Backscattering Spectrometry
  • the inorganic thin film layer has a density of 1.8 g / cm 3 or more, the inorganic thin film layer has a high density and a structure with few defects such as fine voids and cracks. Furthermore, when the inorganic thin film layer is composed of silicon atoms, oxygen atoms, carbon atoms and hydrogen atoms, the average density of the inorganic thin film layer is preferably less than 2.22 g / cm 3 .
  • a curve indicating the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer and the atomic ratio of silicon atoms at each distance is referred to as a silicon distribution curve.
  • a curve indicating the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic ratio of oxygen atoms at each distance is referred to as an oxygen distribution curve.
  • a curve indicating the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic ratio of carbon atoms at each distance is referred to as a carbon distribution curve.
  • the atomic ratio of silicon atoms, the atomic ratio of oxygen atoms, and the atomic ratio of carbon atoms are the distances from the surface of the inorganic thin film layer to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the inorganic thin film layer. It means the ratio of the number of each atom.
  • the atomic ratio of carbon atoms to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the inorganic thin film layer is continuous in the thickness direction of the inorganic thin film layer. It is preferable to change to.
  • the atomic ratio of the carbon atoms continuously changes in the thickness direction means that, for example, in the carbon distribution curve, the atomic ratio of the carbon atoms is a plurality of extreme values within a predetermined displacement range. It represents that the increase and decrease that give the carbon atom are continuously repeated, and does not include a portion where the atomic ratio of carbon changes discontinuously, that is, the atomic ratio of carbon atoms does not increase or decrease monotonously.
  • the atomic ratio and carbon distribution curve obtained from the silicon distribution curve, oxygen distribution curve and carbon distribution curve in the inorganic thin film layer satisfy the conditions (i) and (ii). .
  • the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition represented by Formula (5) in a region of 90% or more in the film thickness direction of the inorganic thin film layer.
  • the carbon distribution curve has at least one extreme value.
  • the carbon distribution curve of the inorganic thin film layer is preferably substantially continuous.
  • the carbon distribution curve being substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, when the distance from the surface of the inorganic thin film layer in the film thickness direction is x [nm] and the atomic ratio of carbon is C, it is preferable to satisfy the formula (6).
  • the carbon distribution curve of the inorganic thin film layer preferably has at least one extreme value.
  • the extreme value here is the maximum value or the minimum value of the atomic ratio of each element with respect to the distance from the surface of the inorganic thin film layer in the film thickness direction.
  • the extreme value is that when the distance from the surface of the inorganic thin film layer in the film thickness direction is changed, the atomic ratio of the element changes from increasing to decreasing, or the atomic ratio of the element changes from decreasing to increasing. Is the value of the atomic ratio.
  • the extreme value can be obtained based on the atomic ratio measured at a plurality of measurement positions in the film thickness direction, for example.
  • the measurement position of the atomic ratio is set such that the interval in the film thickness direction is, for example, 20 nm or less.
  • the measurement results at three or more different measurement positions are compared for a discrete data group including the measurement results at each measurement position. It can be obtained by determining the position that starts or decreases or decreases.
  • the position indicating the extreme value can also be obtained, for example, by differentiating the approximate curve obtained from the discrete data group.
  • the inorganic thin film layer formed so as to satisfy the condition that the carbon distribution curve has at least one extreme value as described above has an increase in the gas permeability after bending with respect to the gas permeability before bending. It becomes less compared with the case where it does not satisfy. That is, by satisfying the above conditions, an effect of suppressing a decrease in gas barrier properties due to bending can be obtained.
  • the inorganic thin film layer is formed so that the number of extreme values of the carbon distribution curve is two or more, the amount of increase is reduced as compared with the case where the number of extreme values of the carbon distribution curve is one. .
  • the increase amount is larger than that in the case where the number of extreme values of the carbon distribution curve is two. Less.
  • the carbon distribution curve has two or more extreme values
  • the distance from the surface of the inorganic thin film layer in the film thickness direction at the position showing the first extreme value, and the second pole adjacent to the first extreme value is preferably in the range of 1 nm to 200 nm, and more preferably in the range of 1 nm to 100 nm. preferable.
  • the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve of the inorganic thin film layer is preferably 0.01 or more.
  • the amount of increase in the gas permeability after bending with respect to the gas permeability before bending is less than that in the case where the condition is not satisfied. That is, by satisfying the above conditions, an effect of suppressing a decrease in gas barrier properties due to bending can be obtained.
  • the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is 0.02 or more, the above effect is enhanced, and when it is 0.03 or more, the above effect is further enhanced.
  • the gas barrier property of the inorganic thin film layer tends to improve as the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve decreases.
  • the absolute value is preferably less than 0.05 (less than 5 at%), more preferably less than 0.04 (less than 4 at%), and even more preferably less than 0.03 (3 at%). %).
  • the total atomic ratio is preferably less than 0.05, more preferably less than 0.04, and still more preferably less than 0.03.
  • the gas barrier property of the inorganic thin film layer can be made uniform and improved.
  • the substantially uniform composition means that in the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve, the number of extreme values existing in each film thickness direction at any two points on the surface of the inorganic thin film layer. Are the same, and the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in each carbon distribution curve is the same or within 0.05.
  • the inorganic thin film layer formed so as to satisfy the above conditions can exhibit a gas barrier property required for a flexible electronic device using an organic EL element, for example.
  • the inorganic thin film layer containing silicon atoms, oxygen atoms, and carbon atoms is preferably formed by chemical vapor deposition (CVD), and among them, plasma chemical vapor deposition (PECVD) using glow discharge plasma or the like. ) Is more preferable.
  • CVD chemical vapor deposition
  • PECVD plasma chemical vapor deposition
  • Examples of source gases include organosilicon compounds containing silicon atoms and carbon atoms.
  • organosilicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propyl Examples include silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane.
  • organosilicon compounds hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the obtained inorganic thin film layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
  • a reaction gas that can react with the source gas to form an inorganic compound such as an oxide or a nitride can be appropriately selected and mixed with the source gas.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • a reactive gas for forming nitride nitrogen and ammonia can be used, for example.
  • These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and the nitride are formed. Can be used in combination with the reaction gas for The flow rate ratio between the source gas and the reaction gas can be adjusted as appropriate according to the atomic ratio of the inorganic material to be deposited.
  • the value of C / Si can be controlled by adjusting the flow ratio of the source gas and the reaction gas.
  • HMDSO hexamethyldisiloxane
  • oxygen used as the reaction gas
  • the ratio of the oxygen flow rate to the HMDSO flow rate O 2 / HMDSO is in the range of 5 to 25, and the value of C / Si is It can be controlled within the above-mentioned range.
  • a carrier gas may be used as necessary.
  • a discharge gas may be used as necessary.
  • carrier gas and discharge gas known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon, etc .; hydrogen can be used.
  • the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 to 50 Pa.
  • FIG. 1 is a schematic view showing an example of a manufacturing apparatus used for manufacturing an inorganic thin film layer included in a gas barrier film, and is a schematic view of an apparatus for forming an inorganic thin film layer by a plasma chemical vapor deposition method.
  • the manufacturing apparatus shown in FIG. 1 includes a feed roll 11, a take-up roll 71, transport rolls 21 to 24, a gas supply pipe 41, a plasma generating power source 51, and magnetic field forming apparatuses installed in film forming rolls 31 and 32, respectively. 61 and 62 are included.
  • the film forming rolls 31 and 32 also serve as electrodes and are roll electrodes described later.
  • At least the film forming roll, the gas supply pipe, and the magnetic field forming apparatus are disposed in a vacuum chamber (not shown) when forming the inorganic thin film layer.
  • This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.
  • Plasma CVD film formation can be performed by a continuous film formation process using plasma.
  • the delivery roll is installed in a state where the film 100 before film formation is wound up, and the film is sent out while being unwound in the longitudinal direction. Further, a winding roll is provided on the end side of the film, and the film after film formation is wound while being pulled and accommodated in a roll shape.
  • the two film forming rolls extend in parallel and face each other. Both rolls are formed of a conductive material and convey the film while rotating respectively.
  • the two film forming rolls preferably have the same diameter, for example, preferably 5 cm or more and 100 cm or less.
  • the base material layer When forming the inorganic thin film layer, the base material layer is transported in close contact with the surface of the pair of roll electrodes, plasma is generated between the pair of electrodes, and the raw material is decomposed in the plasma to be flexible. It is preferable to form an inorganic thin film layer on a base material.
  • a magnet In the pair of electrodes, a magnet is preferably disposed inside the electrodes so that the magnetic flux density is high on the surfaces of the electrodes and the flexible substrate. As a result, the plasma tends to be constrained at a high density on the electrode and the flexible substrate when the plasma is generated.
  • the ultraviolet absorber-containing organic layer is formed on the inorganic thin film layer.
  • the ultraviolet absorber-containing organic layer is formed outside the inorganic thin film layer.
  • the gas barrier film of the present invention is configured to be bonded to the device such that the ultraviolet absorber-containing organic layer is on the outside.
  • the UV absorber-containing organic layer is formed “outside” from the inorganic thin film layer.
  • the UV absorber-containing organic layer is the substrate layer device. Is formed on the side opposite to the laminated surface side.
  • the ultraviolet absorber-containing organic layer may be formed on the inorganic thin film layer on the side opposite to the surface to be bonded to the device, preferably The gas barrier film is formed on the outermost layer opposite to the surface to be bonded to the device.
  • the ultraviolet absorber-containing organic layer preferably has a light transmittance at 380 nm of 20% or less, more preferably 15% or less, still more preferably 10% or less, and even more preferably 5% or less.
  • the light transmittance at 380 nm was measured using a spectrophotometer (UV-Vis near-infrared spectrophotometer V-670 manufactured by JASCO Corporation).
  • the ultraviolet absorber is not particularly limited, and examples thereof include an organic ultraviolet absorber and a fine powder type ultraviolet blocking agent.
  • organic ultraviolet absorbers examples include benzotriazole, triazine, acrylonitrile, benzophenone, aminobutadiene, and salicylate.
  • benzotriazole series examples include 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) phenol]], 2- (2H— Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- ( tert-butyl) phenol and the like.
  • benzotriazole organic UV absorbers include Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350, Sumisorb 400, manufactured by Sumika Chemtex Co., Ltd., TINUVIN PS, TINUVIN 99-2 manufactured by BASF , TINUVIN -2384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, Adeka Stub LA-24, ADEKA STAB LA-29, ADK STAB LA-31, ADK STAB LA-32, ADK STAB LA-36, etc. (Sumisorb, TINUVIN and ADK STAB are all registered trademarks.)
  • triazine group examples include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.
  • Typical commercial products of triazine organic UV absorbers include BASF TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN ⁇ 479, ADEKA Corporation ADEKA STAB LA-46, ADEKA STAB LA-F70, etc. .
  • hindered amine or the like may be used as a light stabilizer.
  • hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5- Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], Dibutylamine, 1,3,5-triazine, N, N-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine, N- (2,2,6,6 And -tetramethyl-4-piperidyl) butylamine polycondensate.
  • Typical commercial products of HALS include TINUVIN 111, TINUVIN 123, TINUVIN 144, TINUVIN 292, TINUVIN 5100 manufactured by BASF, ADEKA Adekastab LA-52, Adekastab LA-57, Adekastab LA-63P, Adekastab LA -68, ADK STAB LA-72, ADK STAB LA-77, ADK STAB LA-81, ADK STAB LA-82, ADK STAB LA-87, ADK STAB LA-402, ADK STAB LA-502, etc.
  • fine particle metal oxides are preferable, and those having an average primary particle diameter in the range of 1 to 100 nm and having an ultraviolet protection effect are more preferable.
  • the metal oxide include titanium oxide, zinc oxide, cerium oxide, iron oxide, and magnesium oxide. One or more, preferably two or more of these particulate metal oxides may be combined.
  • the shape of the fine particle metal oxide is not particularly limited such as spherical, needle-like, rod-like, spindle-like, indefinite shape, or plate shape, and the crystal form is not particularly limited such as amorphous, rutile type, or anatase type.
  • Fine particle metal oxides are conventionally known surface treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, N-acylated lysine treatment, It is preferably surface-treated in advance by acrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, etc., especially selected from silicone, silane, fluorine compound, amino acid compound, metal soap It is preferable that the water-repellent treatment is performed with one or more surface treatment agents.
  • HMZD-50 manufactured by Sumitomo Osaka Cement Co., Ltd. is a typical commercial product of fine metal oxide.
  • the ultraviolet absorber-containing organic layer is preferably a layer obtained by applying an ultraviolet absorber-containing coating agent, drying it as necessary, and curing it by irradiation with ultraviolet rays or electron beams.
  • the UV-absorbing agent-containing coating agent comprises a UV-absorbing agent, a monomer and / or oligomer of a photo-curable resin such as UV- or electron beam-curable resin as a resin component, and an additive, for example, a photopolymerization initiator , A solvent, a dispersant, and the like.
  • the ultraviolet absorbent-containing coating agent can be obtained by dissolving or dispersing the ultraviolet absorbent and, if necessary, additives and the like in the resin component by a known method.
  • the UV absorber or UV blocker in the UV absorber-containing coating agent contains an appropriate amount for adjusting the UV transmittance, but preferably 0.1 based on the amount of the UV absorber-containing coating agent. -50 mass%, more preferably 1-30 mass%.
  • the ultraviolet curable monomer or oligomer, or the electron beam curable monomer or oligomer is not particularly limited as long as it is a monomer or oligomer having a group that can be cross-linked by irradiation with ultraviolet light or electron beam.
  • a monomer or oligomer having a group selected from the group consisting of UV absorber-containing organic layer is epoxy (meth) acrylate, urethane (meth) acrylate, isocyanuric acid (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylate, ethylene glycol (meth) acrylate, polyester Among (meth) acrylates and the like, it is preferable that the main component is a polymer obtained by crosslinking a monomer having a bifunctional or higher acryloyl group or a methacryloyl group. These monomers having a bifunctional or higher functional acryloyl group or methacryloyl group may be used as a mixture of two or more, or may be used as a mixture of a monofunctional (meth) acrylate.
  • UV-absorbing agent-containing coating agents include Toyo Ink Co., Ltd. Lioduras (registered trademark) TYN, Aika Industry Co., Ltd. 705-6 etc. are mentioned.
  • Examples of a method for forming the ultraviolet absorber-containing organic layer include a method by coating.
  • Examples of methods by coating include various conventionally used coating methods such as spray coating, spin coating, bar coating, curtain coating, dipping method, air knife method, slide coating, hopper coating, reverse roll coating, gravure coating, Examples of the method include extrusion coating. It is preferably formed by applying a UV absorber-containing coating agent on the inorganic thin film layer, then drying it as necessary, and curing it by irradiation with ultraviolet rays or electron beams.
  • the thickness of the ultraviolet absorber-containing organic layer is preferably 10 to 10,000 nm.
  • the upper limit of the thickness of the ultraviolet absorber-containing organic layer is more preferably 8000 nm, still more preferably 7000 nm.
  • the lower limit of the thickness of the ultraviolet absorber-containing organic layer is more preferably 50 nm, and still more preferably 100 nm.
  • the thickness of the organic layer containing an ultraviolet absorber is preferably 10 to 5000 nm, more preferably 50 to 5000 nm, and still more preferably 100 to 100 nm depending on the contained ultraviolet absorber, resin component, or ultraviolet absorber-containing coating agent. 5000 nm.
  • the gas barrier film may have an organic layer B as the outermost layer of the gas barrier film.
  • the organic layer B may be formed only on one side of the gas barrier film, or may be formed on both sides.
  • organic layer B matting agent layer, protective layer, antistatic layer, smoothing layer, adhesion improving layer, light shielding layer, antireflection layer, hard coat layer, stress relaxation layer, antifogging layer, antifouling layer, printing A layer, an easily adhesive layer, and the like.
  • the gas barrier film of the present invention has a light transmittance of 20% or less at a wavelength of 380 nm. Thereby, light resistance can be provided to the gas barrier film, UV degradation inside the device below the gas barrier film can be suppressed, or UV degradation of the gas barrier film itself can be suppressed.
  • the gas barrier film of the present invention preferably has a light transmittance at a wavelength of 380 nm of 15% or less, more preferably 10% or less, and even more preferably 5% or less. In the present invention, the light transmittance at a wavelength of 380 nm was measured using a spectrophotometer (UV-Vis near-infrared spectrophotometer V-670 manufactured by JASCO Corporation).
  • the layer configuration of the gas barrier film of the present invention is not particularly limited as long as the base layer, the inorganic thin film layer, and the ultraviolet absorber-containing organic layer are laminated in this order, and are limited to the following examples of the layer configuration. Not a thing.
  • the layer structure specifically, a three-layer structure of base material layer / inorganic thin film layer / ultraviolet absorber-containing organic layer; flexible base material / organic layer A / inorganic thin film layer / ultraviolet absorber-containing organic Layer, organic layer A / flexible substrate / inorganic thin film layer / organic layer containing ultraviolet absorber, inorganic thin film layer / flexible substrate / inorganic thin film layer / organic layer containing ultraviolet absorber, flexible substrate / Inorganic thin film layer / UV absorber-containing organic layer / organic layer B, organic layer B / flexible substrate / inorganic thin film layer / UV absorber-containing organic layer; flexible substrate / organic layer A / Inorganic thin film layer / UV absorber-containing organic layer / organic layer B, inorganic thin film layer / flexible substrate / organic layer A / inorganic thin film layer / ultraviolet absorber-containing organic layer, etc .; Organic layer B / Inorganic thin film layer / flexible substrate / organic layer A / inorganic
  • a further layer C may be provided.
  • layer C include a colorant-containing organic layer, a bleed-out prevention layer, an antireflection layer, an adhesive layer, a transparent conductive layer, an infrared ray blocking layer, and a vacuum ultraviolet ray curable organic layer.
  • the static friction coefficient between one surface of the gas barrier film and the other surface is 0.85 or more and 2.0 or less.
  • the static friction coefficient is determined by dividing a gas barrier film having an upper surface and a lower surface into two sheets and bringing the upper surface of the first gas barrier film and the lower surface of the second gas barrier film into contact with each other. What is necessary is just to measure a coefficient.
  • the coefficient of static friction can be measured in an environment of a temperature of 23 ° C. and a humidity of 50 RH% in accordance with the gradient method of JIS P8147.
  • the surface roughness on both sides of the gas barrier film may be adjusted.
  • the surface roughness of the exposed surface of the inorganic thin film layer and the surface roughness of the exposed surface of the base material layer may be adjusted.
  • the surface roughness of the exposed surface of one inorganic thin film layer and the surface roughness of the exposed surface of the other inorganic thin film layer may be adjusted.
  • the surface roughness of at least one surface of the gas barrier film is increased, the static friction coefficient between the front and back surfaces tends to decrease.
  • the surface roughness of the inorganic thin film layer can be changed, for example, according to conditions such as the pressure in the vacuum chamber (vacuum degree) and film thickness in the film formation conditions of the inorganic thin film layer, and the composition of the inorganic film formation layer.
  • the surface roughness of the inorganic thin film layer is adjusted by adjusting the surface roughness of the flexible base material serving as a base and the surface roughness of the intermediate layer disposed between the inorganic thin film layer and the flexible base material. Can also be adjusted.
  • a corona treatment or the like may be performed.
  • the arithmetic average roughness Ra of the surface of the inorganic thin film layer can be 3 nm or more.
  • the arithmetic average roughness Ra can be obtained by attaching the gas barrier film to an epoxy plate with an adhesive and then observing the surface with a white interference microscope.
  • the arithmetic average roughness Ra is an arithmetic average roughness according to JIS B 0601: 2001.
  • the average of the distances from the horizontal plane to the four corners is 2 mm or less.
  • This average value can be measured as follows. First, the gas barrier film is held for 48 hours under conditions of a temperature of 23 ° C. and a humidity of 50 RH%. Next, a 50 mm square part is cut out from the gas barrier film to obtain a sample. The sample is placed on the horizontal plane so that the center of the sample is in contact with the horizontal plane, and a total of four distances from the horizontal plane to the four corners are obtained. Finally, the average of these 4 points is obtained.
  • the stress of each inorganic thin film layer on the front and back surfaces or balance the stress between the inorganic thin film layer on one side and the coating layer below it. Or reducing the residual stress of the inorganic thin film layer itself, or combining these to balance the stress on both sides.
  • the stress can be adjusted by the film forming pressure and film thickness when forming the inorganic thin film layer, the degree of cure shrinkage when forming the coating layer, and the like.
  • the water vapor permeability of the gas barrier film at 40 ° C. and 90% RH can be 0.1 g / m 2 / day or less, and can be 0.001 g / m 2 / day or less.
  • the water vapor transmission rate can be measured by a Ca corrosion test method according to ISO / WD 15106-7 (Annex C).
  • the gas barrier film of the present invention is a method of separately manufacturing and bonding a base material layer, an inorganic thin film layer, and an ultraviolet absorber-containing organic layer, and forming an inorganic thin film layer and an ultraviolet absorber-containing organic layer on the base material layer. It can be manufactured by a method or the like.
  • the inorganic thin film layer is formed on the flexible base material or the organic layer A laminated on the surface of the flexible base material by using a known vacuum film forming method such as a CVD method using glow discharge plasma. It is preferable to manufacture.
  • the laminated film thus obtained may be formed with a UV absorber-containing organic layer or a further organic layer B by a known method.
  • the inorganic thin film layer is preferably formed by a continuous film forming process.
  • the inorganic thin film layer may be formed while the flexible substrate is conveyed from the feed roll to the take-up roll. Then, you may form an inorganic thin film layer from the top by inverting a sending roll and a winding roll, and conveying a base material in the reverse direction.
  • the gas barrier film of the present invention is a film excellent in gas barrier property and light resistance, in which a decrease in gas barrier property is suppressed even when bent after a light resistance test.
  • the gas barrier film of the present invention can be used as a packaging application for foods, industrial products, pharmaceuticals, etc. that require gas barrier properties.
  • the present invention also provides a flexible electronic device having the gas barrier film of the present invention.
  • the gas barrier film of the present invention can also be used as a flexible substrate for flexible electronic devices (for example, flexible displays) such as liquid crystal display elements, solar cells, and organic EL displays that require higher gas barrier properties.
  • the element may be formed directly on the gas barrier film of the present invention, or after the element is formed on another substrate, the present invention. These gas barrier films may be overlaid from above.
  • ⁇ Thickness direction XPS depth profile measurement of inorganic thin film layer> The atomic ratio in the thickness direction of the inorganic thin film layer of the gas barrier film was measured by X-ray photoelectron spectroscopy.
  • Etching rate (equivalent to SiO 2 thermal oxide film): 0.05nm / sec Etching interval (SiO 2 equivalent value): 10 nm
  • X-ray photoelectron spectrometer Model name “VG Theta Probe” manufactured by Thermo Fisher Scientific Irradiation X-ray: Single crystal spectroscopy AlK ⁇ X-ray spot and size: 800 ⁇ m ⁇ 400 ⁇ m oval.
  • Infrared spectroscopic measurement of inorganic thin film layer surface is Fourier transform infrared spectrophotometer equipped with ATR attachment (PIKE MIRacle) using germanium crystal for prism (manufactured by JASCO Corporation, FT / IR- 460Plus).
  • PIKE MIRacle germanium crystal for prism
  • germanium crystal for prism manufactured by JASCO Corporation, FT / IR- 460Plus
  • a cyclocycloolefin film manufactured by ZEON Corporation, ZEONOR ZF16
  • the gas barrier property was measured by the calcium corrosion method (method described in JP-A-2005-283561) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, and the water vapor permeability of the gas barrier film was determined.
  • Inorganic thin film layer production example 1 The flexible substrate was mounted on a delivery roll in a vacuum chamber, and the inside of the vacuum chamber was reduced to 1 ⁇ 10 ⁇ 3 Pa or less, and then an inorganic thin film layer was formed on the flexible substrate.
  • a plasma CVD apparatus used to form an inorganic thin film layer a base material layer is conveyed in close contact with the surface of a pair of roll electrodes, plasma is generated between the pair of electrodes, and the raw material is decomposed in the plasma. Thus, an inorganic thin film layer was formed on the flexible substrate.
  • a magnet is arranged inside the electrode so that the magnetic flux density is high on the surface of the electrode and the flexible substrate, and when the plasma is generated, the plasma becomes dense on the electrode and the flexible substrate. I was restrained.
  • 100 sccm of hexamethyldisiloxane gas (Standard Cubic Centimeter per Minute, 0 ° C., 1 atm standard) and 1400 sccm of oxygen gas are introduced toward the space between the electrodes serving as a film formation zone, An AC power of 1.2 kW and a frequency of 70 kHz was supplied between the electrode rolls and discharged to generate plasma.
  • a dense inorganic thin film layer was formed on the flexible substrate by plasma CVD.
  • the infrared absorption spectrum did not change even after the corona treatment described later, and showed the above-mentioned absorption intensity ratio.
  • the obtained gas barrier film 1 is in the order of oxygen, silicon, and carbon in order from the largest atomic ratio in the region of 90% or more in the film thickness direction of the inorganic thin film layer, and the carbon distribution in the film thickness direction.
  • the extreme value of the curve was 10 or more, and the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve was 0.02 or more.
  • the thickness of the inorganic thin film layer in the obtained gas barrier film was 320 nm.
  • Inorganic thin film layer production example 2 Production Example 1 except that the supply amount of oxygen gas is 900 sccm, the AC power supplied between the electrode rolls is 0.6 kW, and the exhaust amount is adjusted so that the pressure around the exhaust port in the vacuum chamber is 1 Pa. In the same manner, an inorganic thin film layer was formed on the base material layer.
  • the infrared absorption spectrum did not change even after the corona treatment described later, and showed the above-mentioned absorption intensity ratio.
  • the obtained gas barrier film 1 is in the order of oxygen, silicon, and carbon in the order of the atomic ratio in the region of 90% or more in the film thickness direction of the inorganic thin film layer, and the carbon distribution in the film thickness direction.
  • the extreme value of the curve was 10 or more, and the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve was 0.02 or more.
  • the thickness of the inorganic thin film layer in the obtained gas barrier film was 250 nm.
  • Example 1 After applying a corona treatment on a cycloolefin polymer film (COP film, manufactured by Nippon Zeon Co., Ltd., ZF16, thickness 100 ⁇ m), coating agent 1 (manufactured by Toyochem Co., Ltd., Rioduras (registered trademark) TYAB500LC3NS, with particles) is applied. After applying by gravure coating method and drying at 100 ° C. for 3 minutes, an organic layer with a thickness of 1.5 ⁇ m is irradiated with ultraviolet rays (SP-9, manufactured by USHIO INC.) Under conditions of an integrated light quantity of 500 mJ / cm 2. An easy slip layer was formed as A1.
  • COP film manufactured by Nippon Zeon Co., Ltd., ZF16, thickness 100 ⁇ m
  • coating agent 1 manufactured by Toyochem Co., Ltd., Rioduras (registered trademark) TYAB500LC3NS, with particles
  • an organic layer with a thickness of 1.5 ⁇ m is i
  • coating agent 2 manufactured by Toa Gosei Co., Ltd., Aronix (registered trademark) UV3701
  • a gravure coating method was applied by a gravure coating method. And dried at 100 ° C. for 3 minutes, and then irradiated with ultraviolet rays under the condition of an integrated light quantity of 500 mJ / cm 2 to form a planarizing layer as an organic layer A2 having a thickness of 1.8 ⁇ m to obtain a flexible substrate.
  • An inorganic thin film layer was formed on the organic layer A1 of the obtained flexible substrate under the conditions of Production Example 1, and an inorganic thin film layer was formed on the organic layer A2 under the conditions of Production Example 2.
  • an ultraviolet absorber-containing organic layer was formed on the outermost surface on the organic layer A1 side of the film on which the inorganic thin film layer was formed, to produce a gas barrier film.
  • the UV absorber-containing organic layer is formed by corona treatment on the easy-sliding layer side of the film on which the inorganic thin film layer is formed, and then coating agent 3 (manufactured by ADEKA Co., Ltd., KRX-705-6) is applied by wet coating. After coating and drying at 80 ° C.
  • UV irradiation SP-9, manufactured by Ushio Electric Co., Ltd.
  • SPD-9 manufactured by Ushio Electric Co., Ltd.
  • the obtained gas barrier film had a water vapor transmission rate of 2 ⁇ 10 ⁇ 3 g / (m 2 ⁇ day) under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side.
  • Method
  • Example 2 A gas barrier film was produced in the same manner as in Example 1 except that the thickness of the ultraviolet absorber-containing organic layer was 6.5 ⁇ m.
  • the obtained gas barrier film had a water vapor transmission rate of 2 ⁇ 10 ⁇ 3 g / (m 2 ⁇ day) under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side. )Met.
  • Comparative Example 1 A corona treatment was applied to a COP film (Zeon Corporation (registered trademark) ZF16, 100 ⁇ m thickness, manufactured by Nippon Zeon Co., Ltd.), and then coating agent 4 (Aika Industry Co., Ltd., Z-735-27L, with particles) was applied. After applying by a gravure coating method and drying at 100 ° C. for 2 minutes, ultraviolet irradiation was performed under the condition of an integrated light quantity of 150 mJ / cm 2 to form an ultraviolet absorber-containing organic layer having a thickness of 3.5 ⁇ m as an easy-sliding layer.
  • COP film Zeon Corporation (registered trademark) ZF16, 100 ⁇ m thickness, manufactured by Nippon Zeon Co., Ltd.)
  • coating agent 4 Aika Industry Co., Ltd., Z-735-27L, with particles
  • the coating agent 2 (Aronix (registered trademark) UV3701 manufactured by Toa Gosei Co., Ltd.) is applied to the gravure coating method. And dried at 100 ° C. for 3 minutes, and then irradiated with ultraviolet rays under conditions of an integrated light quantity of 500 mJ / cm 2 to form a planarizing layer as an organic layer A2 having a thickness of 1.8 ⁇ m.
  • An inorganic thin film layer is formed under the conditions of Production Example 1 on the obtained ultraviolet absorber-containing organic layer of the base material, and an inorganic thin film layer is formed under the conditions of Production Example 2 on the organic layer A2 to provide gas barrier properties. A film was produced.
  • Comparative Example 2 A gas barrier film was produced in the same manner as in Comparative Example 1 except that the thickness of the ultraviolet absorbent-containing organic layer was 4.5 ⁇ m.
  • Example 3 A gas barrier film was produced in the same manner as in Example 1 except that the ultraviolet absorber-containing organic layer was not formed.
  • the gas barrier films obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were applied to a light resistance tester (Daipura Wintes Co., Ltd., SWM-03F) having a temperature of 40 ° C. and an illuminance of 765 W / m 2.
  • the light resistance test was performed by leaving it for a period of time. The test was performed by arranging the gas barrier film so that light is incident from the easy-sliding layer surface side of the gas barrier film.
  • the gas barrier film after the light resistance test has an area in which the appearance does not change after being wound once on a mandrel having a radius of 4 mm, without being peeled off, cracked or colored on the barrier layer.
  • the case of 100% was evaluated as “A”
  • the case of 80% or more and less than 100% was evaluated as “B”
  • the case of less than 80% was evaluated as “C”.
  • the results are shown in Table 1.
  • the gas barrier film of the present invention shown in Examples 1 and 2 has an ultraviolet absorber-containing organic layer on the inorganic thin film layer, the inorganic thin film layer does not deteriorate even after the light resistance test, Good adhesion after bending.
  • Comparative Examples 1 and 2 although the light transmittance at a wavelength of 380 nm was low, the inorganic thin film layer was deteriorated after the light resistance test, and the adhesion after bending was low. Therefore, it is understood that the gas barrier film of the present invention is suitably used in a device such as a display device.

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Abstract

L'invention a pour objet de conférer une résistance à la lumière à un film barrière au gaz visant à une résistance à l'humidité mis en œuvre dans un écran flexible, et d'inhiber la dégradation aux UV d'une partie interne de dispositif dans une couche inférieure au film barrière au gaz, et/ou d'inhiber la dégradation aux UV du film barrière au gaz lui-même. Plus précisément, l'invention fournit un film barrière au gaz qui possède dans l'ordre une couche de matériau de base contenant au moins un matériau de base souple, une couche mince inorganique, et une couche organique comprenant un absorbant d'ultraviolet. Ladite couche mince inorganique comprend un atome de silicium, un atome d'oxygène et un atome de carbone. La transmittance de la lumière dudit film barrière au gaz à 380nm, est inférieure ou égale à 20%.
PCT/JP2017/039903 2016-11-11 2017-11-06 Film barrière au gaz, et dispositif contenant celui-ci Ceased WO2018088352A1 (fr)

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JP5281986B2 (ja) * 2009-08-26 2013-09-04 富士フイルム株式会社 積層フィルムおよび複合フィルム
JP5540803B2 (ja) 2010-03-23 2014-07-02 コニカミノルタ株式会社 ガスバリア性フィルムの製造方法
JP5565129B2 (ja) 2010-06-22 2014-08-06 コニカミノルタ株式会社 ガスバリア性フィルム、及びそれを用いた有機素子デバイス
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JP6070411B2 (ja) 2013-05-27 2017-02-01 コニカミノルタ株式会社 ガスバリアー性フィルム、ガスバリアー性フィルムの製造方法及び有機エレクトロルミネッセンス素子
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JP2006297737A (ja) * 2005-04-20 2006-11-02 Fuji Photo Film Co Ltd ガスバリアフィルム
JP2012076386A (ja) * 2010-10-04 2012-04-19 Konica Minolta Holdings Inc 紫外線遮蔽性フィルム及びそれを用いた有機電子デバイス
WO2015098647A1 (fr) * 2013-12-26 2015-07-02 リンテック株式会社 Matériau d'étanchéité de type feuille, feuille d'étanchéité, corps étanchéifié de dispositif électronique et élément électroluminescent organique
WO2016039280A1 (fr) * 2014-09-08 2016-03-17 住友化学株式会社 Film stratifié et dispositif électronique souple

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CN109890607A (zh) 2019-06-14
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