WO2013161785A1 - Pellicule transparente formant barrière aux gaz et dispositif électronique - Google Patents

Pellicule transparente formant barrière aux gaz et dispositif électronique Download PDF

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Publication number
WO2013161785A1
WO2013161785A1 PCT/JP2013/061845 JP2013061845W WO2013161785A1 WO 2013161785 A1 WO2013161785 A1 WO 2013161785A1 JP 2013061845 W JP2013061845 W JP 2013061845W WO 2013161785 A1 WO2013161785 A1 WO 2013161785A1
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Prior art keywords
gas barrier
group
layer
film
barrier layer
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PCT/JP2013/061845
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English (en)
Japanese (ja)
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河村　朋紀
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コニカミノルタ株式会社
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Priority to JP2014512591A priority Critical patent/JP6094577B2/ja
Publication of WO2013161785A1 publication Critical patent/WO2013161785A1/fr

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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
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • 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
    • 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

Definitions

  • the present invention relates to a novel transparent gas barrier film and an electronic device using the same.
  • an organic material such as an organic electroluminescence element utilizing electroluminescence (hereinafter abbreviated as EL) of an organic material, such as a so-called organic EL element or a liquid crystal display element
  • EL electroluminescence
  • Organic materials and electrodes have extremely low resistance to moisture and oxygen, and are easily deteriorated by these gases (for example, water vapor and air) that have entered from the outside.
  • gases for example, water vapor and air
  • a configuration has been studied in which the penetration of these gases into the organic electroluminescent element is suppressed without impairing the external extraction of the emitted light by using a light-transmitting barrier film.
  • Examples of such a light-transmitting barrier film include a vapor-deposited thin film layer containing an inorganic oxide / a gas barrier film layer containing a water-soluble polymer / a vapor-deposited thin film layer containing metal aluminum / a water-soluble polymer.
  • a transparent laminate having a configuration in which gas barrier coating layers are laminated in this order is disclosed (for example, see Patent Document 1).
  • the surface of the coating film using a water-soluble polymer is subjected to plasma treatment to form a strong adhesion treatment layer, and a metal thin film layer using aluminum, nickel, or titanium is provided on top of this to provide gas barrier properties. (See, for example, Patent Document 2).
  • Patent Document 1 and Patent Document 2 both have sufficient light permeability and sufficient barrier properties against moisture and oxygen after being stored in a high-temperature and high-humidity environment. It was difficult to plan.
  • Patent Document 3 a laminated gas barrier film in which a silane coupling agent is provided as an anchor coat layer has been proposed.
  • the technical idea of the method disclosed in Patent Document 3 is that a so-called anchor coat layer has a specific configuration to ensure interlayer adhesion over a long period of time, and at the same time, even after an environmental resistance test,
  • An object of the present invention is to provide a laminated film that does not cause deterioration in performance.
  • a laminated film having gas barrier properties and conductivity and having high durability is desired.
  • adhesion and durability between the base material and the specific functional layer can be achieved, but when forming a plurality of specific functional layers such as a transparent conductive layer such as a gas barrier layer or ITO, It was difficult to ensure mutual adhesion and durability at the interface.
  • the present invention has been made in view of the above problems, and is used as a substrate for various electronic devices such as organic EL elements.
  • the transparent gas barrier has high gas barrier performance and excellent durability (bending resistance).
  • An electronic device using the film and its gas barrier film is provided.
  • the present inventor has obtained a high gas by using a transparent gas barrier film characterized by having at least a gas barrier layer, a smooth layer and a metal layer in this order on a substrate.
  • the present inventors have found that a transparent gas barrier film having barrier properties and excellent durability (bending resistance) can be realized, and the present invention has been achieved.
  • the substrate has at least a gas barrier layer, a smooth layer, and a metal layer in this order, and the metal layer is a layer formed using silver or an alloy containing silver as a main component.
  • Transparent gas barrier film is a layer formed using silver or an alloy containing silver as a main component.
  • the said smooth layer contains the compound which has a nitrogen atom,
  • the transparent gas barrier film of Claim 1 or 2 characterized by the above-mentioned.
  • the gas barrier layer is a gas barrier layer A formed by applying a polysilazane-containing coating solution on a substrate and then performing a modification treatment.
  • the transparent gas barrier film according to one item.
  • the gas barrier layer B includes a carbon atom, a silicon atom, and an oxygen atom, the composition continuously changes in the layer thickness direction, and satisfies the requirements defined in the following (1) and (2).
  • the transparent gas barrier film according to any one of Items 1 to 4, wherein the film is a transparent gas barrier film.
  • the gas barrier layer B in the layer thickness direction of the gas barrier layer B In the carbon distribution curve showing the relationship between the distance from the surface and the ratio of the amount of carbon atoms to the total amount (100 at%) of silicon atoms, oxygen atoms and carbon atoms (referred to as “carbon atom ratio (at%)”).
  • carbon atom ratio (at%) The difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 3.0 at% or more.
  • the gas barrier layer is composed of at least two layers, the first gas barrier layer located on the substrate side is the gas barrier layer B, and the second gas barrier layer located on the outermost layer side is the gas barrier. 6.
  • An electronic device comprising the transparent gas barrier film according to any one of items 1 to 8.
  • a transparent gas barrier film having high gas barrier performance and excellent durability (bending resistance) and its gas barrier film are used as substrates for various electronic devices such as organic EL elements.
  • An electronic device having excellent gas barrier properties and durability (dark spot resistance) can be obtained.
  • the transparent gas barrier film of the present invention has a metal layer for imparting conductivity.
  • the thickness of the metal layer is likely to be stable as the conductivity is increased, but the transparency of the film is likely to be lowered. If the thickness of the metal layer is reduced in order to increase transparency, the continuity of the metal layer tends to be affected by the smoothness of the surface of the substrate that supports it, and the smaller the roughness of the surface of the substrate, the more gas barrier It becomes easy to achieve both transparency and conductivity of the film.
  • the present inventors have found that when a compound having a nitrogen atom is used for the composition of the surface on which the metal layer is formed, good conductivity can be obtained even when the metal layer is thin. It became clear by.
  • a precursor material for forming a gas barrier layer is laminated on a substrate by coating rather than a gas barrier layer formed by a method such as physical or chemical vapor deposition.
  • a better surface smoothness can be obtained with the gas barrier layer formed by the modification treatment.
  • the transparent gas barrier film of the present invention has at least a gas barrier layer, a smooth layer, and a metal layer in this order on a substrate, and the metal layer is formed using silver or an alloy containing silver as a main component.
  • a transparent gas barrier film having a high gas barrier performance and excellent durability (bending resistance) can be realized. This feature is a technical feature common to the inventions according to claims 1 to 8.
  • a base layer containing a compound having a nitrogen atom is further provided between the smooth layer and the metal layer.
  • a smooth layer contains the compound which has a nitrogen atom.
  • the gas barrier layer is preferably formed by applying a polysilazane-containing coating solution on a substrate and then performing a modification treatment.
  • a smooth layer contains the compound which has a urethane bond.
  • the thickness of the smooth layer is preferably in the range of 20 to 500 nm.
  • the electronic device of the present invention comprises the transparent gas barrier film of the present invention.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the transparent gas barrier film of the present invention is characterized by having, on the base material, at least a gas barrier layer, a smooth layer, and a metal layer formed using silver or a silver-based alloy in this order. To do.
  • transparent means that the total light transmittance in the visible light wavelength region measured by a method in accordance with JIS K 7361-1: 1997 (plastic-transparent material total light transmittance test method) is 70% or more. It means that.
  • the transparent gas barrier film of the present invention (hereinafter also simply referred to as a gas barrier film or a barrier film) is a gas containing a metal oxide formed on a substrate such as a resin film by a vapor deposition method such as a plasma CVD method.
  • a barrier layer or a gas barrier layer composed of a polysilazane modified layer formed by applying a liquid containing polysilazane by a wet coating method, drying, and then irradiating vacuum ultraviolet light or the like, and a smooth layer thereon And a metal layer formed by using silver or an alloy containing silver as a main component.
  • FIG. 1 is a schematic cross-sectional view showing a representative example of the layer structure of the transparent gas barrier film of the present invention.
  • FIG. 1A shows a basic configuration of a gas barrier film 1 of the present invention, in which a gas barrier layer 3, a smooth layer 4 and a metal layer 5 are laminated on a substrate 2.
  • the gas barrier film 1 further includes a base layer 6 between the smooth layer 4 and the metal layer 5.
  • the adhesiveness of the gas barrier layer 2 (a vapor deposition layer and a polysilazane modified layer) with respect to the smoothness of the base material 2 and the base material 2 is shown. Therefore, the anchor coat layer 7 may be provided as an intermediate layer.
  • a bleed-out prevention layer 8 is provided on the base 2 for the purpose of preventing the surface (also referred to as the back side) opposite to the side of the gas barrier layer of the base 2 from being scratched or soiled. It may be provided.
  • the base material 2 in the gas barrier film 1 of the present invention is preferably a flexible resin film that can be bent.
  • the substrate 2 is not particularly limited as long as it is a material that can hold a gas barrier layer 3 having gas barrier properties (for example, a vapor deposition layer, a polysilazane modified layer, etc.).
  • the base material 2 for example, acrylic ester, methacrylic ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene ( PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide resin film, organic-inorganic hybrid Heat-resistant transparent film (eg, product name Sila-DEC, manufactured by Chisso Corporation) having silsesquioxane having a basic skeleton as a basic skeleton, and a laminated resin formed by laminating two or more layers of the above film materials Or the like can also be used Irumu.
  • PVC polyvinyl chloride
  • PE PE
  • PP polypropylene
  • PS polystyrene
  • nylon nylon
  • films of polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used from the viewpoint of economy and availability.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • a silsesquioxane having an organic-inorganic hybrid structure is used as a basic skeleton.
  • a heat-resistant transparent film prepared is also preferably used.
  • the thickness of the substrate 2 is preferably in the range of 5 to 500 ⁇ m, more preferably in the range of 25 to 250 ⁇ m.
  • the substrate 2 is preferably transparent.
  • the base material 2 transparent and each layer formed on the base material 2 also having a high light transmittance, a gas barrier film with excellent light transmittance can be obtained.
  • the base material 2 has a light-transmitting property, it is possible to transmit light emitted from the organic EL element or to allow the sunlight toward the solar cell to pass through. Therefore, the organic EL element and the solar cell are sealed. It can also be suitably used as a sealing film (transparent substrate).
  • the base material 2 using the above resin material may be an unstretched film or a stretched film.
  • the base material 2 made of the above resin material can be manufactured by a conventionally known general film forming method.
  • an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.
  • the unstretched substrate is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, and other known methods, such as a substrate transport method (vertical axis) direction, Or the extending
  • the draw ratio in this case can be appropriately selected according to the characteristics of the resin constituting the substrate, but the draw ratio is preferably in the range of 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively. .
  • this base material 2 before forming the gas barrier layer 3 etc., you may give well-known hydrophilization treatments, such as a corona treatment, to the base-material surface.
  • the surface of the substrate 2 applied to the present invention has an object of improving adhesion to the gas barrier layer 3 (for example, a vapor deposition layer or a polysilazane modified layer) formed thereon. From this, an anchor coat layer 7 (described in FIG. 1C) may be formed.
  • the anchor coat layer 7 flattens the rough surface of the substrate 2 on which minute protrusions and the like exist, and irregularities and pinholes are generated in the gas barrier layer 3 and the like formed on the substrate 2 by the protrusions on the surface of the substrate 2. It is provided in order not to exist.
  • an anchor coat layer forming material used for this anchor coat layer for example, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, And alkyl titanates can be used alone or in combination of two or more. Conventionally known additives can be added to these anchor coat layer forming materials. And after dissolving said anchor coat material with a suitable solvent etc. and preparing an anchor coat layer coating liquid, the said anchor coat layer coating liquid is a roller coat, a gravure coat, a knife coat, a dip coat, a spray coat, etc.
  • An anchor coat layer can be formed by coating on a substrate by a known wet coating method and removing the solvent, diluent and the like by drying.
  • the application amount of this anchor coat layer forming material is preferably within a range of 0.1 to 5.0 g / m 2 in a dry state.
  • the anchor coat layer may be formed, for example, by curing a photosensitive resin.
  • the photosensitive resin used for forming the anchor coat layer include a resin composition containing an acrylate compound having a radical reactive unsaturated bond, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved.
  • any mixture of the above resin compositions can be used, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used.
  • a reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.
  • the photosensitive resin composition preferably contains a photopolymerization initiator.
  • a photoinitiator can be used 1 type or in combination of 2 or more types.
  • a method for forming the anchor coat layer 7 on the surface of the base material 2 using such a photosensitive resin composition is not particularly limited. For example, as described above, spin coating, spray coating, blade coating, dip coating are used. It is preferably formed by a wet coating method such as vapor deposition or a dry coating method such as vapor deposition.
  • additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the photosensitive resin as necessary.
  • an appropriate resin or additive may be used for improving the film formability on the formed anchor coat layer or preventing pinholes from being formed on the anchor coat layer.
  • the solvent used when forming the anchor coat layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent includes alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol. , Terpenes such as ⁇ - or ⁇ -terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone and other ketones, toluene, xylene, tetramethylbenzene, etc.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol.
  • Terpenes such as ⁇ - or ⁇ -terpineol, acetone, methyl ethyl ketone, cyclohex
  • the smoothness of the anchor coat layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably in the range of 10 to 30 nm. If Rt is 10 nm or more, the coating property is impaired when the coating means comes into contact with the surface of the anchor coat layer by a coating method such as a wire bar or a wireless bar at the stage of coating a silicon compound (polysilazane solution) described later. It will not be. Moreover, if Rt is 30 nm or less, the unevenness
  • one of the preferred embodiments as an additive to be added when forming the anchor coat layer is a reactive silica particle (hereinafter simply referred to as “photosensitive resin group having a photopolymerizable reactivity” introduced on the surface thereof).
  • photosensitive resin group having a photopolymerizable reactivity introduced on the surface thereof.
  • photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group.
  • the photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be.
  • a photosensitive resin what adjusted solid content by mixing a general-purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.
  • the average particle diameter of the reactive silica particles is preferably within the range of the average particle diameter of 0.001 to 0.1 ⁇ m.
  • the average particle size is preferably within the range of the average particle diameter of 0.001 to 0.1 ⁇ m.
  • the anchor coat layer preferably contains the inorganic particles as described above within a range of 20 to 60% by mass with respect to the total mass of the anchor coat layer.
  • the inorganic particles By containing 20% by mass or more of inorganic particles, the adhesion with the gas barrier layer is improved.
  • the content of the inorganic particles is 60% by mass or less, the film is bent or cracks are prevented when heat treatment is performed, and optical properties such as transparency and refractive index of the gas barrier film are prevented. Can be stably maintained.
  • the polymerizable unsaturated group-modified hydrolyzable silane forms a silyloxy group and is chemically bonded to the silica particles by the hydrolysis reaction of the hydrolyzable silyl group.
  • Such can be used as reactive silica particles.
  • the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl group, and a hydridosilyl group.
  • Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.
  • the thickness of the anchor coat layer is preferably in the range of 1 to 10 ⁇ m, more preferably in the range of 2 to 7 ⁇ m.
  • providing the anchor coat layer facilitates sufficient smoothness as a gas barrier film, and by reducing the thickness to 10 ⁇ m or less, the optical characteristics of the gas barrier film.
  • the balance of the gas barrier film can be easily adjusted, and curling of the gas barrier film when the anchor coat layer is provided only on one surface of the gas barrier film can be easily suppressed.
  • a bleed-out prevention layer 8 is formed on the back surface of the substrate 2 (the surface opposite to the surface on which the gas barrier layer is formed). May be.
  • the bleed-out prevention layer 8 suppresses a phenomenon in which, when a film-like substrate composed of a resin is heated, unreacted oligomers or the like migrate from the substrate to the surface and contaminate the surface of the substrate.
  • it can be provided on the opposite surface of the substrate 2 having an anchor coat layer.
  • the bleed-out prevention layer 8 may basically have the same configuration as the anchor coat layer 7 described above as long as it has a function of suppressing the above phenomenon.
  • a hard coat material can be added to the bleed-out prevention layer 8.
  • the hard coat material may include unsaturated organic compounds having a polymerizable unsaturated group, such as a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or Mention may be made of unitary unsaturated organic compounds having one polymerizable unsaturated group in the molecule.
  • a matting agent As other additives that can be applied to the bleed-out prevention layer, a matting agent can be mentioned.
  • the matting agent inorganic particles having an average particle diameter in the range of 0.1 to 5 ⁇ m are preferable.
  • inorganic particles for example, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like should be used in combination.
  • the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.
  • the bleed-out prevention layer may contain, for example, a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like.
  • thermoplastic resin examples include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like.
  • Vinyl resins, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonate resins Etc.
  • thermosetting resin examples include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicon resin, and the like.
  • the ionizing radiation curable resin is cured by irradiating an ionizing radiation (ultraviolet ray or electron beam) to an ionizing radiation curable paint in which one or more of a photopolymerizable prepolymer or a photopolymerizable monomer is mixed. Things can be used.
  • an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used.
  • this acrylic prepolymer urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used.
  • the photopolymerizable monomer the polyunsaturated organic compounds described above can be used.
  • photopolymerization initiator examples include acetophenone, benzophenone, Michler ketone, benzoin, benzyl methyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl ) -1-propane, ⁇ -acyloxime ester, thioxanthone and the like.
  • the bleed-out prevention layer as described above is prepared by adding a hard coating agent, a matting agent and other components added as necessary, and adding a predetermined dilution solvent to prepare a coating solution. It can form by apply
  • means for irradiating ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like It can be performed by means of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.
  • the thickness of the bleed-out prevention layer is preferably in the range of 1 to 10 ⁇ m, more preferably in the range of 2 to 7 ⁇ m.
  • the gas barrier layer 3 is formed on the substrate 2 or via the anchor coat layer 7.
  • the formation method of the gas barrier layer 3 according to the present invention is not limited. For example, after the gas barrier layer composed of a metal oxide formed by a vapor deposition method or a coating solution containing a polysilazane compound is wet-coated. A gas barrier layer formed by irradiating the formed polysilazane layer with vacuum ultraviolet light and subjecting it to a modification treatment can be mentioned.
  • Gas barrier layer forming method 1 Examples of applicable vapor deposition methods when forming the gas barrier layer 3 on the substrate 2 by vapor deposition include physical vapor deposition and chemical vapor deposition.
  • the physical vapor deposition method is a method in which a target substance, for example, a thin film such as a carbon film is deposited on the surface of the substrate 2 in the gas phase by a physical method.
  • a target substance for example, a thin film such as a carbon film
  • chemical vapor deposition is a gas phase mixed with a source gas containing a target thin film forming component in a gas phase and supplied to an excited discharge gas,
  • a thin film is deposited on the substrate 2 by chemical reaction on the substrate surface or in the gas phase.
  • Known CVD methods such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, plasma CVD method, atmospheric pressure plasma CVD method, etc. Etc.
  • a plasma CVD method can be applied from the viewpoint of film formation speed and processing area, and one method is atmospheric pressure that does not require a vacuum.
  • a plasma CVD method is also preferable.
  • the atmospheric pressure plasma CVD method for performing plasma CVD processing at or near atmospheric pressure does not need to be reduced in pressure and has higher productivity than the plasma CVD method under vacuum, and also has a high plasma density. Therefore, the film formation rate is high, and further, under a high pressure condition of atmospheric pressure, compared with the conditions of a normal CVD method, the mean free path of gas is very short, so that a very homogeneous film can be obtained.
  • the atmospheric pressure or a pressure in the vicinity thereof is within a pressure range of 20 kPa to 110 kPa, and is preferably 93 kPa to 104 kPa in order to obtain the good effects described in the present invention.
  • the excited gas as used in the present invention means that at least part of the molecules in the gas move from the existing state to a higher energy state by obtaining energy, and the excited gas molecules, radicalized gas This includes molecules and gas containing ionized gas molecules.
  • the method for forming the gas barrier layer 3 containing a metal oxide by vapor deposition includes a metal element such as silicon in a discharge space where a high-frequency electric field is generated under atmospheric pressure or a pressure in the vicinity thereof.
  • the pressure between the counter electrodes (discharge space) is set to atmospheric pressure or a pressure in the vicinity thereof, a discharge gas is introduced between the counter electrodes, a high-frequency voltage is applied between the counter electrodes, and the discharge gas is changed to a plasma state, followed by The discharge gas and the raw material gas are mixed and supplied outside the discharge space, and the base material 2 is exposed to this mixed gas (secondary excitation gas) to form the gas barrier layer 3 on the base material 2.
  • the gas barrier layer 3 containing a metal oxide formed by the plasma CVD method in the present invention may be a composite compound such as a metal oxide, a metal nitride, or a metal carbide.
  • the gas barrier layer obtained by the plasma CVD method or the atmospheric pressure plasma CVD method is selected by selecting the organic or inorganic metal compound as the raw material, the conditions such as the decomposition gas, decomposition temperature, input power, etc. Accordingly, a ceramic film of a metal oxide or a mixture of a metal oxide and a metal carbide, a metal nitride, a metal sulfide, or the like can be appropriately formed. For example, if a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, a silicon oxide ceramic film is formed.
  • a zinc compound is used as a raw material compound and carbon disulfide is used as a decomposition gas, a zinc sulfide ceramic film is formed.
  • highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.
  • a raw material for such an inorganic film may be in a gas, liquid, or solid state at normal temperature and pressure as long as it has a typical element or a transition metal element.
  • gas it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation.
  • the solvent may be diluted with a solvent, and examples of the solvent include organic solvents such as methanol, ethanol, n-hexane, and mixed solvents thereof. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence on the film formation can be almost ignored.
  • a decomposition gas for decomposing a raw material gas containing a metal element to obtain an inorganic compound for example, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, suboxide
  • examples thereof include nitrogen gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.
  • a ceramic film of a metal oxide or a mixture of a metal oxide and a metal carbide, a metal nitride, a metal halide, a metal sulfide, etc. can be obtained. it can.
  • a discharge gas that tends to be in a plasma state is mixed with the reactive gas of the raw material gas and the decomposition gas, and the mixed gas is sent to the plasma discharge treatment apparatus.
  • a discharge gas nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
  • a gas barrier layer 3 that is a vapor deposition film is formed by supplying a mixed gas obtained by mixing a discharge gas and a reactive gas to a plasma discharge treatment apparatus.
  • the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, it is preferable to supply the reactive gas with the ratio of the discharge gas being 50% or more of the entire mixed gas.
  • the gas barrier layer 3 formed by the vapor deposition method may be composed of a plurality of layers in which these conditions are changed, and the ratio of the discharge gas to the reactive gas and the discharge conditions are continuously set. It may be composed of a changed film that is non-uniform in the film thickness direction.
  • an electric field is applied to a space in the vicinity of the support (base material 2) to generate a space (plasma space) in which a gas in a plasma state is present.
  • a space plasma space
  • a gas in a plasma state is present.
  • it is sprayed onto the support (base material 2) to form an inorganic thin film.
  • a high percentage of gas is ionized into ions and electrons, and although the temperature of the gas is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions or radicals, the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature.
  • the film forming method that can lower the temperature of the support (base material 2) on which the inorganic material is formed, and can sufficiently form the film on the plastic base material 2 (resin film).
  • this plasma CVD method a thin film having a stable performance can be obtained with a dense film density when a ceramic film is formed on the resin film (base material 2). Further, the residual stress is compressive stress, and a ceramic film having a range of 0.01 to 20 MPa can be stably obtained.
  • Examples of the plasma discharge treatment apparatus that can be applied to the present invention include apparatuses described in Japanese Patent Application Laid-Open Nos. 2004-68143, 2003-49272, and WO 02/48428. .
  • gas barrier layer in which constituent atom distribution is precisely controlled in the layer thickness direction can be preferably applied.
  • the method for forming the gas barrier layer according to the present invention is not particularly limited, but from the viewpoint of forming a gas barrier layer in which the element distribution is precisely controlled, a source gas containing an organosilicon compound and an oxygen gas And a method of forming by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied.
  • this gas barrier layer forming method is also referred to as a magnetic field applied plasma CVD method or a roller CVD method.
  • the gas barrier layer according to the present invention contains carbon atoms, silicon atoms, and oxygen atoms, the composition continuously changes in the layer thickness direction, and satisfies the following requirements (1) and (2) simultaneously: Is preferred.
  • the average atomic ratio of each atom to the total amount (100 at%) of silicon atoms, oxygen atoms and carbon atoms is expressed by the following formula (A) or (B ) In the order of magnitude.
  • the gas barrier layer is used as the region satisfying the relationship defined by the above formula (A) or formula (B). It is preferable that the region be in the range of 90 to 95% of the total layer thickness.
  • the thickness of the gas barrier layer according to the present invention is preferably in the range of 50 to 1000 nm.
  • the average value of the content ratio of carbon atoms in the gas barrier layer according to the present invention can be determined by measuring an XPS depth profile described later.
  • the gas barrier layer according to the present invention contains carbon atoms, silicon atoms and oxygen atoms as constituent elements of the gas barrier layer, and the composition continuously changes in the layer thickness direction.
  • the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy, the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer, the silicon atom, the oxygen atom
  • a carbon distribution curve showing the relationship with the ratio of the amount of carbon atoms to the total amount of carbon atoms (100 at%) referred to as “carbon atom ratio (at%)”
  • carbon atom ratio (at%) a carbon distribution curve showing the relationship with the ratio of the amount of carbon atoms to the total amount of carbon atoms (100 at%)
  • the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) is preferably 5 at% or more.
  • the gas barrier layer according to the present invention has a configuration in which the carbon atom ratio continuously changes with a concentration gradient in a specific region of the gas barrier layer, so that both gas barrier properties and flexibility are achieved. Therefore, this is a preferred embodiment.
  • the carbon distribution curve in the layer preferably has at least one extreme value, and more preferably has at least two extreme values. It is particularly preferred to have at least three extreme values.
  • the carbon distribution curve does not have an extreme value, the gas barrier property when the obtained film of the gas barrier film is bent is insufficient.
  • the gas in the thickness direction of the gas barrier layer at one extreme value and the extreme value adjacent to the extreme value that the carbon distribution curve has.
  • the absolute value of the difference in distance from the surface of the barrier layer is preferably 200 nm or less, and more preferably 100 nm or less.
  • the extreme value of the distribution curve means a measured value of the maximum value or the minimum value of the atomic ratio of the element to the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer.
  • the maximum value is a point where the value of the atomic ratio of an element changes from increasing to decreasing when the distance from the surface of the gas barrier layer is changed, and from the value of the atomic ratio of the element at that point.
  • This also means that the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer is further changed by 20 nm from that point is reduced by 3 at% or more.
  • the minimum value is a point where the value of the atomic ratio of the element changes from decrease to increase when the distance from the surface of the gas barrier layer is changed, and the value of the atomic ratio of the element at that point Rather, the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer from this point is further changed by 20 nm increases by 3 at% or more.
  • the gas barrier layer according to the present invention preferably has an extreme value, and the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is preferably 5 at% or more. It is an aspect.
  • the gas barrier layer according to the present invention is characterized by containing carbon atoms, silicon atoms and oxygen atoms as constituent elements, and the ratio of each atom, Preferred embodiments for the maximum and minimum values are described below.
  • the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio in the carbon distribution curve. Value) is preferably 5 at% or more.
  • the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio is more preferably 6 at% or more, and particularly preferably 7 at% or more.
  • the absolute value of the difference between the maximum value and the minimum value in the oxygen distribution curve is 5 at% or more. Preferably, it is 6 at% or more, more preferably 7 at% or more. When the absolute value is 5 at% or more, the gas barrier property when the obtained gas barrier film is bent is sufficient.
  • the absolute value of the difference between the maximum value and the minimum value in the silicon distribution curve may be less than 5 at%. Preferably, it is less than 4 at%, more preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property and mechanical strength of the obtained gas barrier film are sufficient.
  • the total amount of silicon atoms, oxygen atoms and carbon atoms means silicon atoms. Represents the total at% of oxygen atoms and carbon atoms, and “amount of carbon atoms” means the number of carbon atoms.
  • the term “at%” in the present invention means the atomic ratio of each atom when the total number of silicon atoms, oxygen atoms and carbon atoms is 100%. The same applies to “amount of silicon atoms” and “amount of oxygen atoms” for the silicon distribution curve, oxygen distribution curve, and oxygen carbon distribution curve as shown in FIGS.
  • silicon atoms and oxygen are present in a region of 90% or more of the total layer thickness of the gas barrier layer. It is a preferable aspect that the average atomic ratio of each atom with respect to the total amount of atoms and carbon atoms (100 at%) has an order magnitude relationship represented by the following formula (A) or (B).
  • Formula (A) Carbon average atomic ratio) ⁇ (silicon average atomic ratio) ⁇ (oxygen average atomic ratio)
  • Formula (B) (Oxygen average atomic ratio) ⁇ (silicon average atomic ratio) ⁇ (carbon average atomic ratio) (3.3) Element distribution measurement in the depth direction by X-ray photoelectron spectroscopy
  • the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen-carbon total distribution curve in the thickness direction of the gas barrier layer are as follows: Created by so-called XPS depth profile measurement, in which X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering of argon or the like are used together to sequentially analyze the surface composition while exposing the inside of the sample.
  • XPS X-ray photoelectron spectroscopy
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).
  • the etching time generally correlates with the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer in the layer thickness direction.
  • “Distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer” as calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement Can be adopted.
  • etching rate is 0.05 nm / It is preferable to set to sec (SiO 2 thermal oxide film conversion value).
  • the gas barrier layer is in the film surface direction (direction parallel to the surface of the gas barrier layer). Is substantially uniform.
  • that the gas barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve, and the carbon distribution curve at any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement.
  • the gas barrier film according to the present invention preferably includes at least one gas barrier layer that simultaneously satisfies the requirements (1) and (2) defined in the present invention. May have two or more layers. Furthermore, when two or more such gas barrier layers are provided, the materials of the plurality of gas barrier layers may be the same or different. Further, when two or more such gas barrier layers are provided, such a gas barrier layer may be formed on one surface of the base material, and is formed on both surfaces of the base material. May be. Moreover, as such a plurality of gas barrier layers, a gas barrier layer not necessarily having a gas barrier property may be included.
  • the silicon atom ratio relative to the total amount of silicon atoms, oxygen atoms, and carbon atoms is preferably in the range of 19 to 40 at%, and preferably 30 to 40 at%. % Is more preferable.
  • the oxygen atom ratio with respect to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably in the range of 33 to 67 at%, more preferably in the range of 41 to 62 at%.
  • the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably in the range of 1 to 19 at%, and more preferably in the range of 3 to 19 at%.
  • the thickness of the gas barrier layer formed by the vacuum deposition method according to the present invention is preferably in the range of 5 to 1000 nm, and is preferably in the range of 10 to 1000 nm. More preferably, it is particularly preferably in the range of 100 to 1000 nm.
  • the gas barrier properties such as oxygen gas barrier property and water vapor barrier property are excellent, and the gas barrier property is not deteriorated by bending.
  • gas barrier properties such as oxygen gas barrier property and water vapor barrier property are sufficient.
  • the barrier property tends to be difficult to decrease.
  • the gas barrier layer formation method according to the present invention is not particularly limited as long as it is a thin film formation method capable of realizing the element profile defined in the present invention. From the viewpoint of forming a gas barrier layer in which the element distribution is controlled, a discharge plasma chemical gas having a discharge space between rollers to which a magnetic field is applied using a source gas containing an organosilicon compound and an oxygen gas. A method of forming by a phase growth method is preferable.
  • the gas barrier layer according to the present invention uses an inter-roller discharge plasma processing apparatus to which a magnetic field is applied, winds a resin base material around a pair of film forming rollers, and forms a film forming gas between the pair of film forming rollers. It is a layer formed by plasma chemical vapor deposition by plasma discharge while being supplied. Further, when discharging while applying a magnetic field between the pair of film forming rollers, it is preferable to reverse the polarity between the pair of film forming rollers alternately. Further, as a film forming gas used in such a plasma chemical vapor deposition method, a source gas containing an organosilicon compound and an oxygen gas are used, and the content of the oxygen gas in the film forming gas is within the film forming gas. It is preferable that the amount is less than the theoretical oxygen amount necessary for complete oxidation of the total amount of the organosilicon compound. In the gas barrier film according to the present invention, the gas barrier layer is preferably a layer formed by a continuous film forming process.
  • a plurality of films are formed when plasma is generated. It is preferable to generate a plasma discharge in the formed discharge space while applying a magnetic field between the rollers.
  • a pair of film forming rollers is used, and a resin substrate is wound around each of the pair of film forming rollers. It is preferable to generate plasma by discharging in a state where a magnetic field is applied between the pair of film forming rollers.
  • the film formation rate can be doubled, and a film having the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled. It is possible to form a gas barrier layer that satisfies the requirements (1) and (2) simultaneously.
  • a film forming roller provided with an apparatus that applies at least a pair of magnetic fields;
  • the apparatus preferably includes a plasma power source and is configured to be capable of discharging between a pair of film forming rollers.
  • a gas barrier film can be produced by a roll-to-roll method using a phase growth method.
  • FIG. 2 is a schematic view showing an example of an inter-roller discharge plasma CVD apparatus to which a magnetic field that can be suitably used in the formation of the gas barrier layer according to the present invention is applied.
  • An inter-roller discharge plasma CVD apparatus (hereinafter also referred to as a plasma CVD apparatus) to which a magnetic field shown in FIG. 2 is applied mainly includes a delivery roller 111, transport rollers 121, 122, 123, and 124, and a film formation roller 131. And 132, a film forming gas supply pipe 141, a plasma generating power source 151, magnetic field generators 161 and 162 installed inside the film forming rollers 131 and 132, and a winding roller 171.
  • a vacuum chamber (not shown) is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by this vacuum pump. Yes.
  • each film forming roller generates plasma so that a pair of film forming rollers (the film forming roller 131 and the film forming roller 132) can function as a pair of counter electrodes.
  • the power supply 151 is connected.
  • the space between the film formation roller 131 and the film formation roller 132 can be discharged. Accordingly, plasma can be generated in a space (also referred to as a discharge space) between the film formation roller 131 and the film formation roller 132.
  • the film-forming roller 131 and the film-forming roller 132 are used as electrodes in this way, materials and designs that can be used as electrodes may be changed as appropriate.
  • the pair of film forming rollers (film forming rollers 131 and 132) be arranged so that their central axes are substantially parallel on the same plane. In this way, by arranging a pair of film forming rollers (film forming rollers 131 and 132), the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled.
  • magnetic field generators 161 and 162 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.
  • the film forming roller 131 and the film forming roller 132 known rollers can be appropriately used.
  • the film forming rollers 131 and 132 those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently.
  • the diameters of the film forming rollers 131 and 132 are preferably in the range of 100 to 1000 mm ⁇ , particularly in the range of 100 to 700 mm ⁇ , from the viewpoint of discharge conditions, chamber space, and the like. If the diameter is 100 mm ⁇ or more, it is preferable that the plasma discharge space is not reduced, the productivity is not deteriorated, the total amount of heat of the plasma discharge can be prevented from being applied to the film in a short time, and the residual stress is hardly increased.
  • a diameter of 1000 mm ⁇ or less is preferable because practicality can be maintained in terms of device design including uniformity of the plasma discharge space.
  • the winding roller 171 is not particularly limited as long as it can wind the resin base material 1 on which the gas barrier layer is formed, and a known roller can be used as appropriate.
  • the film forming gas supply pipe 141 one capable of supplying or discharging the source gas and the oxygen gas at a predetermined rate can be appropriately used.
  • the plasma generating power source 151 a conventionally known power source of a plasma generating apparatus can be used. Such a plasma generating power supply 151 supplies power to the film forming roller 131 and the film forming roller 132 connected thereto, and makes it possible to use these as counter electrodes for discharge. As such a plasma generating power supply 151, a plasma CVD method can be carried out more efficiently, so that the polarity of a pair of film forming rollers can be alternately reversed (AC power supply or the like). Is preferably used.
  • the applied power can be in the range of 100 W to 10 kW, and the AC frequency is 50 Hz. More preferably, it can be in the range of -500 kHz.
  • the magnetic field generators 161 and 62 known magnetic field generators can be used as appropriate.
  • the gas barrier layer according to the present invention can be formed by appropriately adjusting the conveyance speed of the substrate. That is, using the plasma CVD apparatus shown in FIG. 2, a magnetic field is generated between a pair of film forming rollers (film forming rollers 131 and 132) while supplying a film forming gas (raw material gas) into the vacuum chamber.
  • the film forming gas (raw material gas or the like) is decomposed by plasma, and on the surface of the resin base material 101 on the film forming roller 131 and on the surface of the resin base material 101 on the film forming roller 132.
  • the gas barrier layer according to the present invention is formed by the plasma CVD method. In such film formation, the resin base material 101 is transported by the delivery roller 111, the film formation roller 131, and the like, respectively, so that the resin base material 101 is formed by a roll-to-roll continuous film formation process.
  • the gas barrier layer is formed on the surface.
  • Source gas It is preferable to use an organosilicon compound containing at least silicon as the source gas constituting the film forming gas used for forming the gas barrier layer according to the present invention.
  • organosilicon compound applicable to the present invention examples include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, and trimethyl.
  • examples include silane, diethylsilane, propylsilane, 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 in film formation and gas barrier properties of the obtained gas barrier layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
  • the film forming gas contains oxygen gas as a reaction gas in addition to the source gas.
  • the oxygen gas is a gas that reacts with the raw material gas to become an inorganic compound such as an oxide.
  • a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • carrier gas and discharge gas known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.
  • such a film forming gas contains a raw material gas containing an organosilicon compound containing silicon and an oxygen gas
  • the ratio of the raw material gas to the oxygen gas is such that the raw material gas and the oxygen gas are completely reacted. It is preferable that the oxygen gas ratio is not excessively higher than the theoretically required oxygen gas ratio. If the ratio of oxygen gas is excessive, it is difficult to obtain the target gas barrier layer in the present invention. Therefore, in order to obtain the desired performance as a barrier film, it is preferable that the total amount of the organosilicon compound in the film-forming gas is less than or equal to the theoretical oxygen amount necessary for complete oxidation.
  • the pressure in the vacuum chamber (degree of vacuum) can be adjusted as appropriate according to the type of source gas, but is preferably in the range of 0.5 Pa to 100 Pa.
  • roller Film Formation In the plasma CVD method using a plasma CVD apparatus or the like as shown in FIG. 2, it is connected to a plasma generation power source 151 in order to discharge between the film formation rollers 131 and 132.
  • the power applied to the electrode drum (installed in the film forming rollers 131 and 132 in FIG. 2) can be adjusted as appropriate according to the type of source gas and the pressure in the vacuum chamber. Although it cannot be generally stated, it is preferably within a range of 0.1 to 10 kW. If the applied power is in such a range, no generation of particles (illegal particles) is observed, and the amount of heat generated during film formation is within the control range.
  • the conveyance speed (line speed) of the resin base material 101 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is within the range of 0.5 to 20 m / min. When the line speed is within the above range, wrinkles due to the heat of the resin base material hardly occur, and the thickness of the formed gas barrier layer can be sufficiently controlled.
  • FIG. 3 shows an example of each element profile in the layer thickness direction based on the XPS depth profile of the gas barrier layer according to the present invention formed as described above.
  • FIG. 3 is a graph showing an example of a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve of the gas barrier layer according to the present invention.
  • symbols A to D represent A as a carbon distribution curve, B as a silicon distribution curve, C as an oxygen distribution curve, and D as an oxygen carbon distribution curve.
  • the gas barrier layer according to the present invention has an extreme value, the difference between the maximum maximum value and the minimum maximum value of the carbon atom ratio is 5 at% or more, and the gas In a region of 90% or more of the total thickness of the barrier layer, the average atomic ratio of each atom to the total amount (100 at%) of silicon atoms, oxygen atoms and carbon atoms is defined by the above formula (A) or (B). It can be seen that the order of magnitude is satisfied.
  • Gas barrier layer formation method 3 Polysilazane modification method
  • the gas barrier film 1 of the present invention can be provided on the substrate 2 by directly providing the gas barrier layer 3 on the substrate 2 or through the anchor coat layer 7 by a polysilazane modification method.
  • the polysilazane modification method in the present invention refers to a process of converting a part or most of a polysilazane compound into silicon oxide or silicon oxynitride by a modification process.
  • a conversion reaction using ultraviolet light capable of a conversion reaction at a lower temperature is preferably used from the viewpoint of adapting to a plastic substrate.
  • the gas barrier layer 3 formed by the polysilazane modification method is formed by applying and drying a liquid containing polysilazane and then applying a modification treatment by irradiation with vacuum ultraviolet light. Contains silicon oxide.
  • the polysilazane compound according to the present invention is a polymer having a silicon-nitrogen bond, such as SiO 2 , Si 3 N 4 having a bond such as Si—N, Si—H, or N—H, and both intermediate solid solutions SiO x N y.
  • a ceramic precursor inorganic polymer Such as a ceramic precursor inorganic polymer.
  • a coating method for coating the coating liquid containing the polysilazane compound a conventionally known appropriate wet coating method can be employed. Specific examples include spin coating, roller coating, flow coating, ink jet, spray coating, printing, dip coating, casting film formation, bar coating, and gravure printing.
  • the thickness of the gas barrier layer 3 can be appropriately set according to the purpose.
  • the thickness after drying is preferably in the range of 1 nm to 100 ⁇ m, more preferably in the range of 10 nm to 10 ⁇ m, and most preferably in the range of 10 nm to 1 ⁇ m.
  • the polysilazane compound is preferably a compound that is ceramicized at a relatively low temperature and modified to silica so that the properties of the base material 2 are not impaired.
  • the following general description in JP-A-8-112879 A compound having a main skeleton composed of units represented by the formula (1) is preferred.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.
  • perhydropolysilazane in which all of R 1 , R 2 , and R 3 are hydrogen atoms is particularly preferable from the viewpoint of denseness as a gas barrier film to be obtained.
  • the adhesiveness with the base material 2 as a base is improved,
  • the ceramic film made of polysilazane which is hard and brittle, can be toughened, and even when the film thickness (average film thickness) is made thicker, the occurrence of cracks can be suppressed. Therefore, perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.
  • Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings.
  • the number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), and there are liquid or solid substances, and the state varies depending on the molecular weight.
  • Mn number average molecular weight
  • These compounds are commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.
  • -240208 obtained by reacting a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (for example, see JP-A-6-299118), and an acetylacetonate complex containing a metal.
  • Acetylacetonate complex-added polysilazane For example, JP-A-6-306329 JP reference.), Fine metal particles of the metal particles added polysilazane obtained by adding (e.g., JP-A-7-196986 JP reference.), And the like.
  • hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers can be used. .
  • hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran.
  • organic solvents may be selected according to characteristics such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.
  • the concentration of polysilazane in the coating solution for forming a gas barrier layer containing a polysilazane compound varies depending on the film thickness of the target polysilazane modified layer and the pot life of the coating solution, but is within the range of 0.2 to 35% by mass. Preferably there is.
  • An amine or metal catalyst may be added to the gas barrier layer forming coating solution containing a polysilazane compound in order to promote conversion to a silicon oxide compound.
  • Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.
  • the polysilazane modified layer (gas barrier layer) formed by the gas barrier layer forming coating solution containing the polysilazane compound used in the present invention preferably has moisture removed before or during the modification treatment. . Therefore, it may be divided into a first drying step for the purpose of removing the organic solvent in the polysilazane modified layer and a second drying step for the purpose of removing the water in the polysilazane modified layer.
  • the organic solvent is mainly removed, so that the drying conditions can be appropriately determined by a method such as heat treatment, and the conditions may be such that moisture is removed at this time.
  • the heat treatment temperature is preferably a high temperature from the viewpoint of rapid processing, but it is preferable to appropriately determine the temperature and treatment time in consideration of thermal damage to the substrate 2 that is a resin film.
  • the heat treatment temperature is preferably set to 150 ° C. or less.
  • the treatment time is preferably set to a short time so that the solvent is removed and thermal damage to the substrate 2 is reduced. If the heat treatment temperature is 150 ° C. or less, the treatment time can be set within 30 minutes.
  • the second drying step is a step for removing moisture from the polysilazane modified layer (gas barrier layer 3).
  • a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature.
  • a preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is ⁇ 8 ° C. (temperature 25 ° C./humidity 10%) or lower, and a more preferable dew point temperature is ⁇ 31 ° C.
  • the pressure for drying under reduced pressure can be selected within the range of normal pressure to 0.1 MPa.
  • Preferred conditions for the second drying step relative to the conditions for the first drying step include, for example, when the solvent is removed at a temperature of 60 to 150 ° C. and a processing time of 1 to 30 minutes as the first drying step.
  • the dew point is 4 ° C. or less, and the treatment time is 5 minutes to 120 minutes.
  • the polysilazane modified layer (gas barrier layer 3) according to the present invention is preferably subjected to a modification treatment while maintaining its state even after moisture is removed by the second drying step.
  • the modification treatment of the polysilazane layer in the present invention refers to a reaction in which part or all of the polysilazane compound is converted into silicon oxide or silicon oxynitride.
  • a known method based on the conversion reaction of the polysilazane compound can be selected.
  • the formation of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a polysilazane compound usually requires a high temperature of 450 ° C. or higher, and it is difficult to adapt to a flexible substrate using a resin film as the base material 2. Therefore, when producing the gas barrier film of the present invention, a conversion reaction using vacuum ultraviolet light capable of a conversion reaction at a lower temperature is preferable from the viewpoint of adaptation to a plastic substrate.
  • the polysilazane coating film from which moisture has been removed is subjected to a modification treatment by ultraviolet light irradiation.
  • Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and form high-density and insulating silicon oxide films and silicon oxynitride films under low-temperature environments. Is possible.
  • This ultraviolet light irradiation excites and activates O 2 and H 2 O, UV absorbers, and polysilazane compounds themselves that contribute to ceramicization. And the ceramicization of the excited polysilazane compound is promoted, and the resulting ceramic film becomes dense. Irradiation with ultraviolet light is effective at any time after the formation of the coating film.
  • the ultraviolet light referred to in the present invention generally refers to ultraviolet light containing electromagnetic waves having a wavelength in the range of 10 to 200 nm called vacuum ultraviolet light.
  • the irradiation intensity and the irradiation time in a range in which the base material 2 carrying the polysilazane layer to be irradiated is not damaged.
  • a 2 kW (80 W / cm ⁇ 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm 2 , preferably 50 to 200 mW /
  • the distance between the substrate and the ultraviolet irradiation lamp can be set so as to be within the range of cm 2 , and irradiation can be performed within the range of 0.1 second to 10 minutes.
  • the substrate temperature during the ultraviolet irradiation treatment is 150 ° C. or higher, the properties of the substrate 2 are impaired in the case of a plastic film or the like such as deformation or deterioration of its strength.
  • a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of the substrate 2.
  • Examples of such ultraviolet ray generating means include, but are not particularly limited to, metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers.
  • the ultraviolet light from the source is reflected by the reflector and then before the modification. A method of applying to the polysilazane layer is desirable.
  • UV irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate 2 to be used.
  • the base material 2 having the gas barrier layer 3 formed by the modification treatment of polysilazane is in the form of a long film
  • ultraviolet rays are continuously produced in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed.
  • the time required for ultraviolet irradiation generally depends on the composition and concentration of the substrate 2 and gas barrier layer 3 to be used, but is generally in the range of 0.1 second to 10 minutes, preferably in the range of 0.5 second to 3 minutes. It is.
  • the oxygen concentration at the time of irradiation with vacuum ultraviolet light (VUV) is preferably in the range of 300 to 10000 ppm (1%), more preferably in the range of 500 to 5000 ppm.
  • VUV vacuum ultraviolet light
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
  • the modification treatment method for the polysilazane layer before modification according to the present invention is treatment by irradiation with vacuum ultraviolet light.
  • the treatment by vacuum ultraviolet light irradiation uses light energy of 100 to 200 nm, preferably light energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and the bonding of atoms is a photon called photon process.
  • This is a method in which a silicon oxide film is formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by only the action.
  • a vacuum ultraviolet light source required for this a rare gas excimer lamp is preferably used.
  • rare gas atoms such as Xe, Kr, Ar, and Ne are referred to as inert gases because they are not chemically bonded to form molecules.
  • a rare gas atom excited atom
  • the rare gas is xenon, e + Xe ⁇ e + Xe * Xe * + Xe + Xe ⁇ Xe 2 * + Xe
  • excimer light vacuum ultraviolet light
  • ⁇ Excimer lamps are characterized by high efficiency because radiation concentrates on one wavelength and almost no other light is emitted. Moreover, since extra light is not radiated
  • Dielectric barrier discharge is a lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. Is a very thin discharge called micro discharge.
  • electrodeless field discharge is also known as a method for efficiently obtaining excimer light emission.
  • the electrodeless field discharge is a discharge due to capacitive coupling, and is also called an RF discharge.
  • the lamp and electrodes and their arrangement may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz.
  • a spatially and temporally uniform discharge can be obtained in this way.
  • the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating organic bonds has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane film can be modified in a short time.
  • the excimer lamp since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy of a single wavelength is irradiated in the ultraviolet region, so that an increase in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for the irradiation to the gas barrier film which makes the base material 2 resin films, such as a polyethylene terephthalate considered that it is easy to receive the influence of a heat
  • the gas barrier film which makes the base material 2 resin films such as a polyethylene terephthalate considered that it is easy to receive the influence of a heat
  • a gas barrier layer formed by subjecting a polysilazane film formed by a gas barrier layer forming coating solution containing a polysilazane compound to a modification treatment is preferably used.
  • a gas barrier layer formed on a substrate a gas barrier layer formed by a modification treatment of a polysilazane compound has an effect of eliminating fine irregularities on the surface, rather than a gas barrier layer formed by a vapor deposition method. It is larger and the load at the time of smoothing with the subsequent smooth layer can be reduced.
  • the configuration of the gas barrier layer according to the present invention may be a gas barrier layer formed by the above-described chemical vapor deposition method or a gas barrier layer formed by a polysilazane modification method, but a more preferable embodiment is a gas barrier layer.
  • the layer is composed of at least two layers, and the first gas barrier layer located on the substrate side contains the carbon atom, silicon atom and oxygen atom described above, and the composition continuously changes in the layer thickness direction,
  • the gas barrier layer B is configured to satisfy the requirements (1) and (2) at the same time, and the second gas barrier layer located on the outermost layer side has the polysilazane-containing coating liquid described above on the gas barrier layer B.
  • a hybrid gas barrier layer unit which is a gas barrier layer formed by applying a modification treatment after coating, is preferable.
  • the gas barrier film of the present invention has a smooth layer 4 on the surface of the gas barrier layer 3 described above.
  • the smooth layer is formed by applying and drying a coating solution for forming a smooth layer containing a compound having a nitrogen atom, for example, a polyol compound and a compound having an isocyanate group, on the gas barrier layer 3. Forming the layer 4 is a preferred embodiment.
  • the smooth layer 4 is formed on at least one surface of the substrate 2.
  • the smooth layer 4 flattens the rough surface of the gas barrier layer 3 where minute protrusions and the like exist, and forms a film on the gas barrier layer 3 by protrusions on the surface of the gas barrier layer 3. It is provided in order to prevent unevenness and pinholes from occurring in 5 etc.
  • a compound having a nitrogen atom is preferable.
  • a compound having at least one urethane bond in the polymer skeleton is preferably used.
  • a cured resin obtained by urethane crosslinking using a known polyol compound having two or more hydroxy groups and a known polyfunctional isocyanate compound having two or more isocyanate groups in one molecule is preferable.
  • Such a range includes a phenoxy resin cross-linked and cured with an isocyanate compound, a copolymer thereof, and a polyvinyl acetal resin.
  • Another purpose of the smooth layer is to improve the adhesion between the gas barrier layer 3 made of a highly inorganic metal oxide or the like and the base layer 6 provided as necessary, which will be described later. Even after the passage of time, good interlayer adhesion can be maintained.
  • the smooth layer 4 on the surface of the gas barrier layer 3 with a flexible resin base material, it can be conveyed and wound when manufactured in a roll-to-roll manner, or bend as a barrier film. An effect of suppressing physical destruction of the gas barrier layer 3 can be expected.
  • Examples of a compound having a urethane bond as a compound having a nitrogen atom particularly preferably used in the smooth layer according to the present invention are shown below.
  • the polyol compound used for forming the smooth layer 4 has two or more hydroxy groups in the molecule.
  • Typical examples thereof include polyester polyol, acrylic polyol, polyurethane polyol, Examples include polyether polyol and polycaprolactone polyol.
  • acrylic polyols examples include acrylic polyol resins manufactured by Toray Fine Chemical Co., Ltd., for example, Cotax LH series LH-455, LH-681, LH-404, LH-307, LH-649, LH- 677, LH-591, LH-650, LH-629, LH-601, LH-633, LH-613, LH-408, LH-615, LH-635 and the like are listed as exemplary compounds.
  • the urethane polyol can be produced from a diisocyanate compound and a hydroxy group-containing compound.
  • the diisocyanate compound include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI), isophorone diisocyanate (IPDI), and tetramethylxylylene diisocyanate (TMXDI) from the viewpoint of light yellowing resistance.
  • HDI hexamethylene diisocyanate
  • XDI xylylene diisocyanate
  • H6XDI hydrogenated xylylene diisocyanate
  • IPDI isophorone diisocyanate
  • TXDI tetramethylxylylene diisocyanate
  • H12MDI hydrogenated diphenylmethane diisocyanate
  • the hydroxy group-containing compound low molecular weight diols,
  • Examples of the low molecular weight diol and triol include ethylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, Examples thereof include trimethylolpropane and hexanetriol.
  • the macropolyol examples include polyether polyols such as polyoxypropylene glycol, polyoxyethylene glycol, polyoxytetramethylene glycol and oxyalkylene copolymers; polycondensates of dicarboxylic acids and glycols, and ⁇ -caprolactone. Polyester polyols such as ring-opening polymers; polycarbonate polyols; polyolefin polyols such as polyol derivatives of polyolefins such as polybutadiene, hydrogenated polybutadiene, and polyisoprene; and epoxy polyols. Among these, polycarbonate polyols and polyether polyols are preferable from the viewpoint of bending resistance and light yellowing resistance.
  • the molecular weight of the macropolyol is preferably in the range of 500 to 5000, more preferably in the range of 500 to 2000.
  • the polyurethane polyol has a urethane bond in the main chain and a hydroxyl group at the terminal.
  • polyether polyols examples include those obtained by polymerizing or copolymerizing alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) and / or heterocyclic ethers (tetrahydrofuran, etc.), specifically, polyethylene glycol.
  • Polypropylene glycol polyethylene-polypropylene glycol (block or random copolymer), polyethylene-tetramethylene glycol (block or random copolymer), polytetramethylene ether glycol, polyhexamethylene ether glycol, poly- ⁇ -valerolactone polyol
  • multivalent such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, etc.
  • Alcohol and an initiator, to which alkylene oxide ethylene oxide, propylene oxide, butylene oxide, etc.
  • alkylene oxide ethylene oxide, propylene oxide, butylene oxide, etc.
  • polyester polyol is more preferably used.
  • polyisocyanates are preferably used as the compound having an isocyanate group used for forming the smooth layer.
  • Specific examples include aliphatic polyisocyanates such as hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, and aromatic polyisocyanates such as xylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene diisocyanate, tolidine diisocyanate, and naphthalene diisocyanate.
  • aliphatic polyisocyanates such as hexamethylene diisocyanate and dicyclohexylmethane diisocyanate
  • aromatic polyisocyanates such as xylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene diisocyanate, tolidine diisocyanate, and naphthal
  • Specific polyisocyanates include, for example, various coronates and millionates sold by Nippon Polyurethane Industry Co., Ltd. having isocyanate groups such as TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate), and HDI (hexamethylene diisocyanate).
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • General-purpose type, quick-drying type, moisture-curing type, non-yellowing type, block type, etc. may be used alone or in combination.
  • Examples of the other nitrogen atom-containing compounds used in the smooth layer according to the present invention include, for example, polyamideimide, polyetherimide, nylon, melamine resin, benzoguanamine resin and other amino resins, alkyl groups, and the like.
  • Examples include organopolysilazane and epoxy, polyester, and acrylic resins modified with amino groups.
  • the interlayer adhesion can be stabilized by the interaction with an adjacent base layer provided as necessary, and when applied to various devices. Moreover, it becomes a gas barrier film which can maintain favorable electroconductivity over a long period of time.
  • the method for forming the smooth layer 4 according to the present invention on the surface of the substrate 2 is not particularly limited.
  • a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a vapor deposition method. It is preferable to form by a dry coating method such as.
  • additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added as necessary.
  • an appropriate resin or additive may be used for improving the film formability on the formed smooth layer 4 and preventing pinholes from being formed on the film formed on the smooth layer 4.
  • a solvent used when forming the smooth layer 4 using a coating solution in which a resin is dissolved or dispersed in a solvent a solvent having low reactivity with an isocyanate group is preferably used.
  • ⁇ - or Terpenes such as ⁇ -terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone and 4-heptanone, and aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene , Ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoe Examples thereof include acetates such as tilether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl
  • the smoothness of the smooth layer 4 is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 80 nm or less. If Rt is 80 nm or less, after laminating a metal layer 5 described later or a base layer 6 provided as necessary, the surfaces of those layers can be smoothed.
  • the thickness of the smooth layer 4 is preferably in the range of 20 to 500 nm, more preferably in the range of 100 to 300 nm.
  • the thickness of the smooth layer 4 is preferably in the range of 20 to 500 nm, more preferably in the range of 100 to 300 nm.
  • the gas barrier film of this invention it is a preferable aspect that it further has the base layer 6 between the smooth layer 4 and the metal layer 5 mentioned later.
  • the underlayer 6 preferably contains an organic compound having at least one atom selected from a nitrogen atom and a sulfur atom, and further preferably contains a compound containing a nitrogen atom.
  • a metal layer 5 formed thereon for example, a layer formed using a compound having a specific relationship with silver (Ag) Preferably there is.
  • the layer thickness of the underlayer is preferably in the range of 5 nm to 1 ⁇ m, and more preferably in the range of 10 to 500 nm.
  • heterocycle having a nitrogen atom as a hetero atom examples include aziridine, azirine, azetidine, azeto, azolidine, azole, azinane, pyridine, azepan, azepine, imidazole, pyrazole, oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, indole, Examples include isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzo-C-cinnoline, porphyrin, chlorin, choline and the like.
  • the compound preferably used as the compound having a heterocyclic ring having a nitrogen atom as a hetero atom is, for example, a compound represented by the following general formula (2) or a compound represented by the following general formula (3): Is exemplified.
  • the transparent gas barrier film 1 of the present invention it is preferable to select and use a compound represented by the general formula (2) or the general formula (3) for the underlayer 6 according to the present invention.
  • Y5 represents the bivalent coupling group which consists of an arylene group, heteroarylene group, or those combination.
  • E51 to E66 and E71 to E88 each represent C (R 3 ) or a nitrogen atom
  • R 3 represents a hydrogen atom or a substituent.
  • at least one of E71 to E79 and at least one of E80 to E88 represent a nitrogen atom.
  • n3 and n4 each represents an integer of 0 to 4, and n3 + n4 is an integer of 2 or more.
  • examples of the arylene group represented by Y5 include o-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, and biphenyldiyl.
  • examples of the heteroarylene group represented by Y5 include a carbazole ring, a carboline ring, a diazacarbazole ring (also referred to as a monoazacarboline ring, and one of the carbon atoms constituting the carboline ring is nitrogen.
  • a ring structure with an atom substitution a triazole ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a quinoxaline ring, a thiophene ring, an oxadiazole ring, a dibenzofuran ring, a dibenzothiophene ring, and an indole ring. And the like.
  • the divalent linking group consisting of an arylene group, a heteroarylene group or a combination thereof represented by Y5
  • a condensed aromatic heterocycle formed by condensation of three or more rings.
  • a group derived from a condensed aromatic heterocyclic ring formed by condensing three or more rings is preferably included, and a group derived from a dibenzofuran ring or a dibenzothiophene ring is preferable.
  • Y5 a condensed aromatic heterocycle formed by condensation of three or more rings.
  • a group derived from a condensed aromatic heterocyclic ring formed by condensing three or more rings is preferably included, and a group derived from a dibenzofuran ring or a dibenzothiophene ring is preferable.
  • Examples of the substituent represented by R 3 in C (R 3 ) represented by E51 to E66 and E71 to E88 in the general formula (2) are alkyl groups (eg, methyl group, ethyl group, propyl group). Group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group etc.), alkenyl group ( For example, vinyl group, allyl group, etc.), alkynyl group (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group Mesity
  • substituents may be further substituted with the above substituents.
  • a plurality of these substituents may be bonded to each other to form a ring.
  • E51 to E58 and 6 or more of E59 to E66 are each represented by C (R 3 ).
  • At least one of E75 to E79 and at least one of E84 to E88 represent a nitrogen atom.
  • any one of E75 to E79 and any one of E84 to E88 represent a nitrogen atom.
  • E71 to E74 and E80 to E83 are each represented by C (R3).
  • E53 is represented by C (R 3 ) and R 3 represents a linking site
  • E61 is also represented by C (R 3 ) at the same time.
  • R 3 preferably represents a linking moiety.
  • E75 and E84 are each preferably represented by a nitrogen atom, and E71 to E74 and E80 to E83 are each preferably represented by C (R 3 ).
  • At least one of T11 and T12 is a nitrogen atom
  • at least one of T21 to T25 is a nitrogen atom
  • at least one of T31 to T35 is a nitrogen atom. It is.
  • R represents a substituent.
  • substituent represented by R include those similar to R 3 in the general formula (2). These substituents may be further substituted with the above substituents.
  • the underlayer according to the present invention includes at least one selected from a nitrogen atom and a sulfur atom described below.
  • the organic compound having the above-mentioned atoms can be appropriately selected and contained.
  • the low molecular organic compound having a nitrogen atom is a compound having a melting point of 80 ° C. or higher and a molecular weight M in the range of 150 to 1200.
  • a nitrogen-containing heterocyclic compound, a phenyl group substituted amine compound, etc. are mentioned.
  • the organic compound having a nitrogen atom has an effective unshared electron pair content [n / M] (ratio of the number n of effective unshared electron pairs to the molecular weight M of the organic compound having a nitrogen atom) is 2.0 ⁇ .
  • the compound is selected to be 10 ⁇ 3 or more, and more preferably 3.9 ⁇ 10 ⁇ 3 or more.
  • the effective unshared electron pair is an unshared electron pair that does not participate in aromaticity and is not coordinated to the metal among the unshared electron pairs of the nitrogen atoms constituting the compound. To do.
  • the aromaticity here means an unsaturated cyclic structure in which atoms having ⁇ electrons are arranged in a ring, and is aromatic according to the so-called “Hückel rule”, and is included in the ⁇ electron system on the ring. Is 4n + 2 (n is an integer of 0 or more).
  • the effective unshared electron pair as described above is such that the unshared electron pair possessed by the nitrogen atom is aromatic regardless of whether or not the nitrogen atom itself provided with the unshared electron pair is a heteroatom constituting the aromatic ring. It is selected based on whether or not it is involved in the family. For example, even if a nitrogen atom is a heteroatom constituting an aromatic ring, if the nitrogen atom has an unshared electron pair that does not participate in aromaticity, the unshared electron pair is an effective unshared electron pair. Counted as one of
  • the number n of effective unshared electron pairs coincides with the number of nitrogen atoms having effective unshared electron pairs.
  • the effective unshared electron pair content [n / M] is based on the mixing ratio of each compound and the effective molecular weight M of the mixed compound.
  • the number n of unshared electron pairs is calculated, and the ratio of the number n of effective unshared electron pairs to the molecular weight M is defined as the effective unshared electron pair content [n / M], and this value is within the predetermined range described above. It is preferable that
  • the low molecular weight organic compound having a nitrogen atom constituting the underlayer the above-described exemplary compound No. 1 having an effective unshared electron pair content [n / M] of 2.0 ⁇ 10 ⁇ 3 or more is used. 1 to 45 are shown, but the present invention is not particularly limited thereto.
  • Exemplified Compound No. In 31 copper phthalocyanine among the unshared electron pairs of nitrogen atoms, the unshared electron pairs of nitrogen atoms not coordinated to copper are counted as effective unshared electron pairs.
  • the compounds exemplified below include the compounds represented by the aforementioned general formula (2) and general formula (3).
  • the above exemplified compound No. Table 1 shows the number n of effective unshared electron pairs, the molecular weight M, and the effective unshared electron pair content [n / M] for 1 to 45.
  • a polymer can also be used as the organic compound having a nitrogen atom.
  • the polymer having a nitrogen atom preferably has a weight average molecular weight in the range of 1,000 to 1,000,000.
  • the polymer having a nitrogen atom is preferably a polymer having a partial structure represented by the following general formula (P1) or a partial structure represented by the following general formula (P2).
  • a 1 represents a divalent nitrogen atom-containing group.
  • Y 1 represents a divalent organic group or a bond.
  • n1 represents the number of repetitions with a weight average molecular weight in the range of 1,000 to 1,000,000.
  • a 2 represents a monovalent nitrogen atom-containing group.
  • n2 represents an integer of 1 or more.
  • n2 is preferably an integer of 1 to 3 from the viewpoint of interaction with silver, and more preferably 1 or 2 from the viewpoint of ease of synthesis.
  • the plurality of A 2 may be the same or different.
  • a 3 and A 4 represent a divalent nitrogen atom-containing group.
  • a 3 and A 4 may be the same or different.
  • n3 and n4 each independently represents 0 or 1.
  • Y 2 represents an (n2 + 2) valent organic group.
  • n1 represents the number of repetitions with a weight average molecular weight in the range of 1,000 to 1,000,000.
  • the polymer having the partial structure represented by the general formula (P1) or (P2) is a homopolymer composed of only a single structural unit derived from the general formula (P1) or (P2). It may be a copolymer (copolymer) composed of only two or more structural units derived from the above general formulas (P1) and / or (P2).
  • the copolymer may be formed by further having another structural unit having no nitrogen atom-containing group.
  • the content of the monomer derived from the other structural unit has the effect of the polymer having a nitrogen atom according to the present invention.
  • it is not particularly limited as long as it is not impaired, it is preferably in the range of 10 to 75 mol%, more preferably in the range of 20 to 50 mol% in the monomers derived from all structural units.
  • the terminal of the polymer having the partial structure represented by the general formula (P1) or (P2) is not particularly limited and is appropriately defined depending on the type of raw material (monomer) used. is there.
  • the monovalent nitrogen atom-containing group represented by A 2 is not particularly limited as long as it is an organic group having a nitrogen atom.
  • nitrogen atom-containing groups include amino groups, dithiocarbamate groups, thioamide groups, cyano groups (—CN), isonitrile groups (—N + ⁇ C ⁇ ), isocyanate groups (—N ⁇ C ⁇ O). ), A thioisocyanate group (—N ⁇ C ⁇ S), or a group containing a substituted or unsubstituted nitrogen-containing aromatic ring.
  • PN1 to 41 Specific examples (PN1 to 41) of monomers constituting the polymer having a nitrogen atom applicable to the present invention are shown below, but are not particularly limited thereto.
  • the polymer having a nitrogen atom is composed of the following monomers having a repeating number in a range of a weight average molecular weight of 1,000 to 1,000,000.
  • low molecular organic compounds and polymers having nitrogen atoms applicable to the underlayer can be synthesized by known and well-known methods.
  • the organic compound having a sulfur atom applicable to the underlayer has a sulfide bond, disulfide bond, mercapto group, sulfone group, thiocarbonyl bond, etc. in the molecule. is doing. Among these, it is preferable to have a sulfide bond or a mercapto group.
  • the organic compound having a sulfur atom is preferably a compound represented by the following general formulas (A) to (D).
  • R 1 -SR 2 In General Formula (A), R 1 and R 2 each independently represent a substituent.
  • R 3 -SSR 4 In the general formula (B), R 3 and R 4 each independently represent a substituent.
  • R 6 represents a substituent
  • examples of the substituent represented by R 1 and R 2 include an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group).
  • alkyl group eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group.
  • substituents may be further substituted with these substituents, or may be linked to each other to form a ring.
  • examples of the substituent represented by R 3 and R 4 include the same substituents as the substituents represented by R 1 and R 2 in the general formula (A).
  • examples of the substituent represented by R 5 include the same substituents as the substituents represented by R 1 and R 2 in the general formula (A).
  • examples of the substituent represented by R 6 include the same substituents as the substituents represented by R 1 and R 2 in the general formula (A).
  • a polymer may be used as the organic compound having a sulfur atom.
  • the polymer having a sulfur atom preferably has a weight average molecular weight in the range of 1,000 to 1,000,000.
  • PS1 to 14 Specific examples (PS1 to 14) of monomers constituting the polymer having a sulfur atom are shown below, but are not particularly limited thereto.
  • the polymer having a sulfur atom is composed of the following monomers having a number of repetitions in a range where the weight average molecular weight is 1,000 to 1,000,000.
  • the numerical values added outside the parentheses represent the constituent ratio (also referred to as molar ratio or composition ratio) of each monomer unit.
  • Table 2 shows the weight average molecular weight of the polymer composed of the above monomer units.
  • the organic compound and polymer having a sulfur atom applicable to the present invention can be synthesized by a known and well-known method.
  • the weight average molecular weight of the polymer having a nitrogen atom or sulfur atom applicable to the present invention is a value measured under the following measurement conditions in a room temperature (25 ° C.) environment.
  • Calibration curve: Prepared with standard polystyrene (standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw 1000,000 to 500, a calibration curve (also referred to as calibration curve) was prepared, and the measurement object (This was used to calculate the weight average molecular weight.
  • the weight average molecular weight of the polystyrene used in the sample was set at approximately equal intervals.
  • the formation method of the underlayer include methods that can be usually used, such as a vapor deposition method, a CVD method, and a coating method (for example, a cast method, a spin coat method, etc.). Among these, the coating method is preferable because of its excellent production rate.
  • a solution is prepared by dissolving the organic compound according to the present invention in a suitable solvent, this solution is coated on a transparent support, dried, and then heat-treated. There is a way.
  • Other additives surfactant, viscosity modifier, preservative, etc. may be added to the solution as necessary.
  • the solvent is not particularly limited as long as it can dissolve an organic compound or the like, but is an alcohol such as isopropanol or n-butanol, or a halogen-containing halogen atom in which a hydrogen atom of an alcohol such as hexafluoroisopropanol or tetrafluoropropanol is substituted with a halogen atom.
  • an alcohol such as isopropanol or n-butanol
  • a halogen-containing halogen atom in which a hydrogen atom of an alcohol such as hexafluoroisopropanol or tetrafluoropropanol is substituted with a halogen atom.
  • Examples include alcohol, dimethyl sulfoxide, dimethylformamide and the like. These may be used alone or in combination of two or more.
  • alcohol halogen-containing alcohol, or a mixed solvent thereof is preferable.
  • the concentration (solid content concentration) of the organic compound (including other additives) in the solution is not particularly limited, but is preferably in the range of 0.005 to 0.5% by mass.
  • the coating method is not particularly limited, and examples thereof include spin coating, casting from a solution, dip coating, blade coating, wire bar coating, gravure coating, and spray coating. Furthermore, patterning can also be performed by a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.
  • a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.
  • the heat treatment conditions after coating are not particularly limited as long as the underlayer can be formed, but are preferably in the range of room temperature (25 ° C.) to 180 ° C., more preferably in the range of 60 to 120 ° C. is there.
  • the heat treatment time is preferably in the range of 10 seconds to 10 minutes, more preferably in the range of 30 seconds to 5 minutes. And the like. Of these, the vapor deposition method is preferably applied.
  • the gas barrier film of the present invention is characterized by having a metal layer 5 on the smooth layer 4 as shown in FIG.
  • the metal constituting the metal layer includes, for example, copper, tin, lead, aluminum, platinum, palladium, iridium, gold, zinc, nickel, titanium, zirconium, silver or an alloy thereof, or an oxide thereof.
  • the present invention is characterized in that the metal layer is a layer formed using silver or an alloy containing silver as a main component.
  • the metal layer 5 according to the present invention is a layer composed of silver or an alloy containing silver as a main component.
  • the metal layer 5 according to the present invention is formed on the smooth layer 4 as shown in FIG. 1 (a) or on the underlayer 6 as shown in FIGS. 1 (b) and 1 (c). Is a layer.
  • a method for forming the metal layer 5 As a method for forming the metal layer 5 according to the present invention, a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, etc. A method using a dry process such as the above can be selected as appropriate. Among the film forming methods, the vapor deposition method is preferably applied.
  • the metal layer 5 can be formed on the smooth layer 4 or the underlayer 6 so that it can have sufficient conductivity without a high-temperature annealing treatment after the film formation. Accordingly, high-temperature annealing treatment or the like after film formation may be performed.
  • Examples of the alloy mainly composed of silver (Ag) constituting the metal layer 5 include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), and silver indium (AgIn). ) And the like.
  • the metal layer 5 as described above may have a structure in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.
  • the metal layer 5 preferably has a thickness in the range of 4 to 12 nm. If the film thickness is 12 nm or less, the absorption component or reflection component of the layer can be controlled, and the high permeability of the transparent gas barrier film can be maintained.
  • Organic EL panel >> The gas barrier film of the present invention described above can be used as a sealing film for sealing electronic devices such as solar cells, liquid crystal display elements, and organic EL elements.
  • Organic EL device As an example of the organic EL element, a bottom emission type organic electroluminescence element will be described.
  • FIG. 4 is an example of an electronic device of the present invention, and is a cross-sectional configuration diagram illustrating an example of an organic electroluminescent element to which the transparent gas barrier film of the present invention is applied.
  • a transparent gas barrier film 1 is provided on a transparent substrate 2 and a light emitting functional layer 10 and a counter electrode 16 are laminated in this order on the transparent substrate 2.
  • the organic electroluminescent element 20 shown in FIG. 4 is provided on the transparent substrate 2, and in order from the transparent substrate 2 side, the gas barrier layer 3, the smooth layer 4, the base layer 6, the metal layer 5, The light emitting functional layer 10 and the counter electrode 16 are laminated.
  • the metal layer 5 of the transparent gas barrier film 1 is used as an anode.
  • Such an organic electroluminescent element 20 is configured as a bottom emission type in which emitted light h is extracted from at least the transparent substrate 2 side.
  • a transparent material having optical transparency is selected and used as the base material 2 constituting the transparent gas barrier film 1 of the present invention.
  • the overall layer structure of the organic electroluminescent device 20 is not limited and may be a general layer structure.
  • the hole injection layer 11 / hole transport layer 12 / light emitting layer 13 / electron transport layer 14 / electron injection layer 15 are formed on the metal layer 5 of the transparent gas barrier film 1 functioning as an anode.
  • a configuration in which the counter electrode 16 serving as a cathode is stacked on top of each other in this order is exemplified. However, among these, it is an indispensable constituent requirement to have at least the light emitting layer 13 made of an organic material.
  • the electron transport layer 14 also serves as the electron injection layer 15 and may be provided as the electron transport layer 14 having electron injection properties.
  • the light emitting functional layer 10 employs various constituent layers as necessary, and illustration thereof is omitted.
  • a hole blocking layer or an electron blocking layer is provided. May be.
  • the light emitting functional layer 3 is directly provided on the metal layer 5 functioning as an anode.
  • the auxiliary electrode 17 may be provided in contact with the metal layer 5 for the purpose of reducing the resistance of the metal layer 5 of the transparent gas barrier film 1 used as the anode. .
  • the counter electrode 16 provided as a cathode above the light emitting functional layer 10 is made of a metal, an alloy, an organic or inorganic conductive compound, a mixture thereof, or the like. Specific examples include metals such as gold (Au), oxide semiconductors such as copper iodide (CuI), ITO, ZnO, TiO 2 , and SnO 2 .
  • the counter electrode 16 as described above can be produced by forming these conductive materials as a thin film by a method such as vapor deposition or sputtering.
  • the sheet resistance as the counter electrode 16 is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually in the range of 5 nm to 5 ⁇ m, preferably in the range of 5 to 200 nm.
  • sealing material 18 for sealing the bottom emission type organic electroluminescent element 20 does not need to have a light transmission property.
  • the sealing material 18 covers the organic electroluminescent element 20, is a plate-shaped (film-shaped) sealing member, and is fixed to the transparent substrate 2 side by the adhesive 19, or It may be a sealing film. Such a sealing material 18 is provided so as to cover at least the light emitting functional layer 3 in a state where the metal layer 5 of the transparent gas barrier film 1 and the terminal portion of the counter electrode 16 in the organic electroluminescent element 20 are exposed. Yes.
  • the plate-like (film-like) sealing material 18 include a glass substrate, a polymer substrate, a metal substrate, and the like, and these substrate materials may be used as a thin film.
  • the glass substrate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal substrate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • the organic electroluminescent element can be made into a thin film
  • a polymer substrate or a metal substrate formed into a thin film can be preferably used as the sealing material.
  • the polymer substrate in the form of a film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less, and JIS K 7129-1992.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by a method in accordance with the above is 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less. It is preferable.
  • the above substrate material may be processed into a concave plate shape and used as the sealing material 18.
  • the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.
  • An adhesive 19 for fixing such a plate-shaped sealing material 18 to the transparent gas barrier film 1 or the counter electrode 16 side was sandwiched between the sealing material 18 and the transparent substrate 2. It is used as a sealant for sealing the organic electroluminescent element 20.
  • Specific examples of such an adhesive 19 include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, moisture curing types such as 2-cyanoacrylates, and the like. Can be mentioned.
  • examples of the adhesive 19 include an epoxy-based thermal and chemical curing type (two-component mixing). Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • the adhesive 19 is preferably one that can be adhesively cured from room temperature to 80 ° C. Further, a desiccant may be dispersed in the adhesive 19.
  • Application of the adhesive 19 to the bonded portion may be performed using a commercially available dispenser or may be printed like screen printing.
  • OPSTA Z7535 which is a UV curable organic / inorganic hybrid hard coat material manufactured by JSR Corporation
  • the coating film was cured under a curing condition of 1.0 J / cm 2 using a high-pressure mercury lamp in an air atmosphere to form a bleed-out prevention layer.
  • OPSTA Z7501 which is a UV curable organic / inorganic hybrid hard coat material manufactured by JSR Corporation was applied using a wire bar under the condition that the film thickness after application and drying was 4 ⁇ m. Then, after drying at 80 ° C. for 3 minutes, it was cured under a curing condition of 1.0 J / cm 2 using a high-pressure mercury lamp in an air atmosphere to form an anchor coat layer.
  • the obtained anchor coat layer was measured according to the surface roughness specified in JIS B 0601. As a result, the maximum cross-sectional height Rt (p) in the roughness curve was 16 nm.
  • the (average) film thickness after drying was 250 nm, it was coated on the anchor coat layer of the above-prepared substrate, and dried for 1 minute in dry air at a temperature of 50 ° C. and a dew point of ⁇ 5 ° C. Next, it was treated with dry air at a temperature of 95 ° C. and a dew point of ⁇ 5 ° C. for 2 minutes to form a polysilazane-containing layer on the anchor coat layer of the substrate.
  • ⁇ Modification treatment of polysilazane layer The surface of the formed polysilazane layer was irradiated with vacuum ultraviolet light (excimer modification treatment) under the following apparatus and modification conditions to modify the polysilazane layer to form a gas barrier layer.
  • a two-component polyurethane resin paint (first solution: Washin coat MP-6103A (solid normal acid solution having a solid content of 40% by mass) / tolylene diisocyanate-based modified isocyanate resin (having an isocyanate group) Material), second liquid: Washin coat MP-6103B (toluene / methyl ethyl ketone mixed solution with a solid content concentration of 30% by mass) / modified polyester resin (polyol)) is mixed, resulting in a solid content concentration of 10% by mass as a coating solution
  • a coating solution for forming a smooth layer was prepared by diluting with a 1: 1 mixed solvent of methyl ethyl ketone: methyl isobutyl ketone.
  • this coating solution for forming a smooth layer after coating using a wire bar under the condition that the film thickness after drying is 200 nm, drying is performed at 80 ° C. for 3 minutes as a drying condition, and then in an environment of 40 ° C. And left for 48 hours.
  • the maximum cross-sectional height Rt (p) in the roughness curve was 20 nm or less.
  • the surface roughness is calculated from an uneven cross-sectional curve continuously measured by a detector having a stylus having a minimum tip radius with an AFM (atomic force microscope), and the measurement direction is 30 ⁇ m with a stylus having a minimum tip radius.
  • the inside of the section was measured many times, and the average roughness regarding the amplitude of fine unevenness was obtained.
  • the base material formed up to the smooth layer was fixed to a base material holder of a vacuum vapor deposition apparatus by facing a vapor deposition mask for forming a vapor deposition region in a pattern. Subsequently, the compound A shown below was put into a resistance heating boat made of tantalum. These substrate holder and heating boat were attached to the first vacuum chamber of the vacuum deposition apparatus. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.
  • the first vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, and then heated by energizing a heating boat containing the following compound A, at a deposition rate of 0.1 to 0.2 nm / sec.
  • An underlayer having a thickness of 25 nm was provided on the smooth layer.
  • the base material formed up to the base layer was transferred to the second vacuum chamber while being vacuumed, and after the second vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, the heating boat containing silver was energized and heated. .
  • a metal layer having a thickness of 5 nm composed of silver was formed at a deposition rate of 0.1 to 0.2 nm / second, and a gas barrier film 1 was produced.
  • a gas barrier film 2 was produced in the same manner as in the production of the gas barrier film 1 except that the smooth layer was not formed.
  • a gas barrier film 3 was produced in the same manner as in the production of the gas barrier film 1 except that the formation of the underlayer was omitted.
  • a parallel plate type electrode pair was used as the plasma discharge device.
  • a base material formed up to the gas barrier layer was placed between the electrodes, and a mixed gas was introduced to form a thin film.
  • a ground (ground) electrode a 200 mm ⁇ 200 mm ⁇ 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed film, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried.
  • the electrode was cured by ultraviolet irradiation and sealed, and the dielectric surface thus coated was polished, smoothed, and processed to have an Rmax of 5 ⁇ m.
  • an electrode obtained by coating a dielectric on a hollow square pure titanium pipe under the same conditions as the ground electrode was used as the application electrode.
  • a plurality of application electrodes were prepared, and a plurality of application electrodes were provided at positions facing the ground electrode to form a discharge space.
  • a power source for generating plasma a high frequency power source CF-5000-13M manufactured by Pearl Industry Co., Ltd. was used, and 5 W / cm 2 of power was supplied at a frequency of 13.56 MHz.
  • a mixed gas having the following composition is introduced between the electrodes to form a plasma state, the substrate is subjected to atmospheric pressure plasma treatment, and a tin-doped indium oxide (ITO) film is formed to a thickness of 100 nm on the gas barrier layer. Then, a gas barrier film 4 was produced.
  • ITO indium oxide
  • ⁇ Mixed gas composition> Discharge gas: Helium 98.5% by volume Reactive gas 1: 0.25% by volume of oxygen Reactive gas 2: Indium acetylacetonate 1.2% by volume Reactive gas 3: Dibutyltin diacetate 0.05% by volume [Preparation of Gas Barrier Film 5: Present Invention]
  • a gas barrier film 5 was produced in the same manner except that the method for forming the gas barrier layer was changed to the following method.
  • a gas barrier layer (deposition layer) was formed by an evaporation method.
  • the first to third vapor deposition layers each contained a metal oxide (silicon oxide), and the thicknesses of the first to third vapor deposition layers were 100 nm, 30 nm, and 30 nm, respectively, for a total of 160 nm. .
  • the maximum cross-sectional height Rt (p) in the roughness curve was 30 nm or less.
  • the maximum cross-sectional height Rt (p) in the roughness curve was 40 nm or less.
  • the maximum cross-sectional height Rt (p) in the roughness curve was 40 nm or less.
  • Gas barrier films 9 to 15 were produced in the same manner as in the production of the gas barrier film 1 except that the thickness of the smooth layer to be formed was changed to the thickness shown in Table 1.
  • a gas barrier layer was formed using a plasma CVD method using a magnetic field application method.
  • the surface of the resin substrate opposite to the surface on which the anchor layer is formed is in contact with the film forming roller.
  • a gas barrier layer was formed on the anchor layer under the following film formation conditions (plasma CVD conditions) under the condition that the thickness was 300 nm.
  • ⁇ Plasma CVD conditions Feed rate of source gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute) Supply amount of oxygen gas (O 2 ): 500 sccm Degree of vacuum in the vacuum chamber: 3Pa Applied power from the power source for plasma generation: 0.8 kW Frequency of power source for plasma generation: 70 kHz Resin substrate transport speed: 2 m / min ⁇ Measurement of element distribution profile> The XPS depth profile measurement was performed on the formed gas barrier layer under the following conditions to obtain a silicon element distribution, an oxygen element distribution, a carbon element distribution, and an oxygen carbon distribution at a distance from the surface of the thin film layer in the layer thickness direction. .
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 10 nm
  • X-ray photoelectron spectrometer Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific Irradiation
  • X-ray Single crystal spectroscopy AlK ⁇ X-ray spot and its size: 800 ⁇ 400 ⁇ m ellipse From the silicon element distribution, oxygen element distribution, carbon element distribution and oxygen carbon distribution in the whole layer region measured as described above, the continuous change region in each element composition Presence / absence, presence / absence of extreme value, difference between maximum and minimum values of carbon atomic ratio, and average atomic ratio of silicon atoms, oxygen atoms, and carbon atoms in a region of 90% or more of the total thickness.
  • a gas barrier film 18 was produced in the same manner as in the production of the gas barrier film 17 except that the formation of the gas barrier layer and the formation of the underlayer were changed to the following methods.
  • the performance evaluation of the gas barrier film is caused by the water barrier property (measurement of the water vapor transmission rate immediately after the production and the water vapor transmission rate after the bending process) and the organic EL device using the gas barrier film, resulting from the gas barrier film. Evaluation of light emission unevenness resistance (dark spot resistance) of the organic EL element was performed.
  • Vapor deposition equipment JEE-400 vacuum vapor deposition equipment manufactured by JEOL Ltd.
  • Constant temperature and humidity oven Yamato Humidic Chamber IG47M Metal that reacts with water and corrodes: Calcium (granular)
  • Water vapor impermeable metal Aluminum ( ⁇ 3-5mm, granular)
  • Metallic calcium was vapor-deposited on the gas barrier layer (deposition layer, polysilazane modified layer) surface of the gas barrier films 1 to 16 using a vacuum evaporation apparatus (vacuum evaporation apparatus JEE-400 manufactured by JEOL Ltd.).
  • the metal calcium vapor deposition surface is bonded and bonded to quartz glass having a thickness of 0.2 mm via a sealing ultraviolet curable resin (manufactured by Nagase ChemteX) and irradiated with ultraviolet rays.
  • a sealing ultraviolet curable resin manufactured by Nagase ChemteX
  • An evaluation cell was produced.
  • the obtained sample (evaluation cell) was stored under high temperature and high humidity of 40 ° C. and 90% RH, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water was calculated.
  • a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample was stored under the same high temperature and high humidity conditions of 40 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 10000 hours.
  • the water content of each gas barrier film thus measured was classified into the following five stages, and the water vapor barrier property was evaluated.
  • Water content is less than 1 ⁇ 10 ⁇ 5 g / m 2 / day 4: Water content is 1 ⁇ 10 ⁇ 5 g / m 2 / day or more and less than 1 ⁇ 10 ⁇ 4 g / m 2 / day 3 : Moisture content is 1 ⁇ 10 ⁇ 4 g / m 2 / day or more, less than 1 ⁇ 10 ⁇ 3 g / m 2 / day 2: Moisture content is 1 ⁇ 10 ⁇ 3 g / m 2 / day or more, 1 ⁇ 10 ⁇ 2 g / m 2 / day less than 1: water content is 1 ⁇ 10 ⁇ 2 g / m 2 / day or more (measurement of water vapor permeability after bending treatment: evaluation of bending resistance) After each gas barrier film was bent 100 times with the gas barrier layer forming surface facing outward so that the radius of curvature was 5 mm, the water vapor permeability was measured by the same method as above,
  • Degradation degree of water vapor transmission rate [(water vapor transmission rate after bending test ⁇ water vapor transmission rate before bending test) / water vapor transmission rate before bending test)] ⁇ 100 (%)
  • the degree of deterioration of the water vapor transmission rate was evaluated by classifying into the following five stages.
  • FIG. 5 shows the unprocessed gas barrier films 1A to 18A that were not subjected to the bending treatment and the gas barrier films 1B to 18B that were subjected to the bending treatment, which were prepared in the evaluation of the gas barrier film, according to the following method.
  • Organic EL elements 1A to 18A gas barrier film unbent treatment
  • organic EL elements 1B to 18B with gas barrier film bent process having the structure described above were prepared, and the light emission spots of the organic EL elements due to the gas barrier film ( Dark spot resistance) was evaluated.
  • the produced gas barrier films 1A to 18A and samples 1B to 18B are cut to 100 mm ⁇ 80 mm to form a gas barrier film substrate (1).
  • the gas barrier film substrate having the metal layer is isopropyl. It was ultrasonically cleaned with alcohol and dried with dry nitrogen gas.
  • This gas barrier film substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of ⁇ -NPD is put into a molybdenum resistance heating boat, and 200 mg of CBP as a host compound is put into another resistance heating boat made of molybdenum.
  • 200 mg of Bathocuproin (BCP) is put in a molybdenum resistance heating boat, 100 mg of Ir-1 is put in another resistance heating boat made of molybdenum, and 200 mg of Alq 3 is put in another resistance heating boat made of molybdenum, and is attached to a vacuum deposition apparatus. It was.
  • the heating boat containing ⁇ -NPD was heated by heating, and the deposition rate was 0.1 nm / second so that it was positioned at the center of the transparent support substrate.
  • the hole transport layer was provided by vapor-depositing in an area of 80 mm ⁇ 60 mm. Further, the heating boat containing CBP and Ir-1 was energized and heated, and a light emitting layer was provided by co-evaporation on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing BCP was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a hole blocking layer having a thickness of 10 nm. Further, the heating boat containing Alq 3 is further heated by energization, and is deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport layer having a thickness of 40 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.
  • organic EL elements 1A to 18A gas barrier film unbent
  • Treatment and organic EL elements 1B to 18B (with gas barrier film bending treatment) were produced.
  • the luminance unevenness which can be visually discerned on the 3rd day was not observed, and all the generated dark spots were in a size (0.1 mm or less) which cannot be easily visually observed.
  • the non-light emitting area was 2.0% or more and less than 10% of the total light emitting area.
  • Luminance unevenness and dark spots visually observable were observed on day 0, and after 120 days, the total non-light-emitting area of the dark spots was 2.0% or more and less than 10% of the total light-emitting area.
  • Table 1 shows the evaluation results of the gas barrier film obtained as described above and the evaluation results when applied to an organic EL element.
  • the transparent gas barrier film having the structure defined in the present invention is superior in water vapor barrier properties and durability (bending resistance) to the comparative example. Furthermore, it can be seen that the electronic device (organic EL element) to which the transparent gas barrier film is applied is superior in dark spot resistance and durability (bending resistance) to the comparative example, and the occurrence of uneven brightness is reduced.
  • the transparent gas barrier film of the present invention has high gas barrier performance and has excellent durability (bending resistance), and gas barrier properties and durability (dark spot resistance) of various electronic devices such as organic EL elements.
  • the substrate can be suitably used as an excellent substrate.

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Abstract

La présente invention vise à concevoir une pellicule transparente formant barrière aux gaz, destinée à être utilisée en tant que substrat pour différents types de dispositifs électroniques, tels que des éléments électroluminescents organiques, et qui présente de très bonnes performances de barrière aux gaz et une haute durabilité (résistance au pliage), ainsi qu'un dispositif électronique présentant d'excellentes performances de barrière aux gaz et une haute durabilité (résistance à la formation de taches sombres) employant la pellicule formant barrière aux gaz. La pellicule transparente formant barrière aux gaz selon l'invention est caractérisée en ce qu'elle comporte au moins une couche formant barrière aux gaz, une couche d'égalisation et une couche métallique dans cet ordre sur un matériau de base, et la couche métallique est une couche formée en utilisant de l'argent ou un alliage comprenant de l'argent en tant que composant principal.
PCT/JP2013/061845 2012-04-26 2013-04-23 Pellicule transparente formant barrière aux gaz et dispositif électronique WO2013161785A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014148407A1 (fr) * 2013-03-21 2014-09-25 コニカミノルタ株式会社 Conducteur transparent
WO2015083706A1 (fr) * 2013-12-02 2015-06-11 コニカミノルタ株式会社 Film de barrière contre les gaz et procédé pour sa production
WO2015098672A1 (fr) * 2013-12-26 2015-07-02 住友化学株式会社 Film stratifié et dispositif électronique souple
WO2015098670A1 (fr) * 2013-12-26 2015-07-02 住友化学株式会社 Film stratifié, dispositif électroluminescent organique, dispositif de conversion photoélectrique, et dispositif d'affichage à cristaux liquides
WO2015115510A1 (fr) * 2014-01-31 2015-08-06 コニカミノルタ株式会社 Film de barrière contre les gaz et procédé pour sa fabrication
WO2015147221A1 (fr) * 2014-03-27 2015-10-01 コニカミノルタ株式会社 Film de barrière vis-à-vis des gaz et procédé de fabrication pour film de barrière vis-à-vis des gaz
WO2015152075A1 (fr) * 2014-03-31 2015-10-08 リンテック株式会社 Corps stratifié barrière contre les gaz, élément de dispositif électronique, et dispositif électronique
WO2016174950A1 (fr) * 2015-04-28 2016-11-03 コニカミノルタ株式会社 Élément électroluminescent organique
EP4340578A1 (fr) * 2022-09-16 2024-03-20 Samsung Display Co., Ltd. Dispositif d'affichage et son procédé de fabrication

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001358495A (ja) * 2000-06-16 2001-12-26 Toppan Printing Co Ltd 防汚処理を施した透明電磁波シールドフィルム
JP2004181793A (ja) * 2002-12-04 2004-07-02 Dainippon Printing Co Ltd ガスバリア性積層材及びその製造方法
JP2004291492A (ja) * 2003-03-27 2004-10-21 Matsushita Electric Works Ltd 光反射板、及びこの光反射板を備えた照明器具
JP2006058896A (ja) * 2000-02-01 2006-03-02 Mitsui Chemicals Inc プラズマディスプレイ用フィルタ、表示装置およびその製造方法
WO2006030762A1 (fr) * 2004-09-13 2006-03-23 Sumitomo Metal Mining Co., Ltd. Film conducteur transparent, procede de fabrication dudit film, materiau de base conducteur transparent et dispositif luminescent
JP2007168085A (ja) * 2005-12-19 2007-07-05 Toppan Printing Co Ltd 高ガスバリア性を有する積層体
WO2009148045A1 (fr) * 2008-06-06 2009-12-10 コニカミノルタホールディングス株式会社 Base de résine thermo-protectrice et élément de construction utilisant celle-ci
WO2011078156A1 (fr) * 2009-12-21 2011-06-30 コニカミノルタオプト株式会社 Film miroir, son procede de production, et dispositif de reflexion pour generateur d'energie thermique solaire utilisant ce film miroir

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006058896A (ja) * 2000-02-01 2006-03-02 Mitsui Chemicals Inc プラズマディスプレイ用フィルタ、表示装置およびその製造方法
JP2001358495A (ja) * 2000-06-16 2001-12-26 Toppan Printing Co Ltd 防汚処理を施した透明電磁波シールドフィルム
JP2004181793A (ja) * 2002-12-04 2004-07-02 Dainippon Printing Co Ltd ガスバリア性積層材及びその製造方法
JP2004291492A (ja) * 2003-03-27 2004-10-21 Matsushita Electric Works Ltd 光反射板、及びこの光反射板を備えた照明器具
WO2006030762A1 (fr) * 2004-09-13 2006-03-23 Sumitomo Metal Mining Co., Ltd. Film conducteur transparent, procede de fabrication dudit film, materiau de base conducteur transparent et dispositif luminescent
JP2007168085A (ja) * 2005-12-19 2007-07-05 Toppan Printing Co Ltd 高ガスバリア性を有する積層体
WO2009148045A1 (fr) * 2008-06-06 2009-12-10 コニカミノルタホールディングス株式会社 Base de résine thermo-protectrice et élément de construction utilisant celle-ci
WO2011078156A1 (fr) * 2009-12-21 2011-06-30 コニカミノルタオプト株式会社 Film miroir, son procede de production, et dispositif de reflexion pour generateur d'energie thermique solaire utilisant ce film miroir

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014148407A1 (fr) * 2013-03-21 2014-09-25 コニカミノルタ株式会社 Conducteur transparent
JPWO2014148407A1 (ja) * 2013-03-21 2017-02-16 コニカミノルタ株式会社 透明導電体
WO2015083706A1 (fr) * 2013-12-02 2015-06-11 コニカミノルタ株式会社 Film de barrière contre les gaz et procédé pour sa production
WO2015098670A1 (fr) * 2013-12-26 2015-07-02 住友化学株式会社 Film stratifié, dispositif électroluminescent organique, dispositif de conversion photoélectrique, et dispositif d'affichage à cristaux liquides
CN105848880A (zh) * 2013-12-26 2016-08-10 住友化学株式会社 层叠膜和柔性电子器件
WO2015098672A1 (fr) * 2013-12-26 2015-07-02 住友化学株式会社 Film stratifié et dispositif électronique souple
US10704148B2 (en) 2013-12-26 2020-07-07 Sumitomo Chemical Company, Limited Laminated film and flexible electronic device
WO2015115510A1 (fr) * 2014-01-31 2015-08-06 コニカミノルタ株式会社 Film de barrière contre les gaz et procédé pour sa fabrication
WO2015147221A1 (fr) * 2014-03-27 2015-10-01 コニカミノルタ株式会社 Film de barrière vis-à-vis des gaz et procédé de fabrication pour film de barrière vis-à-vis des gaz
WO2015152075A1 (fr) * 2014-03-31 2015-10-08 リンテック株式会社 Corps stratifié barrière contre les gaz, élément de dispositif électronique, et dispositif électronique
JPWO2015152075A1 (ja) * 2014-03-31 2017-04-13 リンテック株式会社 ガスバリア性積層体、電子デバイス用部材および電子デバイス
WO2016174950A1 (fr) * 2015-04-28 2016-11-03 コニカミノルタ株式会社 Élément électroluminescent organique
EP4340578A1 (fr) * 2022-09-16 2024-03-20 Samsung Display Co., Ltd. Dispositif d'affichage et son procédé de fabrication

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