WO2023153307A1 - Film barrière aux gaz, son procédé de production, plaque de polarisation avec couche barrière aux gaz et dispositif d'affichage d'image - Google Patents

Film barrière aux gaz, son procédé de production, plaque de polarisation avec couche barrière aux gaz et dispositif d'affichage d'image Download PDF

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WO2023153307A1
WO2023153307A1 PCT/JP2023/003384 JP2023003384W WO2023153307A1 WO 2023153307 A1 WO2023153307 A1 WO 2023153307A1 JP 2023003384 W JP2023003384 W JP 2023003384W WO 2023153307 A1 WO2023153307 A1 WO 2023153307A1
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layer
gas barrier
film
barrier film
less
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PCT/JP2023/003384
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English (en)
Japanese (ja)
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帆奈美 伊藤
一裕 中島
徹 梅本
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日東電工株式会社
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Publication of WO2023153307A1 publication Critical patent/WO2023153307A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a gas barrier film, a method for producing the same, a polarizing plate with a gas barrier layer, and an image display device.
  • resin film substrates are being used instead of glass substrates. Since resin films have higher permeability to gases such as water vapor and oxygen than glass, it has been proposed to use a gas barrier film having a gas barrier layer for the purpose of suppressing deterioration of display elements caused by these gases.
  • Organic EL elements may have defects called “dark spots” due to the infiltration of even a small amount of moisture, and high gas barrier properties (water vapor blocking properties) are required.
  • Silicon nitride (SiN) and silicon oxynitride (SiON) are known as materials having excellent gas barrier properties.
  • bendable display devices flexible displays, foldable displays, etc.
  • display elements such as organic EL elements are formed on flexible substrates
  • the gas barrier film is required to have no cracks in the gas barrier layer (flex resistance) when the film is folded.
  • Patent Document 1 proposes a gas barrier film including a silicon nitride layer and a silicon oxide layer as a gas barrier film having excellent transparency and bending resistance.
  • Patent Document 1 has room for improvement in terms of increasing the transparency, bending resistance, and gas barrier properties of the gas barrier film.
  • the present invention has been made in view of the above problems, and aims to provide a gas barrier film excellent in transparency, flex resistance, and gas barrier properties, a method for producing the same, and a polarizing plate with a gas barrier layer using the gas barrier film, and It is to provide an image display device.
  • the present invention includes the following aspects.
  • a gas barrier film comprising a transparent film substrate and a gas barrier layer disposed directly or indirectly on at least one main surface of the transparent film substrate,
  • the gas barrier layer has a silicon oxycarbide layer containing silicon, oxygen and carbon as constituent elements,
  • the silicon oxycarbide layer has a first layer, a second layer and a third layer in this order from the transparent film substrate side,
  • the carbon content in the first layer and the carbon content in the third layer are both less than 0.1 atomic % with respect to a total of 100 atomic % of silicon, oxygen and carbon
  • the carbon content in the second layer is 0.1 atomic % or more with respect to a total of 100 atomic % of silicon, oxygen and carbon
  • the thickness ratio of the second layer is 20% or more and 70% or less with respect to 100% of the total thickness of the first layer, the second layer and the third layer,
  • the carbon content at the point where the carbon content with respect to the total of 100 atomic % of silicon, oxygen and carbon shows the maximum value when the composition analysis in the
  • C max atomic % is C max atomic %
  • C min atomic % is the carbon content at the point where the carbon content with respect to the total 100 atomic % of silicon, oxygen and carbon shows the minimum value, the value obtained by subtracting C min from C max is 6.0 or less.
  • the thickness ratio of the second layer is 20% or more and 55% or less with respect to 100% of the total thickness of the first layer, the second layer and the third layer [1] or [ 2].
  • a method for producing a gas barrier film according to any one of [1] to [7], A method for producing a gas barrier film, comprising introducing an organosilicon compound and oxygen into a chamber of a film-forming apparatus having a pair of film-forming rolls as a pair of counter electrodes, and forming the silicon oxycarbide layer by a chemical vapor deposition method. .
  • a polarizing plate with a gas barrier layer comprising the gas barrier film according to any one of [1] to [7] above and a polarizer.
  • An image display device comprising the gas barrier film according to any one of [1] to [7] and an image display cell.
  • An image display device comprising the polarizing plate with a gas barrier layer according to [9] and an image display cell.
  • the present invention it is possible to provide a gas barrier film excellent in transparency, flex resistance, and gas barrier properties, a method for producing the same, and a polarizing plate with a gas barrier layer and an image display device using the gas barrier film.
  • FIG. 1 is a cross-sectional view showing an example of a gas barrier film according to the present invention
  • FIG. FIG. 4 is a cross-sectional view showing another example of the gas barrier film according to the present invention
  • FIG. 4 is a cross-sectional view showing another example of the gas barrier film according to the present invention
  • FIG. 4 is a cross-sectional view showing another example of the gas barrier film according to the present invention
  • FIG. 4 is a cross-sectional view showing another example of the gas barrier film according to the present invention
  • 1 is a configuration diagram showing an example of a film forming apparatus used in a method for producing a gas barrier film according to the present invention
  • FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of the polarizing plate with a gas barrier layer which concerns on this invention. It is a sectional view showing an example of an image display device concerning the present invention.
  • the number average primary particle diameter of the particles is the circle of 100 primary particles measured using a scanning electron microscope and image processing software (e.g., "ImageJ” manufactured by the National Institutes of Health), unless otherwise specified. It is the number average value of equivalent diameters (Heywood diameter: diameter of a circle having the same area as the projected area of primary particles).
  • Layered material (more specifically, transparent film substrate, gas barrier layer, silicon oxycarbide layer, first layer, second layer, third layer, hard coat layer, adhesive layer, polarizer, etc.) ” refers to a plane orthogonal to the thickness direction of the layered material.
  • the thickness of the gas barrier layer and each layer constituting the gas barrier layer can be determined using X-ray photoelectron spectroscopy. It is a value obtained by converting the etching time of the layer when analyzing the composition in the direction using the value of the sputtering rate for SiO 2 .
  • the numerical value of the “thickness” of the gas barrier layer and the layered material other than each layer constituting the gas barrier layer is the “average thickness”.
  • the average thickness of the layered material is obtained by observing a cross section of the layered material cut in the thickness direction with an electron microscope, randomly selecting 10 measurement points from the cross-sectional image, and measuring the thickness of the selected 10 measurement points. Arithmetic mean of 10 measurements obtained.
  • Refractive index refers to the refractive index for light with a wavelength of 550 nm in an atmosphere at a temperature of 23°C.
  • the flow rate unit “sccm (Standard Cubic Centimeter per Minute)” is the flow rate unit “mL/min” under standard conditions (temperature: 0° C., pressure: 101.3 kPa).
  • system may be added after the name of the compound to generically refer to the compound and its derivatives.
  • polymer name is expressed by adding "system” after the compound name, it means that the repeating unit of the polymer is derived from the compound or its derivative.
  • acryl and methacryl may be collectively referred to as "(meth)acryl”.
  • a gas barrier film according to a first embodiment of the present invention has a transparent film substrate and a gas barrier layer directly or indirectly arranged on at least one main surface of the transparent film substrate.
  • the gas barrier layer has a silicon oxycarbide layer containing silicon, oxygen and carbon as constituent elements.
  • the silicon oxycarbide layer has a first layer, a second layer and a third layer in this order from the transparent film substrate side.
  • the carbon content in the first layer is less than 0.1 atomic % with respect to 100 atomic % in total of silicon, oxygen and carbon.
  • the carbon content in the third layer is less than 0.1 atomic % with respect to 100 atomic % in total of silicon, oxygen and carbon.
  • the carbon content in the second layer is 0.1 atomic % or more with respect to 100 atomic % in total of silicon, oxygen and carbon.
  • the thickness ratio of the second layer is 20% or more and 70% or less with respect to 100% of the total thickness of the first, second and third layers.
  • the method of analyzing the composition in the thickness direction of the silicon oxycarbide layer using X-ray photoelectron spectroscopy is the same method as in Examples described later or a method based thereon.
  • X-ray photoelectron spectroscopy may be referred to as "XPS”.
  • carbon content when the total of silicon, oxygen and carbon is 100 atomic % is sometimes simply referred to as “carbon content”.
  • the ratio of the thickness of the second layer to the total thickness of 100% of the first layer, the second layer and the third layer may be simply referred to as the "second layer thickness ratio".
  • the carbon content at the point (measurement point) where the carbon content shows the maximum value is described as "C max atomic %". I have something to do.
  • the carbon content at the location (measurement location) where the carbon content is the minimum value is described as "C min atomic %”. I have something to do.
  • the carbon content in the first layer is less than 0.1 atomic %
  • any measurement point in the first layer also means that the carbon content is less than 0.1 atomic %.
  • the measurement interval of the elemental composition is, for example, within the range of 30 seconds or more and 90 seconds or less (2.5 nm or more and 7.5 nm or less), preferably 60 seconds (5 nm).
  • the composition analysis in the thickness direction of the silicon oxycarbide layer is performed at intervals of 5 nm
  • the thickness direction (depth direction) of the silicon oxycarbide layer is sequentially 0 nm (etching start position), 5 nm, 10 nm, 15 nm
  • Composition analysis is performed at positions of 20 nm, 25 nm, and so on.
  • the measurement results of the carbon content when performing composition analysis in the thickness direction of the silicon oxycarbide layer at intervals of 5 nm are, for example, 0 nm: less than 0.1 atomic %, 5 nm: less than 0.1 atomic %, 10 nm: 0.1 atomic % or more, 15 nm: 0.1 atomic % or more, 25 nm: less than 0.1 atomic %, the second layer is formed in the thickness direction from the surface (etching start position) of the silicon oxycarbide layer. is in the range of 10 nm or more and 15 nm or less.
  • the transparency and bending resistance of the silicon oxycarbide layer tend to decrease when the carbon content in the silicon oxycarbide layer is too high or too low.
  • the carbon content in the silicon oxycarbide layer is too low, the surface of the silicon oxycarbide layer tends to be too rough and the gas barrier properties of the silicon oxycarbide layer tend to decrease. be.
  • the difference between the maximum and minimum carbon content in the silicon oxycarbide layer becomes too large, the silicon oxycarbide layer becomes a film with a non-uniform composition. , the gas barrier properties of the silicon oxycarbide layer tend to decrease.
  • the thickness ratio of the second layer having a relatively high carbon content is 20% or more and 70% or less, so the carbon content of the entire silicon oxycarbide layer is is in an appropriate range, and the silicon oxycarbide layer has good transparency and bending resistance. Therefore, according to the first embodiment, it is possible to provide a gas barrier film having excellent transparency and bending resistance.
  • the value obtained by subtracting C min from C max is preferably 2.0 or more, more preferably 3.0 or more. , 4.0 or more.
  • the second layer thickness ratio is preferably 20% or more and 60% or less, more preferably 20% or more and 55% or less, in order to obtain a gas barrier film that is more excellent in transparency and flex resistance. is more preferred.
  • the ratio of the thickness of the first layer to the total thickness of 100% of the first layer, the second layer, and the third layer and The thickness ratio of each of the third layers is preferably 10% or more and 50% or less, and more preferably 20% or more and 45% or less.
  • the thickness ratio of the first layer and the thickness ratio of the third layer may be the same value or different values.
  • Condition 1 The second layer thickness ratio is 20% or more and 55% or less, and the value obtained by subtracting Cmin from Cmax is 2.0 or more and 6.0 or less.
  • Condition 2 The second layer thickness ratio is 45% or more and 55% or less, and the value obtained by subtracting Cmin from Cmax is 5.0 or more and 6.0 or less.
  • Condition 3 The second layer thickness ratio is 20% or more and 30% or less, and the value obtained by subtracting Cmin from Cmax is 4.0 or more and 5.0 or less.
  • FIG. 1 is a cross-sectional view showing an example of the gas barrier film according to the first embodiment.
  • a gas barrier film 10 shown in FIG. 1 is a laminate having a transparent film substrate 11 and a gas barrier layer 12 directly disposed on one main surface 11 a of the transparent film substrate 11 .
  • the gas barrier layer 12 is composed of a silicon oxycarbide layer 13 containing silicon, oxygen and carbon as constituent elements.
  • the silicon oxycarbide layer 13 has a first layer 14, a second layer 15 and a third layer 16 in this order from the transparent film substrate 11 side.
  • the carbon content in the first layer 14 is less than 0.1 atomic percent.
  • the carbon content in the third layer 16 is less than 0.1 atomic percent.
  • the carbon content in the second layer 15 is 0.1 atomic % or more.
  • the thickness ratio of the second layer 15 is 20% or more and 70% or less with respect to 100% of the total thickness of the first layer 14, the second layer 15 and the third layer 16. In the silicon oxycarbide layer 13, the value obtained by subtracting Cmin from Cmax is 6.0 or less.
  • the measurement point showing the minimum carbon content exists in at least one of the first layer 14 and the third layer 16 .
  • the second layer 15 has the maximum carbon content.
  • the minimum carbon content of the first layer 14 and the minimum carbon content of the third layer 16 are not particularly limited, and both may be 0.0 atomic %.
  • the carbon content rate changes continuously in the thickness direction of the silicon oxycarbide layer 13 .
  • the gas barrier layer 21 has the silicon oxycarbide layer 13 and the gas barrier layer 22 disposed on the main surface 16a of the silicon oxycarbide layer 13 opposite to the transparent film substrate 11 side.
  • the gas barrier layer 22 is preferably a silicon oxynitride layer containing silicon, oxygen and nitrogen as constituent elements.
  • the gas barrier film according to the first embodiment may have gas barrier layers on both main surfaces of the silicon oxycarbide layer. Moreover, the gas barrier film according to the first embodiment may have a gas barrier layer only on the main surface of the silicon oxycarbide layer on the transparent film substrate side. Further, in the gas barrier film according to the first embodiment, the gas barrier layer may include two or more silicon oxycarbide layers, for example, two silicon oxycarbide layers and three silicon oxynitride layers. Alternating laminates may also be used. The gas barrier layer may have a laminate structure of four layers or a laminate structure of six or more layers.
  • the gas barrier layer may be indirectly arranged on the main surface of the transparent film substrate.
  • the gas barrier film 30 shown in FIG. 3 has a hard coat layer 31 arranged between the transparent film substrate 11 and the gas barrier layer 12 (silicon oxycarbide layer 13).
  • the gas barrier layer 12 is indirectly arranged on the main surface of the transparent film substrate 11 .
  • the hard coat layer 31 is a layer that enhances mechanical properties such as hardness and elastic modulus of the gas barrier film 30 . If the main surface of the hard coat layer 31 on the side of the gas barrier layer 12 is smooth, the gas barrier property of the gas barrier layer 12 formed thereon is enhanced, and the water vapor transmission rate tends to decrease.
  • the arithmetic mean height Sa of the main surface of the hard coat layer 31 on the side of the gas barrier layer 12 may be 1.5 nm or less or 1.0 nm or less.
  • the arithmetic mean height Sa is calculated in accordance with ISO 25178 from the three-dimensional surface shape in the range of 1 ⁇ m ⁇ 1 ⁇ m measured with an atomic force microscope (AFM).
  • the hard coat layer 31 may contain particles with a number average primary particle diameter of less than 1.0 ⁇ m (hereinafter sometimes referred to as "nanoparticles"). For example, when the hard coat layer 31 contains nanoparticles, fine irregularities are formed on the surface of the hard coat layer 31, and adhesion between the hard coat layer 31 and the gas barrier layer 12 tends to be improved.
  • the gas barrier film according to the first embodiment may be provided with gas barrier layers on both main surfaces of the transparent film substrate in order to further improve gas barrier properties.
  • a gas barrier layer having a laminated structure may be provided on each of both main surfaces of the transparent film substrate.
  • the elemental composition of the gas barrier layer 41 may be the same as or different from the elemental composition of the gas barrier layer 12 .
  • the layer structure of the gas barrier layer 41 may be the same as or different from the layer structure of the gas barrier layer 12 .
  • the gas barrier layer 41 preferably has a silicon oxycarbide layer.
  • the silicon oxycarbide layer in the gas barrier layer 41 should have a carbon content of less than 0.1 atomic % from the transparent film substrate 11 side.
  • the gas barrier film according to the first embodiment may further have an adhesive layer.
  • the gas barrier film 50 shown in FIG. 5 has an adhesive layer 51 in addition to the configuration of the gas barrier film 40 .
  • an adhesive layer 51 is arranged on the main surface 16a of the gas barrier layer 12 (silicon oxycarbide layer 13) opposite to the transparent film substrate 11 side.
  • a release liner may be temporarily attached to the main surface of the pressure-sensitive adhesive layer 51 opposite to the silicon oxycarbide layer 13 side.
  • the release liner protects the surface of the pressure-sensitive adhesive layer 51, for example, until the gas barrier film 50 is attached to the polarizing plate 101 (see FIG. 7), which will be described later.
  • Plastic films made of acrylic, polyolefin, cyclic polyolefin, polyester or the like are preferably used as the constituent material of the release liner.
  • the thickness of the release liner is, for example, 5 ⁇ m or more and 200 ⁇ m or less.
  • the surface of the release liner is preferably subjected to release treatment. Examples of release agent materials used in release treatment include silicone-based materials, fluorine-based materials, long-chain alkyl-based materials, fatty acid amide-based materials, and the like.
  • the transparent film substrate 11 is, for example, a layer that serves as a base for forming a gas barrier layer.
  • the transparent film substrate 11 may have flexibility.
  • the gas barrier layer can be formed by a roll-to-roll method, so the productivity of the gas barrier layer can be improved.
  • a gas barrier film in which a gas barrier layer is provided on a flexible film also has the advantage of being applicable to flexible devices and foldable devices.
  • the visible light transmittance of the transparent film substrate 11 is preferably 80% or higher, more preferably 90% or higher.
  • the thickness of the transparent film substrate 11 is not particularly limited, but from the viewpoint of strength, handleability, etc., it is preferably 5 ⁇ m or more and 200 ⁇ m or less, more preferably 10 ⁇ m or more and 150 ⁇ m or less, and 30 ⁇ m or more and 100 ⁇ m or less. is more preferred.
  • resin material that constitutes the transparent film substrate 11 a resin material that is excellent in transparency, mechanical strength and thermal stability is preferable.
  • resin materials include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) Examples include acrylic resins, cyclic polyolefin resins (more specifically, norbornene resins, etc.), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
  • Corona treatment, plasma treatment, flame treatment, ozone treatment, glow treatment, saponification treatment, and coupling agent are applied to the main surface of the transparent film substrate 11 on which the gas barrier layer is formed, for the purpose of improving adhesion with the gas barrier layer.
  • Surface modification treatment such as treatment with may be applied.
  • the surface layer of the transparent film substrate 11 on which the gas barrier layer is formed may be a primer layer (not shown).
  • the primer layer When the surface layer on which the gas barrier layer is formed is the primer layer, the adhesion between the transparent film substrate 11 and the gas barrier layer tends to be high.
  • Examples of materials constituting the primer layer include metals (or semi-metals) such as silicon, nickel, chromium, tin, gold, silver, platinum, zinc, indium, titanium, tungsten, aluminum, zirconium, and palladium; alloys (or metalloids); oxides, fluorides, sulfides or nitrides of these metals (or metalloids);
  • the thickness of the primer layer is, for example, 1 nm or more and 20 nm or less, preferably 1 nm or more and 15 nm or less, and more preferably 1 nm or more and 10 nm or less.
  • the silicon oxycarbide layer 13 is a layer mainly having a gas barrier function in the gas barrier layer, and is a layer made of a material containing silicon, oxygen and carbon as main constituent elements.
  • the silicon oxycarbide layer 13 employs, for example, a chemical vapor deposition method (CVD method) as a film forming method, and uses a film forming apparatus shown in FIG. It is obtained by successively forming three layers 16 under the same conditions.
  • CVD method chemical vapor deposition method
  • FIG. 6 uses a film forming apparatus shown in FIG. It is obtained by successively forming three layers 16 under the same conditions.
  • the first layer 14, the second layer 15 and the third layer 16 are continuously formed under the same conditions, for example, using a transmission electron microscope.
  • the silicon oxycarbide layer 13 may contain a small amount of elements such as hydrogen and nitrogen that are taken in from the raw materials during film formation, the transparent film substrate 11 and the external environment.
  • the content of elements other than silicon, oxygen, and carbon is preferably 3 atomic % or less, more preferably 1 atomic % or less, and 0.5 atomic % or less. It is even more preferable to have Among the elements constituting the silicon oxycarbide layer 13, the total content of silicon, oxygen and carbon is preferably 90 atomic % or more, more preferably 95 atomic % or more, and 97 atomic % or more. More preferably, it may be 99 atomic % or more, 99.5 atomic % or more, or 99.9 atomic % or more.
  • total etching time means the time from the start to the end of the etching of the silicon oxycarbide layer 13 when the composition analysis in the thickness direction of the silicon oxycarbide layer 13 is performed by the same method as in Examples described later or a method based thereon. means the time of
  • x is preferably 1.5 or more and 2.5 or less, y is preferably 0.01 or more and 0.5 or less, and x is 1.8. It is more preferable that y is not less than 2.2 and y is not less than 0.05 and not more than 0.2.
  • the method for forming the silicon oxycarbide layer 13 is not particularly limited, and may be a dry coating method or a wet coating method.
  • the silicon oxycarbide layer 13 is preferably formed by a CVD method, more preferably by a plasma CVD method.
  • organosilicon compounds hexamethyldisiloxane is particularly preferred because it can suppress incorporation of impurities into the film and can form a film with high transparency and gas barrier properties.
  • organosilicon compound as the silicon source also serves as a carbon source
  • an organic compound containing no silicon may be used as the carbon source in addition to the organosilicon compound.
  • Oxygen sources include oxygen, carbon monoxide, carbon dioxide, and the like. Oxygen (oxygen gas) is preferable as the oxygen source from the viewpoint of handleability.
  • the composition of the silicon oxycarbide layer 13 can be appropriately adjusted by changing the introduction amount of the oxygen source (or the oxygen source and the carbon source) relative to the silicon source.
  • the thickness of the silicon oxycarbide layer 13 is preferably 10 nm or more and 500 nm or less, more preferably 50 nm or more and 400 nm or less, and 80 nm or more and 300 nm or less. is more preferred.
  • the total thickness of the gas barrier layer is 20 nm or more and 1000 nm or less from the viewpoint of achieving both high gas barrier properties and transparency. preferably 50 nm or more and 800 nm or less.
  • the hard coat layer 31 contains, for example, a binder resin and nanoparticles.
  • a binder resin curable resins such as thermosetting resins, photocurable resins and electron beam curable resins are preferably used.
  • curable resins include polyester resins, acrylic resins, urethane resins, acrylic urethane resins, amide resins, silicone resins, silicate resins, epoxy resins, melamine resins, and oxetane resins. mentioned.
  • One or more curable resins can be used.
  • acrylic resins acrylic urethane resins, and epoxy resins are preferable because they have high hardness and can be photocured, and acrylic resins and acrylic urethane resins. More preferably, one or more selected from the group consisting of
  • the number average primary particle diameter of the nanoparticles contained in the hard coat layer 31 is preferably 15 nm or more, more preferably 20 nm or more, from the viewpoint of enhancing dispersibility in the binder resin. From the viewpoint of forming fine irregularities that contribute to improved adhesion, the number average primary particle diameter of the nanoparticles contained in the hard coat layer 31 is preferably 90 nm or less, more preferably 70 nm or less. It is more preferably 50 nm or less.
  • Inorganic oxides are preferable as materials for nanoparticles.
  • examples of inorganic oxides include metal (or metalloid) oxides such as silica, titanium oxide, aluminum oxide, zirconium oxide, niobium oxide, zinc oxide, tin oxide, cerium oxide, and magnesium oxide.
  • the inorganic oxide may be a composite oxide of multiple (semi)metals.
  • silica is preferable because it has a high adhesion improving effect. That is, silica particles (nanosilica particles) are preferable as the nanoparticles.
  • a functional group such as an acrylic group or an epoxy group may be introduced into the surface of the inorganic oxide particles as nanoparticles for the purpose of enhancing adhesion and affinity with the resin.
  • the hard coat layer 31 is formed by applying the hard coat composition onto the transparent film substrate 11, and optionally removing the solvent and curing the resin.
  • the hard coat composition contains, for example, the above binder resin and nanoparticles, and optionally contains a solvent capable of dissolving or dispersing these components.
  • the resin component in the hard coat composition is a curable resin
  • the hard coat composition preferably contains an appropriate polymerization initiator.
  • the resin component in the hard coat composition is a photocurable resin
  • the hard coat composition preferably contains a photopolymerization initiator.
  • any suitable method such as bar coating, roll coating, gravure coating, rod coating, slot orifice coating, curtain coating, fountain coating, comma coating, etc. can be used. can be adopted.
  • Adhesive layer 51 As a constituent material of the adhesive layer 51, an adhesive having a high visible light transmittance is preferably used.
  • adhesives constituting the adhesive layer 51 include acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyvinyl ethers, vinyl acetate-vinyl chloride copolymers, modified polyolefins, epoxy resins, and fluorine resins. , natural rubber, synthetic rubber or the like as a base polymer can be appropriately selected and used.
  • the thickness of the adhesive layer 51 is preferably 5 ⁇ m or more and 100 ⁇ m or less.
  • the refractive index of the adhesive layer 51 is, for example, 1.4 or more and 1.5 or less.
  • the water vapor transmission rate of the gas barrier film is preferably 0.10 g/m 2 ⁇ day or less, more preferably 0.08 g/m 2 ⁇ day or less, as a standardized value based on a gas barrier film having a gas barrier layer with a thickness of 100 nm. is more preferable. From the viewpoint of suppressing deterioration of the protection object such as the organic EL element, the lower the water vapor transmission rate, the better.
  • the lower limit of the water vapor transmission rate of the gas barrier film is not particularly limited, it is generally 1.0 ⁇ 10 ⁇ 5 g/m 2 ⁇ day as the normalized value.
  • the water vapor transmission rate (WVTR) is measured under conditions of a temperature of 40° C. and a relative humidity difference of 90%, according to the description in JIS K 7129:2008 Annex B (Mocon method).
  • the light transmittance of the gas barrier film is preferably 80% or higher, more preferably 90% or higher.
  • Light transmittance is the Y value of the CIE tristimulus values specified in JlS Z8781-3:2016.
  • the light transmittance of the gas barrier film can be adjusted, for example, by changing the second layer thickness ratio.
  • the method for manufacturing the gas barrier film according to the second embodiment is a suitable method for manufacturing the gas barrier film according to the first embodiment described above. Therefore, descriptions of components that overlap with those of the above-described first embodiment may be omitted.
  • an organosilicon compound eg, hexamethyldisiloxane
  • a step of introducing oxygen and forming a silicon oxycarbide layer by a CVD method is provided.
  • FIG. 6 is a configuration diagram showing an example of a film forming apparatus used in the method for producing a gas barrier film according to the second embodiment.
  • the film forming apparatus shown in FIG. 6 includes a delivery roll 71, transport rolls 72, 73, 74 and 75, film forming rolls 76 and 77 as a pair of opposing electrodes, a winding roll 78, and a film forming gas. and a gas supply port 79 for A plurality of gas supply ports 79 may be provided.
  • a magnetic field generator (not shown) is installed inside each of the film forming rolls 76 and 77 .
  • at least the film forming rolls 76 and 77, the gas supply port 79, and the power source for plasma generation are arranged in a vacuum chamber (not shown).
  • the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.
  • the film forming rolls 76 and 77 are each provided with a power source for plasma generation so that the pair of film forming rolls (film forming rolls 76 and 77) can function as a pair of opposing electrodes. (not shown). Therefore, in the film forming apparatus shown in FIG. 6, by supplying power from the plasma generation power supply, it is possible to discharge the space between the film forming rolls 76 and 77, thereby forming a film. Plasma can be generated in the space between the roll 76 and the film forming roll 77 .
  • the central axes of the pair of film forming rolls (film forming rolls 76 and 77) should be substantially parallel on the same plane. are preferably arranged in the same direction.
  • the gas barrier film according to the first embodiment can be easily formed by adopting various conditions in the plasma CVD method exemplified in the explanation of the gas barrier film according to the first embodiment. can be manufactured.
  • the above-described gas barrier film 10 see FIG.
  • a film forming gas (more specifically, an organic silicon compound, oxygen, etc.) is supplied into the vacuum chamber while a pair of film forming rolls ( By generating a plasma discharge between the film-forming rolls 76 and 77), the film-forming gas is decomposed by the plasma, and in both the film-forming region near the film-forming roll 76 and the film-forming region near the film-forming roll 77, A silicon oxycarbide layer 13 (see FIG. 1) is formed on a transparent film substrate 11 (see FIG. 1).
  • a film forming gas more specifically, an organic silicon compound, oxygen, etc.
  • the decomposition amount of the vaporized organosilicon compound is relatively large at a location relatively far from the gas supply port 79 .
  • the amount of decomposition of the vaporized organosilicon compound is relatively small at locations relatively close to the gas supply port 79 . Therefore, the silicon oxycarbide layer 13 obtained using the film forming apparatus shown in FIG. 6 has a relatively high carbon content in the central portion in the thickness direction of the layer.
  • the transparent film substrate 11 is conveyed by the delivery roll 71, the conveying roll 72, and the like, and the transparent film substrate 11 is formed by a roll-to-roll continuous film formation process. A silicon oxycarbide layer 13 is formed thereon.
  • film deposition apparatus conditions At least one of the embracing angles (hereinafter collectively referred to as “film deposition apparatus conditions”) is changed, the film formation region near the film formation roll 76 and the film formation roll 77 near the film formation roll 77 change.
  • the distribution of the introduced film forming gas changes along the circumferential direction of the film forming roll. Therefore, by changing at least one of the film forming apparatus conditions, the carbon content of the silicon oxycarbide layer 13 (see FIG. 1) can be changed in the thickness direction.
  • the "holding angle” indicates the range of angles in which the film contacts the outer peripheral surface of the film forming roll in the circumferential direction, expressed by the central angle of the film forming roll.
  • the height H of the gas supply port 79 has a high correlation with the second layer thickness ratio.
  • the height H of the gas supply port 79 is preferably 100 mm or more and 200 mm or less, more preferably 150 mm or more and 180 mm or less. It is more preferable to have
  • the height H of each of the plurality of gas supply ports 79 may be the same or different.
  • the silicon oxycarbide layer 13 is formed using the film forming apparatus shown in FIG. can also be adjusted by changing at least one of
  • a polarizing plate with a gas barrier layer according to the third embodiment includes the gas barrier film according to the first embodiment and a polarizer.
  • FIG. 7 is a cross-sectional view showing an example of a polarizing plate with a gas barrier layer according to the third embodiment.
  • a polarizing plate 100 with a gas barrier layer shown in FIG. 7 has the above-described gas barrier film 50 and a polarizing plate 101 .
  • the polarizing plate 101 is arranged on the main surface 51a of the adhesive layer 51 opposite to the silicon oxycarbide layer 13 side. That is, the polarizing plate 101 and the silicon oxycarbide layer 13 are bonded together with the adhesive layer 51 interposed therebetween.
  • the polarizing plate 100 with a gas barrier layer shown in FIG. 7 has a gas barrier film 50 (gas barrier film 40)
  • the gas barrier film of the polarizing plate with a gas barrier layer according to the third embodiment is not limited to the gas barrier film 50.
  • it may be the gas barrier film 10, the gas barrier film 20, or the gas barrier film 30.
  • the polarizing plate 101 includes a polarizer (not shown), and generally transparent protective films (not shown) as polarizer protective films are laminated on both main surfaces of the polarizer.
  • a transparent protective film may not be provided on one principal surface or both principal surfaces of the polarizer.
  • a polarizer for example, a hydrophilic polymer film such as a polyvinyl alcohol film is uniaxially stretched after adsorbing a dichroic substance such as iodine or a dichroic dye.
  • a transparent resin film composed of a cellulose resin, a cyclic polyolefin resin, an acrylic resin, a phenylmaleimide resin, a polycarbonate resin, or the like is preferably used.
  • a gas barrier film may be used as the transparent protective film.
  • the polarizing plate 101 may include an optical functional film laminated on one or both main surfaces of a polarizer via an appropriate adhesive layer or pressure-sensitive adhesive layer as necessary.
  • the optical functional film include retardation plates, viewing angle widening films, viewing angle limiting (peep prevention) films, brightness improving films, and the like.
  • the polarizing plate 101 and the silicon oxycarbide layer 13 are bonded together with the adhesive layer 51 interposed therebetween.
  • the configuration is not limited to that shown in FIG. 7, and for example, the gas barrier layer may be directly provided on the polarizer.
  • the gas barrier layer may be directly provided on the transparent protective film arranged adjacent to the polarizer.
  • the gas barrier layer-attached polarizing plate according to the third embodiment includes the gas barrier film according to the first embodiment, and therefore has excellent transparency, flexibility, and gas barrier properties.
  • An image display device includes the gas barrier film according to the first embodiment or the polarizing plate with a gas barrier layer according to the third embodiment, and an image display cell.
  • FIG. 8 is a cross-sectional view showing an example of an image display device according to the fourth embodiment.
  • An image display device 200 shown in FIG. 8 includes a gas barrier layer-attached polarizing plate 100 having a gas barrier film 50 and an image display cell 202 .
  • the image display cell 202 includes a substrate 203 and display elements 204 provided on the substrate 203 .
  • the gas barrier layer 41 and the display element 204 are bonded together with the adhesive layer 201 interposed therebetween.
  • the image display device 200 shown in FIG. 8 has the gas barrier film 50 (gas barrier film 40)
  • the gas barrier film of the image display device according to the fourth embodiment is not limited to the gas barrier film 50.
  • the gas barrier film 10 it may be the gas barrier film 20 or the gas barrier film 30;
  • the same adhesives as those exemplified as the adhesive constituting the adhesive layer 51 described above can be used.
  • the adhesive that forms the adhesive layer 201 and the adhesive that forms the adhesive layer 51 may be of the same type or of different types.
  • the preferable range of the thickness of the adhesive layer 201 is, for example, the same as the preferable range of the thickness of the adhesive layer 51 described above.
  • the thickness of the adhesive layer 201 and the thickness of the adhesive layer 51 may be the same or different.
  • a glass substrate or a plastic substrate is used as the substrate 203 .
  • the substrate 203 does not have to be transparent, and a highly heat-resistant film such as a polyimide film may be used as the substrate 203 .
  • Examples of the display element 204 include an organic EL element, a liquid crystal element, an electrophoretic display element (electronic paper), and the like.
  • a touch panel sensor (not shown) may be arranged on the viewing side of the image display cell 202 .
  • the image display cell 202 is, for example, top emission type.
  • the organic EL element includes, for example, a metal electrode (not shown), an organic light emitting layer (not shown), and a transparent electrode (not shown) in this order from the substrate 203 side.
  • the organic light-emitting layer may include an electron-transporting layer, a hole-transporting layer, etc. in addition to the organic layer that itself functions as a light-emitting layer.
  • the transparent electrode is a metal oxide layer or a metal thin film and transmits light from the organic light emitting layer.
  • a back sheet (not shown) may be provided on the back side of the substrate 203 for the purpose of protecting and reinforcing the substrate 203 .
  • the metal electrode of the organic EL element is light reflective. Therefore, when external light enters the inside of the image display cell 202, the light is reflected by the metal electrodes, and the reflected light is visually recognized as a mirror surface from the outside.
  • a circularly polarizing plate as the polarizing plate 101 on the viewing side of the image display cell 202, the re-emission of light reflected by the metal electrode to the outside is prevented, and the visibility and design of the screen of the image display device 200 are improved. can improve sexuality.
  • the circularly polarizing plate has, for example, a retardation film on the main surface of the polarizer on the image display cell 202 side.
  • the transparent protective film arranged adjacent to the polarizer may be a retardation film.
  • the transparent film substrate 11 of the gas barrier film 50 may be a retardation film. Lamination of the polarizer and the retardation film when the retardation film has a retardation of ⁇ / 4 and the angle formed by the slow axis direction of the retardation film and the absorption axis direction of the polarizer is 45 °
  • the body functions as a circular polarizer for suppressing re-emission of reflected light from the metal electrode.
  • the retardation film that constitutes the circularly polarizing plate may be a laminate of two or more layers of films.
  • a broadband circularly polarizing plate that functions as a circularly polarizing plate over a wide band of visible light is obtained. can get.
  • the image display cell 202 may be of a bottom emission type in which a transparent electrode, an organic light emitting layer and a metal electrode are laminated in this order on a substrate.
  • a transparent substrate is used, and the transparent substrate is arranged on the viewing side.
  • a gas barrier film may be used as the transparent substrate.
  • the image display device includes the gas barrier film according to the first embodiment, it is possible to suppress deterioration of the display element caused by gas (for example, water vapor).
  • gas for example, water vapor
  • Example 1 A 40 ⁇ m-thick cyclic polyolefin film (“Zeonor (registered trademark) film ZF-14” manufactured by Nippon Zeon Co., Ltd.) as a transparent film substrate was set in a film forming apparatus, and the pressure in the vacuum chamber was reduced to 1 ⁇ 10 ⁇ 3 Pa. . Next, while the film was running, a silicon oxycarbide layer (gas barrier layer) having a thickness of 176 nm was formed by CVD at a substrate temperature of 12° C. to obtain a gas barrier film of Example 1.
  • the frequency of the power source for plasma generation was set to 80 kHz, and plasma was generated by discharging under the conditions of an applied power of 1.0 kW, and hexamethyldisiloxane (HMDSO): 25 sccm. , and oxygen: under flow conditions of 700 sccm, a gas was introduced between the film-forming rolls (between the electrodes) in the vacuum chamber, and the film was formed at a pressure of 1.0 Pa. Note that HMDSO was vaporized by heating and introduced into the vacuum chamber.
  • HMDSO hexamethyldisiloxane
  • Example 2 A gas barrier film of Example 2 was produced in the same manner as in Example 1, except that the applied power was changed to 0.6 kW, the HMDSO flow rate condition was changed to 15 sccm, and the thickness of the silicon oxycarbide layer was changed to 186 nm. did.
  • Comparative Example 1 A gas barrier film of Comparative Example 1 was produced in the same manner as in Example 1, except that the HMDSO flow rate condition was changed to 15 sccm and the thickness of the gas barrier layer was changed to 197 nm.
  • Comparative Example 2 A gas barrier film of Comparative Example 2 was produced in the same manner as in Example 1, except that the flow conditions of HMDSO were changed to 20 sccm and the thickness of the silicon oxycarbide layer was changed to 173 nm.
  • Comparative Example 3 Example except that the applied power was changed to 2.0 kW, the flow rate condition of HMDSO was changed to 50 sccm, the thickness of the silicon oxycarbide layer was changed to 203 nm, and the pressure during film formation was changed to 1.6 Pa.
  • a gas barrier film of Comparative Example 3 was produced in the same manner as in Example 1.
  • Comparative Example 4 Same as Example 1 except that the applied power was changed to 0.3 kW, the HMDSO flow condition was changed to 50 sccm, the oxygen flow condition was changed to 100 sccm, and the thickness of the silicon oxycarbide layer was changed to 250 nm.
  • a gas barrier film of Comparative Example 4 was produced by the method.
  • composition analysis of gas barrier layer Using an X-ray photoelectron spectrometer equipped with an Ar ion gun (“Quantera SXM” manufactured by ULVAC-Phi, Inc.), the gas barrier layer was etched from the main surface of the gas barrier layer opposite to the transparent film substrate side under the following conditions. , the composition analysis in the thickness direction of the gas barrier layer was performed by XPS, and the content of each element (Si, O, N and C) was calculated at each measurement point in the thickness direction. Peaks corresponding to the binding energies of 2p of Si, 1s of O, 1s of N, and 1s of C obtained from the wide scan spectrum were used to calculate the content of each element.
  • the second layer thickness ratio was calculated from the content of each element calculated at each measurement point in the thickness direction. Detailed measurement conditions are shown below. Since the surface layer of the gas barrier layer tends to have a large carbon content due to contamination, the content of each element was calculated assuming that the carbon content was 0 atomic % at the measurement points at the start of etching.
  • the water vapor transmission rate (WVTR) of each gas barrier film was measured under the conditions of a temperature of 40° C. and a relative humidity difference of 90% according to the description in JIS K 7129:2008 Annex B (Mocon method). Then, the obtained WVTR was converted into a value (hereinafter sometimes referred to as "normalized WVTR") normalized based on the gas barrier layer having a thickness of 100 nm.
  • the normalized WVTR of Example 1 is a value calculated by multiplying the measured value (WVTR) obtained by the above measuring method by 176/100.
  • the light transmittance (Y value) of each gas barrier film was measured with a spectrophotometer ("U4100" manufactured by Hitachi High-Tech Science). When the light transmittance was 90% or more, it was evaluated as “excellent in transparency”. On the other hand, when the light transmittance was less than 90%, it was evaluated as "not excellent in transparency”.
  • Each gas barrier film was cut into a strip having a width of 25 mm and a length of 150 mm to obtain a test piece for evaluation of bending resistance.
  • the test piece was set in a bending tester ("DLDMLH-FS" manufactured by Yuasa System Co., Ltd.), and bending test was performed 1000 times under the conditions of bending diameter: 6 mm or 5 mm, bending speed: 1 time/second.
  • bending diameter refers to the diameter of the inner circumference of the arc-shaped bent portion when the test piece is bent in an arc-shaped manner in the bending test.
  • the second layer thickness ratio was 20% or more and 70% or less.
  • C max -C min was 6.0 or less.
  • Examples 1 and 2 As shown in Table 1, in Examples 1 and 2, the normalized WVTR was 0.10 g/m 2 ⁇ day or less. Therefore, Examples 1 and 2 were excellent in gas barrier properties. In Examples 1 and 2, the light transmittance was 90% or more. Therefore, Examples 1 and 2 were excellent in transparency. In Examples 1 and 2, the evaluation of bending resistance was A or B. Therefore, Examples 1 and 2 were excellent in bending resistance.
  • the second layer thickness ratio was less than 20%. In Comparative Examples 3 and 4, the second layer thickness ratio exceeded 70%. In Comparative Example 3, C max -C min exceeded 6.0. In Comparative Example 1, the gas barrier layer did not contain carbon.
  • Comparative Examples 1 to 3 were not excellent in gas barrier properties.
  • the light transmittance was less than 90%. Therefore, Comparative Examples 1 and 4 were not excellent in transparency.
  • the flex resistance was evaluated as C. Therefore, Comparative Examples 1, 2 and 4 were not excellent in bending resistance.
  • the present invention can provide a gas barrier film with excellent transparency, flexibility and gas barrier properties.

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Abstract

L'invention concerne un film barrière aux gaz (10) qui comprend un substrat de film transparent (11) et une couche barrière aux gaz (12). La couche barrière aux gaz (12) comprend une couche d'oxycarbure de silicium (13). La couche d'oxycarbure de silicium (13) comprend une première couche (14), une deuxième couche (15) et une troisième couche (16). La teneur en carbone dans la première couche (14) et la teneur en carbone dans la troisième couche (16) sont inférieures à 0,1 % at. La teneur en carbone dans la deuxième couche (15) est supérieure ou égale à 0,1 % at. Le pourcentage d'épaisseur de la deuxième couche (15) est de 20 à 70 %. En ce qui concerne la couche d'oxycarbure de silicium (13), lorsque la teneur en carbone en un emplacement où la teneur en carbone est observée comme étant la plus haute est notée Cmax % at., et lorsque la teneur en carbone en un emplacement où la teneur en carbone est observée comme étant la plus faible est notée Cmin % at., la valeur obtenue en soustrayant Cmin de Cmax est inférieure ou égale à 6,0.
PCT/JP2023/003384 2022-02-10 2023-02-02 Film barrière aux gaz, son procédé de production, plaque de polarisation avec couche barrière aux gaz et dispositif d'affichage d'image WO2023153307A1 (fr)

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US20110195259A1 (en) * 2010-02-10 2011-08-11 Kwangjin Song Metallizable and Metallized Polyolefin Films and a Process of Making Same
JP2012081630A (ja) * 2010-10-08 2012-04-26 Sumitomo Chemical Co Ltd ガスバリア性積層フィルム
JP2012179763A (ja) * 2011-02-28 2012-09-20 Nitto Denko Corp 透明ガスバリアフィルム、透明ガスバリアフィルムの製造方法、有機エレクトロルミネッセンス素子、太陽電池および薄膜電池
WO2013146964A1 (fr) * 2012-03-27 2013-10-03 住友化学株式会社 Feuille stratifiée, dispositif à diodes électroluminescentes organiques, convertisseur photoélectrique et écran à cristaux liquides
WO2015098672A1 (fr) * 2013-12-26 2015-07-02 住友化学株式会社 Film stratifié et dispositif électronique souple
WO2018168671A1 (fr) * 2017-03-17 2018-09-20 コニカミノルタ株式会社 Revêtement formant barrière aux gaz, film formant barrière aux gaz, procédé de production d'un revêtement formant barrière aux gaz et procédé de production d'un film formant barrière aux gaz
WO2019054318A1 (fr) * 2017-09-13 2019-03-21 住友化学株式会社 Film barrière aux gaz et dispositif électronique souple
JP2022124227A (ja) * 2021-02-15 2022-08-25 日東電工株式会社 ガスバリアフィルムおよびその製造方法、ならびに偏光板および画像表示装置

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110195259A1 (en) * 2010-02-10 2011-08-11 Kwangjin Song Metallizable and Metallized Polyolefin Films and a Process of Making Same
JP2012081630A (ja) * 2010-10-08 2012-04-26 Sumitomo Chemical Co Ltd ガスバリア性積層フィルム
JP2012179763A (ja) * 2011-02-28 2012-09-20 Nitto Denko Corp 透明ガスバリアフィルム、透明ガスバリアフィルムの製造方法、有機エレクトロルミネッセンス素子、太陽電池および薄膜電池
WO2013146964A1 (fr) * 2012-03-27 2013-10-03 住友化学株式会社 Feuille stratifiée, dispositif à diodes électroluminescentes organiques, convertisseur photoélectrique et écran à cristaux liquides
WO2015098672A1 (fr) * 2013-12-26 2015-07-02 住友化学株式会社 Film stratifié et dispositif électronique souple
WO2018168671A1 (fr) * 2017-03-17 2018-09-20 コニカミノルタ株式会社 Revêtement formant barrière aux gaz, film formant barrière aux gaz, procédé de production d'un revêtement formant barrière aux gaz et procédé de production d'un film formant barrière aux gaz
WO2019054318A1 (fr) * 2017-09-13 2019-03-21 住友化学株式会社 Film barrière aux gaz et dispositif électronique souple
JP2022124227A (ja) * 2021-02-15 2022-08-25 日東電工株式会社 ガスバリアフィルムおよびその製造方法、ならびに偏光板および画像表示装置

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