WO2023153307A1 - Gas barrier film, method for producing the same, polarizing plate with gas barrier layer and image display device - Google Patents

Gas barrier film, method for producing the same, polarizing plate with gas barrier layer and image display device Download PDF

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Publication number
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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French (fr)
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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    • 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

A gas barrier film (10) has a transparent film substrate (11) and a gas barrier layer (12). The gas barrier layer (12) includes a silicon oxycarbide layer (13). The silicon oxycarbide layer (13) includes a first layer (14), a second layer (15), and a third layer (16). The carbon content in the first layer (14) and the carbon content in the third layer (16) are less than 0.1 at%. The carbon content in the second layer (15) is at least 0.1 at%. The thickness percentage of the second layer (15) is 20-70%. Regarding the silicon oxycarbide layer (13), when the carbon content at a location where the carbon content is found to be greatest is noted as Cmax at%, and the carbon content at a location where the carbon content is found the smallest is noted as Cmin at%, the value obtained by subtracting Cmin from Cmax is 6.0 or less.

Description

ガスバリアフィルム及びその製造方法、並びにガスバリア層付き偏光板及び画像表示装置GAS BARRIER FILM, METHOD FOR MANUFACTURING THE SAME, POLARIZING PLATE WITH GAS BARRIER LAYER, AND IMAGE DISPLAY DEVICE
　本発明は、ガスバリアフィルム及びその製造方法、並びにガスバリア層付き偏光板及び画像表示装置に関する。 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.
　画像表示装置の軽量化・薄型化・フレキシブル化に伴って、ガラス基板の代わりに樹脂フィルム基板が用いられるようになっている。樹脂フィルムは、ガラスに比べて水蒸気や酸素等のガス透過性が高いため、これらのガスに起因する表示素子の劣化を抑制する目的で、ガスバリア層を備えたガスバリアフィルムを用いることが提案されている。 As image display devices become lighter, thinner, and more flexible, 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. there is
　有機ＥＬ素子は、わずかな水分の浸入に起因して「ダークスポット」と呼ばれる欠点が生じる場合があり、高いガスバリア性（水蒸気遮断性）が要求される。ガスバリア性に優れる材料として、窒化ケイ素（ＳｉＮ）及び酸窒化ケイ素（ＳｉＯＮ）が知られている。 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.
　また、可撓性基板上に有機ＥＬ素子等の表示素子を形成した折り曲げ可能な表示装置（フレキシブルディスプレイ、フォルダブルディスプレイ等）が実用化されている。このため、ガスバリアフィルムは、折り曲げた際、ガスバリア層にクラックが生じないこと（耐屈曲性）が要求されている。 In addition, bendable display devices (flexible displays, foldable displays, etc.) in which display elements such as organic EL elements are formed on flexible substrates have been put to practical use. Therefore, the gas barrier film is required to have no cracks in the gas barrier layer (flex resistance) when the film is folded.
　例えば、特許文献１では、透明性及び耐屈曲性に優れるガスバリアフィルムとして、窒化ケイ素層と酸化ケイ素層とを備えるガスバリアフィルムが提案されている。 For example, 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.
国際公開第２０１９／１８７９７８号WO2019/187978
　しかしながら、特許文献１に開示される技術には、ガスバリアフィルムの透明性、耐屈曲性及びガスバリア性を高めることについて、改善の余地がある。 However, the technology disclosed in Patent Document 1 has room for improvement in terms of increasing the transparency, bending resistance, and gas barrier properties of the gas barrier film.
　本発明は、上記課題に鑑みてなされたものであり、その目的は、透明性、耐屈曲性及びガスバリア性に優れるガスバリアフィルム及びその製造方法、並びに当該ガスバリアフィルムを用いたガスバリア層付き偏光板及び画像表示装置を提供することである。 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.
＜本発明の態様＞
　本発明には、以下の態様が含まれる。 <Aspect of the present invention>
The present invention includes the following aspects.
［１］透明フィルム基材と、前記透明フィルム基材の少なくとも一方の主面に直接的又は間接的に配置されたガスバリア層とを有するガスバリアフィルムであって、
　前記ガスバリア層は、構成元素としてケイ素、酸素及び炭素を含む酸炭化ケイ素層を有し、
　前記酸炭化ケイ素層は、前記透明フィルム基材側から第１層、第２層及び第３層をこの順に有し、
　前記第１層中の炭素含有率、及び前記第３層中の炭素含有率が、ケイ素、酸素及び炭素の合計１００原子％に対して、いずれも０．１原子％未満であり、
　前記第２層中の炭素含有率が、ケイ素、酸素及び炭素の合計１００原子％に対して、０．１原子％以上であり、
　前記第２層の厚み比率が、前記第１層、前記第２層及び前記第３層の合計厚み１００％に対して、２０％以上７０％以下であり、
　Ｘ線光電子分光法を用いて前記酸炭化ケイ素層の厚み方向における組成分析を行った際に、ケイ素、酸素及び炭素の合計１００原子％に対する炭素含有率が最大値を示す箇所の当該炭素含有率をＣｍａｘ原子％とし、ケイ素、酸素及び炭素の合計１００原子％に対する炭素含有率が最小値を示す箇所の当該炭素含有率をＣｍｉｎ原子％としたとき、ＣｍａｘからＣｍｉｎを引いた値が６．０以下である、ガスバリアフィルム。 [1] 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 thickness direction of the silicon oxycarbide layer is performed using X-ray photoelectron spectroscopy. is C max atomic %, and 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.
［２］前記Ｃｍａｘから前記Ｃｍｉｎを引いた値が２．０以上である、前記［１］に記載のガスバリアフィルム。 [2] The gas barrier film according to [1], wherein the value obtained by subtracting the C min from the C max is 2.0 or more.
［３］前記第２層の厚み比率が、前記第１層、前記第２層及び前記第３層の合計厚み１００％に対して、２０％以上５５％以下である、前記［１］又は［２］に記載のガスバリアフィルム。 [3] 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].
［４］前記酸炭化ケイ素層の厚みが、１０ｎｍ以上５００ｎｍ以下である、前記［１］～［３］のいずれか一つに記載のガスバリアフィルム。 [4] The gas barrier film according to any one of [1] to [3], wherein the silicon oxycarbide layer has a thickness of 10 nm or more and 500 nm or less.
［５］ＪｌＳ　Ｚ８７８１－３：２０１６で規定されるＣＩＥ三刺激値のＹ値が、９０％以上である、前記［１］～［４］のいずれか一つに記載のガスバリアフィルム。 [5] The gas barrier film according to any one of [1] to [4] above, wherein the Y value of the CIE tristimulus values defined in JlS Z8781-3:2016 is 90% or more.
［６］前記透明フィルム基材と前記ガスバリア層との間に配置された、個数平均一次粒子径１．０μｍ未満のシリカ粒子を含むハードコート層を更に有する、前記［１］～［５］のいずれか一つに記載のガスバリアフィルム。 [6] Any of the above [1] to [5], further comprising a hard coat layer containing silica particles having a number average primary particle diameter of less than 1.0 μm, disposed between the transparent film substrate and the gas barrier layer. The gas barrier film according to any one.
［７］前記ガスバリア層の前記透明フィルム基材側とは反対側に配置された粘着剤層を更に有する、前記［１］～［６］のいずれか一つに記載のガスバリアフィルム。 [7] The gas barrier film according to any one of [1] to [6], further comprising an adhesive layer disposed on the side of the gas barrier layer opposite to the transparent film substrate side.
［８］前記［１］～［７］のいずれか一つに記載のガスバリアフィルムの製造方法であって、
　一対の対向電極として一対の成膜ロールを有する成膜装置のチャンバー内に、有機ケイ素化合物及び酸素を導入して、化学気相成長法により前記酸炭化ケイ素層を形成する、ガスバリアフィルムの製造方法。 [8] 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. .
［９］前記［１］～［７］のいずれか一つに記載のガスバリアフィルムと、偏光子とを備える、ガスバリア層付き偏光板。 [9] 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.
［１０］前記［１］～［７］のいずれか一つに記載のガスバリアフィルムと、画像表示セルとを備える、画像表示装置。 [10] An image display device comprising the gas barrier film according to any one of [1] to [7] and an image display cell.
［１１］前記［９］に記載のガスバリア層付き偏光板と、画像表示セルとを備える、画像表示装置。 [11] An image display device comprising the polarizing plate with a gas barrier layer according to [9] and an image display cell.
［１２］前記画像表示セルは、有機ＥＬ素子を含む、前記［１０］又は［１１］に記載の画像表示装置。 [12] The image display device according to [10] or [11], wherein the image display cell includes an organic EL element.
　本発明によれば、透明性、耐屈曲性及びガスバリア性に優れるガスバリアフィルム及びその製造方法、並びに当該ガスバリアフィルムを用いたガスバリア層付き偏光板及び画像表示装置を提供できる。 According to 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.
本発明に係るガスバリアフィルムの一例を示す断面図である。1 is a cross-sectional view showing an example of a gas barrier film according to the present invention; FIG. 本発明に係るガスバリアフィルムの他の例を示す断面図である。FIG. 4 is a cross-sectional view showing another example of the gas barrier film according to the present invention; 本発明に係るガスバリアフィルムの他の例を示す断面図である。FIG. 4 is a cross-sectional view showing another example of the gas barrier film according to the present invention; 本発明に係るガスバリアフィルムの他の例を示す断面図である。FIG. 4 is a cross-sectional view showing another example of the gas barrier film according to the present invention; 本発明に係るガスバリアフィルムの他の例を示す断面図である。FIG. 4 is a cross-sectional view showing another example of the gas barrier film according to the present invention; 本発明に係るガスバリアフィルムの製造方法に使用される成膜装置の一例を示す構成図である。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. 本発明に係るガスバリア層付き偏光板の一例を示す断面図である。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. 本発明に係る画像表示装置の一例を示す断面図である。It is a sectional view showing an example of an image display device concerning the present invention.
　以下、本発明の好適な実施形態について説明する。まず、本明細書中で使用される用語について説明する。粒子の個数平均一次粒子径は、何ら規定していなければ、走査型電子顕微鏡及び画像処理ソフトウェア（例えば、アメリカ国立衛生研究所製「ＩｍａｇｅＪ」）を用いて測定した、１００個の一次粒子の円相当径（ヘイウッド径：一次粒子の投影面積と同じ面積を有する円の直径）の個数平均値である。 A preferred embodiment of the present invention will be described below. First, the terms used in this specification will be explained. 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).
　層状物（より具体的には、透明フィルム基材、ガスバリア層、酸炭化ケイ素層、第１層、第２層、第３層、ハードコート層、粘着剤層、偏光子等）の「主面」とは、層状物の厚み方向に直交する面をさす。ガスバリア層、及びガスバリア層を構成する各層（より具体的には、酸炭化ケイ素層、第１層、第２層、第３層等）の厚みは、Ｘ線光電子分光法を用いて層の厚み方向における組成を分析した際の層のエッチング時間を、ＳｉＯ２に対するスパッタ速度の値を用いて換算した値である。ガスバリア層及びガスバリア層を構成する各層以外の層状物の「厚み」の数値は、「平均厚み」である。層状物の平均厚みは、層状物を厚み方向に切断した断面を電子顕微鏡で観察し、断面画像から無作為に測定箇所を１０箇所選択し、選択した１０箇所の測定箇所の厚みを測定して得られた１０個の測定値の算術平均値である。 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 (more specifically, the silicon oxycarbide layer, the first layer, the second layer, the third layer, etc.) 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.
　「屈折率」とは、温度２３℃の雰囲気下における波長５５０ｎｍの光に対する屈折率をいう。流量の単位「ｓｃｃｍ（Ｓｔａｎｄａｒｄ　Ｃｕｂｉｃ　Ｃｅｎｔｉｍｅｔｅｒ　ｐｅｒ　Ｍｉｎｕｔｅ）」は、標準状態（温度：０℃、圧力：１０１．３ｋＰａ）における流量の単位「ｍＬ／分」である。 "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).
　以下、化合物名の後に「系」を付けて、化合物及びその誘導体を包括的に総称する場合がある。化合物名の後に「系」を付けて重合体名を表す場合には、重合体の繰り返し単位が化合物又はその誘導体に由来することを意味する。また、アクリル及びメタクリルを包括的に「（メタ）アクリル」と総称する場合がある。 In the following, "system" may be added after the name of the compound to generically refer to the compound and its derivatives. When the 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. Moreover, acryl and methacryl may be collectively referred to as "(meth)acryl".
　以下の説明において参照する図面は、理解しやすくするために、それぞれの構成要素を主体に模式的に示しており、図示された各構成要素の大きさ、個数、形状等は、図面作成の都合上から実際とは異なる場合がある。また、説明の都合上、後に説明する図面において、先に説明した図面と同一構成部分については、同一符号を付して、その説明を省略する場合がある。 The drawings referred to in the following description mainly show each component schematically for the sake of easy understanding. It may be different from the actual from above. Also, for convenience of description, in the drawings described later, the same components as those in the drawings described earlier may be denoted by the same reference numerals, and the description thereof may be omitted.
＜第１実施形態：ガスバリアフィルム＞
　本発明の第１実施形態に係るガスバリアフィルムは、透明フィルム基材と、透明フィルム基材の少なくとも一方の主面に直接的又は間接的に配置されたガスバリア層とを有する。ガスバリア層は、構成元素としてケイ素、酸素及び炭素を含む酸炭化ケイ素層を有する。酸炭化ケイ素層は、透明フィルム基材側から第１層、第２層及び第３層をこの順に有する。第１層中の炭素含有率は、ケイ素、酸素及び炭素の合計１００原子％に対して、０．１原子％未満である。第３層中の炭素含有率は、ケイ素、酸素及び炭素の合計１００原子％に対して、０．１原子％未満である。第２層中の炭素含有率は、ケイ素、酸素及び炭素の合計１００原子％に対して、０．１原子％以上である。第２層の厚み比率は、第１層、第２層及び第３層の合計厚み１００％に対して、２０％以上７０％以下である。Ｘ線光電子分光法を用いて酸炭化ケイ素層の厚み方向における組成分析を行った際に、ケイ素、酸素及び炭素の合計１００原子％に対する炭素含有率が最大値を示す箇所の当該炭素含有率をＣｍａｘ原子％とし、ケイ素、酸素及び炭素の合計１００原子％に対する炭素含有率が最小値を示す箇所の当該炭素含有率をＣｍｉｎ原子％としたとき、ＣｍａｘからＣｍｉｎを引いた値が６．０以下である。 <First Embodiment: Gas Barrier Film>
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. When composition analysis in the thickness direction of the silicon oxycarbide layer is performed using X-ray photoelectron spectroscopy, the carbon content at the point where the carbon content with respect to the total 100 atomic% of silicon, oxygen and carbon shows the maximum value When C max atomic % and C min atomic % is the carbon content at the point where the carbon content in 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.
　Ｘ線光電子分光法を用いて酸炭化ケイ素層の厚み方向における組成分析を行う方法は、後述する実施例と同じ方法又はそれに準ずる方法である。以下、Ｘ線光電子分光法を「ＸＰＳ」と記載することがある。また、ケイ素、酸素及び炭素の合計を１００原子％としたときの炭素含有率を、単に「炭素含有率」と記載することがある。また、第１層、第２層及び第３層の合計厚み１００％に対する、第２層の厚み比率を、単に「第２層厚み比率」と記載することがある。また、ＸＰＳを用いて酸炭化ケイ素層の厚み方向における組成分析を行った際に、炭素含有率が最大値を示す箇所（測定箇所）の当該炭素含有率を、「Ｃｍａｘ原子％」と記載することがある。また、ＸＰＳを用いて酸炭化ケイ素層の厚み方向における組成分析を行った際に、炭素含有率が最小値を示す箇所（測定箇所）の当該炭素含有率を、「Ｃｍｉｎ原子％」と記載することがある。「第１層中の炭素含有率が０．１原子％未満である」とは、ＸＰＳを用いて酸炭化ケイ素層の厚み方向における組成分析を行った際、第１層中のいずれの測定箇所においても炭素含有率が０．１原子％未満であることを意味する。「第３層中の炭素含有率が０．１原子％未満である」とは、ＸＰＳを用いて酸炭化ケイ素層の厚み方向における組成分析を行った際、第３層中のいずれの測定箇所においても炭素含有率が０．１原子％未満であることを意味する。「第２層中の炭素含有率が０．１原子％以上である」とは、ＸＰＳを用いて酸炭化ケイ素層の厚み方向における組成分析を行った際、第２層中のいずれの測定箇所においても炭素含有率が０．１原子％以上であることを意味する。 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. Hereinafter, X-ray photoelectron spectroscopy may be referred to as "XPS". Also, the carbon content when the total of silicon, oxygen and carbon is 100 atomic % is sometimes simply referred to as "carbon content". Also, 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". In addition, when the composition analysis in the thickness direction of the silicon oxycarbide layer is performed using XPS, 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. In addition, when the composition analysis in the thickness direction of the silicon oxycarbide layer is performed using XPS, 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 %" means that when the composition analysis in the thickness direction of the silicon oxycarbide layer is performed using XPS, any measurement point in the first layer also means that the carbon content is less than 0.1 atomic %. "The carbon content in the third layer is less than 0.1 atomic %" means that when the composition analysis in the thickness direction of the silicon oxycarbide layer is performed using XPS, any measurement point in the third layer also means that the carbon content is less than 0.1 atomic %. "The carbon content in the second layer is 0.1 atomic % or more" means that when the composition analysis in the thickness direction of the silicon oxycarbide layer is performed using XPS, any measurement point in the second layer also means that the carbon content is 0.1 atomic % or more.
　なお、ＸＰＳにより酸炭化ケイ素層の厚み方向における組成分析を行う際、元素組成の測定間隔は、例えば３０秒以上９０秒以下（２．５ｎｍ以上７．５ｎｍ以下）の範囲内であり、好ましくは６０秒（５ｎｍ）である。例えば５ｎｍ間隔で酸炭化ケイ素層の厚み方向における組成分析が行われる場合、酸炭化ケイ素層の表面から厚み方向（深さ方向）に順に、０ｎｍ（エッチングの開始位置）、５ｎｍ、１０ｎｍ、１５ｎｍ、２０ｎｍ、２５ｎｍ・・・の位置で組成分析が行われる。また、５ｎｍ間隔で酸炭化ケイ素層の厚み方向における組成分析を行った際の炭素含有率の測定結果が、例えば、０ｎｍ：０．１原子％未満、５ｎｍ：０．１原子％未満、１０ｎｍ：０．１原子％以上、１５ｎｍ：０．１原子％以上、２５ｎｍ：０．１原子％未満となった場合は、第２層は、酸炭化ケイ素層の表面（エッチングの開始位置）から厚み方向に１０ｎｍ以上１５ｎｍ以下の範囲である。 When performing composition analysis in the thickness direction of the silicon oxycarbide layer by XPS, 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). For example, when 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. In addition, 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.
　第１実施形態によれば、透明性、耐屈曲性及びガスバリア性に優れるガスバリアフィルムを提供できる。その理由は、以下のように推測される。 According to the first embodiment, it is possible to provide a gas barrier film with excellent transparency, bending resistance, and gas barrier properties. The reason is presumed as follows.
　本発明者らの検討によれば、酸炭化ケイ素層の透明性及び耐屈曲性は、酸炭化ケイ素層中の炭素含有率が高すぎても低すぎても低下する傾向がある。また、本発明者らの検討によれば、酸炭化ケイ素層中の炭素含有率が低すぎると、酸炭化ケイ素層の表面が粗くなりすぎて、酸炭化ケイ素層のガスバリア性が低下する傾向がある。また、本発明者らの検討によれば、酸炭化ケイ素層中の炭素含有率の最大値と最小値の差が大きくなりすぎると、酸炭化ケイ素層が不均一な組成の膜となり、その結果、酸炭化ケイ素層のガスバリア性が低下する傾向がある。 According to the studies of the present inventors, 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. In addition, according to the studies of the present inventors, if 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. Further, according to the studies of the present inventors, if 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.
　第１実施形態に係るガスバリアフィルムでは、比較的炭素含有率が高い第２層の厚み比率（第２層厚み比率）が２０％以上７０％以下であるため、酸炭化ケイ素層全体の炭素含有率が適度な範囲となり、酸炭化ケイ素層の透明性及び耐屈曲性が良好となる。よって、第１実施形態によれば、透明性及び耐屈曲性に優れるガスバリアフィルムを提供できる。 In the gas barrier film according to the first embodiment, the thickness ratio of the second layer having a relatively high carbon content (second layer thickness ratio) 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.
　また、第１実施形態に係るガスバリアフィルムでは、第２層厚み比率が２０％以上７０％以下であり、かつＣｍａｘからＣｍｉｎを引いた値が６．０以下であるため、酸炭化ケイ素層全体の炭素含有率が適度な範囲となり、かつ酸炭化ケイ素層が比較的均一な組成の膜となる。よって、第１実施形態によれば、ガスバリア性に優れるガスバリアフィルムを提供できる。 In addition, in the gas barrier film according to the first embodiment, the second layer thickness ratio is 20% or more and 70% or less, and the value obtained by subtracting Cmin from Cmax is 6.0 or less, so the silicon oxycarbide layer The overall carbon content is in an appropriate range, and the silicon oxycarbide layer has a relatively uniform composition. Therefore, according to the first embodiment, a gas barrier film having excellent gas barrier properties can be provided.
　第１実施形態において、耐屈曲性により優れるガスバリアフィルムを得るためには、ＣｍａｘからＣｍｉｎを引いた値が、２．０以上であることが好ましく、３．０以上であることがより好ましく、４．０以上であることが更に好ましい。 In the first embodiment, in order to obtain a gas barrier film with more excellent 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.
　第１実施形態において、透明性及び耐屈曲性により優れるガスバリアフィルムを得るためには、第２層厚み比率が、２０％以上６０％以下であることが好ましく、２０％以上５５％以下であることがより好ましい。 In the first embodiment, 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.
　第１実施形態において、透明性、耐屈曲性及びガスバリア性により優れるガスバリアフィルムを得るためには、第１層、第２層及び第３層の合計厚み１００％に対する、第１層の厚み比率及び第３層の厚み比率が、それぞれ、１０％以上５０％以下であることが好ましく、２０％以上４５％以下であることがより好ましい。第１実施形態では、第１層の厚み比率及び第３層の厚み比率が、同じ値であってもよく、互いに異なる値であってもよい。 In the first embodiment, in order to obtain a gas barrier film that is more excellent in transparency, flex resistance, and gas barrier properties, 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. In the first embodiment, the thickness ratio of the first layer and the thickness ratio of the third layer may be the same value or different values.
　第１実施形態において、透明性、耐屈曲性及びガスバリア性に更に優れるガスバリアフィルムを得るためには、下記条件１を満たすことが好ましく、耐屈曲性に特に優れるガスバリアフィルムを得るためには、下記条件２を満たすことが好ましく、ガスバリア性に特に優れるガスバリアフィルムを得るためには、下記条件３を満たすことが好ましい。
　条件１：第２層厚み比率が２０％以上５５％以下であり、かつＣｍａｘからＣｍｉｎを引いた値が２．０以上６．０以下である。
　条件２：第２層厚み比率が４５％以上５５％以下であり、かつＣｍａｘからＣｍｉｎを引いた値が５．０以上６．０以下である。
　条件３：第２層厚み比率が２０％以上３０％以下であり、かつＣｍａｘからＣｍｉｎを引いた値が４．０以上５．０以下である。 In the first embodiment, in order to obtain a gas barrier film that is more excellent in transparency, flex resistance, and gas barrier properties, it is preferable to satisfy Condition 1 below. It is preferable to satisfy Condition 2, and in order to obtain a gas barrier film having particularly excellent gas barrier properties, it is preferable to satisfy Condition 3 below.
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.
　以下、第１実施形態について、図面を参照しながら詳述する。図１は、第１実施形態に係るガスバリアフィルムの一例を示す断面図である。図１に示すガスバリアフィルム１０は、透明フィルム基材１１と、透明フィルム基材１１の一方の主面１１ａに直接的に配置されたガスバリア層１２とを有する積層体である。ガスバリア層１２は、構成元素としてケイ素、酸素及び炭素を含む酸炭化ケイ素層１３からなる。 The first embodiment will be described in detail below with reference to the drawings. 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.
　酸炭化ケイ素層１３は、透明フィルム基材１１側から第１層１４、第２層１５及び第３層１６をこの順に有する。第１層１４中の炭素含有率は０．１原子％未満である。第３層１６中の炭素含有率は０．１原子％未満である。第２層１５中の炭素含有率は０．１原子％以上である。第２層１５の厚み比率は、第１層１４、第２層１５及び第３層１６の合計厚み１００％に対して、２０％以上７０％以下である。また、酸炭化ケイ素層１３では、ＣｍａｘからＣｍｉｎを引いた値が６．０以下である。 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.
　ＸＰＳを用いて酸炭化ケイ素層１３の厚み方向における組成分析を行った際、炭素含有率が最小値を示す測定箇所は、第１層１４及び第３層１６の少なくとも一方に存在する。また、ＸＰＳを用いて酸炭化ケイ素層１３の厚み方向における組成分析を行った際、炭素含有率が最大値を示す測定箇所は、第２層１５に存在する。なお、第１層１４の炭素含有率の最小値、及び第３層１６の炭素含有率の最小値は、特に限定されず、いずれも０．０原子％であってもよい。 When the composition analysis in the thickness direction of the silicon oxycarbide layer 13 is performed using XPS, the measurement point showing the minimum carbon content exists in at least one of the first layer 14 and the third layer 16 . In addition, when the composition analysis in the thickness direction of the silicon oxycarbide layer 13 is performed using XPS, 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 %.
　透明性、耐屈曲性及びガスバリア性により優れるガスバリアフィルムを得るためには、酸炭化ケイ素層１３の厚み方向において、炭素含有率が連続的に変化することが好ましい。 In order to obtain a gas barrier film that is more excellent in transparency, bending resistance, and gas barrier properties, it is preferable that the carbon content rate changes continuously in the thickness direction of the silicon oxycarbide layer 13 .
　また、透明性、耐屈曲性及びガスバリア性により優れるガスバリアフィルムを得るためには、透過型電子顕微鏡により酸炭化ケイ素層１３の断面を暗視野像で観察した際、第１層１４と第２層１５との間、及び第２層１５と第３層１６との間のいずれについても界面が存在しないことが好ましい。 In addition, in order to obtain a gas barrier film that is more excellent in transparency, flex resistance, and gas barrier properties, when observing a cross section of the silicon oxycarbide layer 13 in a dark field image with a transmission electron microscope, the first layer 14 and the second layer 15 and between the second layer 15 and the third layer 16. Preferably, there is no interface.
　第１実施形態に係るガスバリアフィルムの構成は、図１に示すガスバリアフィルム１０の構成に限定されない。例えば、第１実施形態に係るガスバリアフィルムは、図２に示すガスバリアフィルム２０のように、ガスバリア層が、酸炭化ケイ素層以外のガスバリア性を有する層（以下、「ガスバリア性層」と記載する）を有していてもよい。なお、酸炭化ケイ素層とガスバリア性層とを有するガスバリア層の断面を、透過型電子顕微鏡により暗視野像で観察した際、酸炭化ケイ素層とガスバリア性層との間には界面が存在することが好ましい。ガスバリアフィルム２０では、ガスバリア層２１が、酸炭化ケイ素層１３と、酸炭化ケイ素層１３の透明フィルム基材１１側とは反対側の主面１６ａに配置されたガスバリア性層２２とを有する。ガスバリア性により優れるガスバリアフィルムを得るためには、ガスバリア性層２２は、構成元素としてケイ素、酸素及び窒素を含む酸窒化ケイ素層であることが好ましい。 The configuration of the gas barrier film according to the first embodiment is not limited to the configuration of the gas barrier film 10 shown in FIG. For example, in the gas barrier film according to the first embodiment, like the gas barrier film 20 shown in FIG. 2, the gas barrier layer is a layer having gas barrier properties other than a silicon oxycarbide layer (hereinafter referred to as "gas barrier layer"). may have When a cross section of a gas barrier layer having a silicon oxycarbide layer and a gas barrier layer is observed in a dark field image with a transmission electron microscope, an interface exists between the silicon oxycarbide layer and the gas barrier layer. is preferred. In the gas barrier film 20, 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. In order to obtain a gas barrier film with better gas barrier properties, the gas barrier layer 22 is preferably a silicon oxynitride layer containing silicon, oxygen and nitrogen as constituent elements.
　第１実施形態に係るガスバリアフィルムは、酸炭化ケイ素層の両主面にガスバリア性層を備えていてもよい。また、第１実施形態に係るガスバリアフィルムは、酸炭化ケイ素層の透明フィルム基材側の主面のみにガスバリア性層を備えていてもよい。また、第１実施形態に係るガスバリアフィルムでは、ガスバリア層が、２層以上の酸炭化ケイ素層を含んでいてもよく、例えば、２層の酸炭化ケイ素層と３層の酸窒化ケイ素層との交互積層体であってもよい。ガスバリア層は、４層の積層構造又は６層以上の積層構造であってもよい。 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.
　また、第１実施形態に係るガスバリアフィルムは、ガスバリア層が透明フィルム基材の主面に間接的に配置されていてもよい。例えば、図３に示すガスバリアフィルム３０は、透明フィルム基材１１とガスバリア層１２（酸炭化ケイ素層１３）との間に配置されたハードコート層３１を有する。ガスバリアフィルム３０では、ガスバリア層１２が透明フィルム基材１１の主面に間接的に配置されている。ハードコート層３１は、ガスバリアフィルム３０の硬度や弾性率等の機械的特性を高める層である。ハードコート層３１のガスバリア層１２側の主面が平滑であれば、その上に形成されるガスバリア層１２のガスバリア性が高められ、水蒸気透過率が小さくなる傾向がある。ハードコート層３１のガスバリア層１２側の主面の算術平均高さＳａは、１．５ｎｍ以下又は１．０ｎｍ以下であってもよい。算術平均高さＳａは、原子間力顕微鏡（ＡＦＭ）により測定した１μｍ×１μｍの範囲の三次元表面形状から、ＩＳＯ　２５１７８に準じて算出される。 Further, in the gas barrier film according to the first embodiment, the gas barrier layer may be indirectly arranged on the main surface of the transparent film substrate. For example, 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). In the gas barrier film 30 , 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 μm×1 μm measured with an atomic force microscope (AFM).
　ハードコート層３１は、個数平均一次粒子径が１．０μｍ未満の粒子（以下、「ナノ粒子」と記載することがある）を含んでいてもよい。例えば、ハードコート層３１がナノ粒子を含むことにより、ハードコート層３１の表面に微細な凹凸が形成され、ハードコート層３１とガスバリア層１２との密着性が向上する傾向がある。 The hard coat layer 31 may contain particles with a number average primary particle diameter of less than 1.0 μm (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.
　また、第１実施形態に係るガスバリアフィルムは、ガスバリア性をより向上させるため、透明フィルム基材の両主面にガスバリア層が設けられていてもよい。例えば、図４に示すガスバリアフィルム４０は、透明フィルム基材１１の一方の主面１１ａに配置されたガスバリア層１２（酸炭化ケイ素層１３）と、透明フィルム基材１１のもう一方の主面１１ｂに配置されたガスバリア層４１とを有する。第１実施形態に係るガスバリアフィルムでは、透明フィルム基材の両主面のそれぞれに、積層構造のガスバリア層が設けられていてもよい。 In addition, 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. For example, the gas barrier film 40 shown in FIG. and a gas barrier layer 41 disposed on the . In the gas barrier film according to the first embodiment, a gas barrier layer having a laminated structure may be provided on each of both main surfaces of the transparent film substrate.
　ガスバリア層４１の元素組成は、ガスバリア層１２の元素組成と同一でも異なっていてもよい。また、ガスバリア層４１の層構成は、ガスバリア層１２の層構成と同一でも異なっていてもよい。ただし、透明性、耐屈曲性及びガスバリア性により優れるガスバリアフィルムを得るためには、ガスバリア層４１が酸炭化ケイ素層を有することが好ましい。また、透明性、耐屈曲性及びガスバリア性に更に優れるガスバリアフィルムを得るためには、ガスバリア層４１中の酸炭化ケイ素層が、透明フィルム基材１１側から、炭素含有率０．１原子％未満の第１層、炭素含有率０．１原子％以上の第２層及び炭素含有率０．１原子％未満の第３層をこの順に有し、第２層の厚み比率が、第１層、第２層及び第３層の合計厚み１００％に対して２０％以上７０％以下であり、ＣｍａｘからＣｍｉｎを引いた値が６．０以下であることが好ましい。 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 . Moreover, 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 . However, in order to obtain a gas barrier film that is more excellent in transparency, bending resistance, and gas barrier properties, the gas barrier layer 41 preferably has a silicon oxycarbide layer. In addition, in order to obtain a gas barrier film with further excellent transparency, flex resistance, and gas barrier properties, 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. A first layer of, a second layer having a carbon content of 0.1 atomic % or more, and a third layer having a carbon content of less than 0.1 atomic % in this order, and the thickness ratio of the second layer is the first layer, It is preferably 20% or more and 70% or less with respect to 100% of the total thickness of the second layer and the third layer, and the value obtained by subtracting Cmin from Cmax is 6.0 or less.
　また、第１実施形態に係るガスバリアフィルムは、粘着剤層を更に有していてもよい。例えば、図５に示すガスバリアフィルム５０は、ガスバリアフィルム４０の構成に加え、粘着剤層５１を有する。ガスバリアフィルム５０では、ガスバリア層１２（酸炭化ケイ素層１３）の透明フィルム基材１１側とは反対側の主面１６ａに粘着剤層５１が配置されている。 In addition, the gas barrier film according to the first embodiment may further have an adhesive layer. For example, 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 . In the gas barrier film 50, 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.
　粘着剤層５１の酸炭化ケイ素層１３側とは反対側の主面には、はく離ライナー（不図示）が仮着されていてもよい。はく離ライナーは、例えば、ガスバリアフィルム５０を後述する偏光板１０１（図７参照）と貼り合わせるまでの間、粘着剤層５１の表面を保護する。はく離ライナーの構成材料としては、アクリル、ポリオレフィン、環状ポリオレフィン、ポリエステル等から形成されたプラスチックフィルムが好適に用いられる。はく離ライナーの厚みは、例えば、５μｍ以上２００μｍ以下である。はく離ライナーの表面には、離型処理が施されていることが好ましい。離型処理に使用される離型剤の材料としては、シリコーン系材料、フッ素系材料、長鎖アルキル系材料、脂肪酸アミド系材料等が挙げられる。 A release liner (not shown) 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 μm or more and 200 μm 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.
　以上、図面を参照しながら第１実施形態に係るガスバリアフィルムの構成について説明した。次に、第１実施形態に係るガスバリアフィルムの要素について説明する。 The configuration of the gas barrier film according to the first embodiment has been described above with reference to the drawings. Next, elements of the gas barrier film according to the first embodiment will be described.
［透明フィルム基材１１］
　透明フィルム基材１１は、例えば、ガスバリア層形成の土台となる層である。透明フィルム基材１１は、可撓性を有していてもよい。基材として可撓性のフィルムを用いることにより、ロールトゥロール方式でガスバリア層を形成可能であるため、ガスバリア層の生産性が高められる。また、可撓性フィルム上にガスバリア層が設けられたガスバリアフィルムは、フレキシブルデバイスやフォルダブルデバイスにも適用できるとの利点を有する。 [Transparent film substrate 11]
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. By using a flexible film as the base material, 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.
　透明フィルム基材１１の可視光透過率は、好ましくは８０％以上、より好ましくは９０％以上である。透明フィルム基材１１の厚みは、特に限定されないが、強度や取扱性等の観点から、５μｍ以上２００μｍ以下であることが好ましく、１０μｍ以上１５０μｍ以下であることがより好ましく、３０μｍ以上１００μｍ以下であることが更に好ましい。 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 μm or more and 200 μm or less, more preferably 10 μm or more and 150 μm or less, and 30 μm or more and 100 μm or less. is more preferred.
　透明フィルム基材１１を構成する樹脂材料としては、透明性、機械強度及び熱安定性に優れる樹脂材料が好ましい。樹脂材料の具体例としては、トリアセチルセルロース等のセルロース系樹脂、ポリエステル系樹脂、ポリエーテルスルホン系樹脂、ポリスルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂、（メタ）アクリル系樹脂、環状ポリオレフィン系樹脂（より具体的には、ノルボルネン系樹脂等）、ポリアリレート系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、及びこれらの混合物が挙げられる。 As the resin material that constitutes the transparent film substrate 11, a resin material that is excellent in transparency, mechanical strength and thermal stability is preferable. Specific examples of 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.
　透明フィルム基材１１のガスバリア層が形成される主面に、ガスバリア層との密着性向上等の目的で、コロナ処理、プラズマ処理、フレーム処理、オゾン処理、グロー処理、ケン化処理、カップリング剤による処理等の表面改質処理を施してもよい。 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.
　透明フィルム基材１１は、ガスバリア層が形成される側の表層がプライマー層（不図示）であってもよい。ガスバリア層が形成される側の表層がプライマー層である場合、透明フィルム基材１１とガスバリア層との密着性が高くなる傾向がある。プライマー層を構成する材料としては、例えば、ケイ素、ニッケル、クロム、スズ、金、銀、白金、亜鉛、インジウム、チタン、タングステン、アルミニウム、ジルコニウム、パラジウム等の金属（又は半金属）；これらの金属（又は半金属）の合金；これらの金属（又は半金属）の酸化物、フッ化物、硫化物又は窒化物等が挙げられる。プライマー層の厚みは、例えば、１ｎｍ以上２０ｎｍ以下であり、好ましくは１ｎｍ以上１５ｎｍ以下であり、より好ましくは１ｎｍ以上１０ｎｍ以下である。 The surface layer of the transparent film substrate 11 on which the gas barrier layer is formed may be a primer layer (not shown). 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.
［酸炭化ケイ素層１３］
　酸炭化ケイ素層１３は、ガスバリア層におけるガスバリア機能を主に担う層であり、ケイ素、酸素及び炭素を主たる構成元素とする材料からなる層である。酸炭化ケイ素層１３は、例えば、成膜方法として化学気相成長法（ＣＶＤ法）を採用し、後述する図６に示す成膜装置を用いて、第１層１４、第２層１５及び第３層１６を同じ条件で連続的に成膜することにより得られる。後述する図６に示す成膜装置を用いて、第１層１４、第２層１５及び第３層１６を同じ条件で連続的に成膜することにより、例えば、透過型電子顕微鏡を用いて得られる断面の暗視野像において、第１層１４と第２層１５との間、及び第２層１５と第３層１６との間のいずれについても界面が存在しない酸炭化ケイ素層１３が得られる。 [Silicon oxycarbide layer 13]
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. By using the film forming apparatus shown in FIG. 6 to be described later, 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. A silicon oxycarbide layer 13 in which there is no interface between the first layer 14 and the second layer 15 and between the second layer 15 and the third layer 16 in a dark field image of the cross section obtained. .
　酸炭化ケイ素層１３は、成膜時の原料、透明フィルム基材１１及び外部環境から取り込まれる少量の水素・窒素等の元素を含んでいてもよい。酸炭化ケイ素層１３において、ケイ素、酸素及び炭素以外の元素の含有率は、それぞれ、３原子％以下であることが好ましく、１原子％以下であることがより好ましく、０．５原子％以下であることが更に好ましい。酸炭化ケイ素層１３を構成する元素のうち、ケイ素、酸素及び炭素の合計含有率は、９０原子％以上であることが好ましく、９５原子％以上であることがより好ましく、９７原子％以上であることが更に好ましく、９９原子％以上、９９．５原子％以上又は９９．９原子％以上であってもよい。 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. In the silicon oxycarbide layer 13, 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.
　酸炭化ケイ素層１３に含まれる酸炭化ケイ素の組成は、一般式ＳｉＯｘＣｙで表される。以下、一般式ＳｉＯｘＣｙのｘを、単に「ｘ」と記載することがある。また、一般式ＳｉＯｘＣｙのｙを、単に「ｙ」と記載することがある。なお、特に断りがない限り、ｘ及びｙは、酸炭化ケイ素層１３の厚み方向の中央部（総エッチング時間の１／２が経過したとき）における組成比のｘ及びｙをさす。上記「総エッチング時間」とは、後述する実施例と同じ方法又はそれに準ずる方法で酸炭化ケイ素層１３の厚み方向における組成分析を行った際における、酸炭化ケイ素層１３のエッチングの開始から終了までの時間を意味する。 The composition of the silicon oxycarbide contained in the silicon oxycarbide layer 13 is represented by the general formula SiO x Cy . Hereinafter, x in the general formula SiO x Cy may be simply referred to as "x". Also, y in the general formula SiO x Cy may be simply described as "y". Unless otherwise specified, x and y refer to the composition ratio x and y at the central portion in the thickness direction of the silicon oxycarbide layer 13 (when 1/2 of the total etching time has elapsed). The above-mentioned "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
　ガスバリア性及び透明性により優れるガスバリアフィルムを得るためには、ｘが１．５以上２．５以下であり、かつｙが０．０１以上０．５以下であることが好ましく、ｘが１．８以上２．２以下であり、かつｙが０．０５以上０．２以下であることがより好ましい。 In order to obtain a gas barrier film with excellent gas barrier properties and transparency, 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.
　酸炭化ケイ素層１３の成膜方法は、特に限定されず、ドライコーティング法でもウェットコーティング法でもよいが、酸炭化ケイ素層１３の厚み方向における炭素含有率を上記範囲内に容易に調整するためには、酸炭化ケイ素層１３を、ＣＶＤ法により成膜することが好ましく、プラズマＣＶＤ法により成膜することがより好ましい。 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.
　透明フィルム基材１１として可撓性フィルムを用い、可撓性フィルム上にガスバリア層（例えば、酸炭化ケイ素層１３）を形成（成膜）する場合は、ロールトゥロール方式でＣＶＤ成膜を実施することにより、生産性を向上できる。ロールトゥロール方式のＣＶＤ成膜装置は、成膜ロールが一対の対向電極の一方又は両方の電極を構成しており、成膜ロール上をフィルムが走行する際に、フィルム上に薄膜が形成される。２つの成膜ロールが一対の対向電極を構成している場合は、それぞれの成膜ロール上で薄膜が形成されるため、成膜速度を２倍に向上できる。なお、ＣＶＤ法による成膜方法を説明する際の「上に」との表現は、ＣＶＤ成膜装置内の方向とは無関係であり、「に接して」と同義である。 When a flexible film is used as the transparent film substrate 11 and a gas barrier layer (for example, the silicon oxycarbide layer 13) is formed (film-formed) on the flexible film, CVD film formation is performed by a roll-to-roll method. productivity can be improved. In a roll-to-roll type CVD film forming apparatus, a film forming roll constitutes one or both electrodes of a pair of opposed electrodes, and a thin film is formed on the film when the film runs on the film forming rolls. be. When two film-forming rolls constitute a pair of opposing electrodes, a thin film is formed on each of the film-forming rolls, so the film-forming speed can be doubled. In addition, the expression "above" when explaining the film forming method by the CVD method has no relation to the direction in the CVD film forming apparatus, and has the same meaning as "in contact with".
　ＣＶＤ法により酸炭化ケイ素層１３を成膜する際のケイ素の供給源（ケイ素源）としては、毒性が低く、膜中への窒素の取り込みを抑制できることから有機ケイ素化合物が好ましく、ヘキサメチルジシラザン、ヘキサメチルジシロキサン、１，１，３，３－テトラメチルジシロキサン、テトラメチルシラン、ビニルトリメトキシシラン、ビニルトリメチルシラン、ジメチルジメトキシシラン、テトラメトキシシラン、メチルトリメトキシシラン、ジメチルジエトキシシラン、トリメチルメトキシシラン、テトラエトキシシラン、ジエチルジエトキシシラン、メチルジメトキシシラン、及びメチルジエトキシシロキサンからなる群より選択される一種以上がより好ましい。これらの有機ケイ素化合物の中でも、膜中への不純物の取り込みを抑制可能であり、透明性及びガスバリア性の高い膜を形成可能であることからヘキサメチルジシロキサンが特に好ましい。ケイ素源としての有機ケイ素化合物は炭素源も兼ねているが、有機ケイ素化合物に加えて、炭素源として、ケイ素を含まない有機化合物を用いてもよい。 As the source of silicon (silicon source) for forming the silicon oxycarbide layer 13 by the CVD method, an organosilicon compound is preferable because it has low toxicity and can suppress the incorporation of nitrogen into the film, and hexamethyldisilazane. , hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, tetramethylsilane, vinyltrimethoxysilane, vinyltrimethylsilane, dimethyldimethoxysilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, More preferably, one or more selected from the group consisting of trimethylmethoxysilane, tetraethoxysilane, diethyldiethoxysilane, methyldimethoxysilane, and methyldiethoxysiloxane. Among these 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. Although the 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.
　酸炭化ケイ素層１３を成膜するためには、通常、ケイ素源に加えて、酸素源となるガスを導入する。酸素源としては、酸素、一酸化炭素、二酸化炭素等が挙げられる。取り扱い性の観点から、酸素源としては酸素（酸素ガス）が好ましい。 In order to form the silicon oxycarbide layer 13, normally, in addition to the silicon source, an oxygen source gas is introduced. 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.
　ヘキサメチルジシロキサンと酸素を用いてＣＶＤ法により酸炭化ケイ素層１３を成膜する場合、酸素の導入量（流量）は、ヘキサメチルジシロキサン（気体）の導入量（流量）に対して、体積比で１０倍以上が好ましく、１５倍以上又は２０倍以上であってもよい。成膜速度を適切に維持する観点から、酸素の導入量は、ヘキサメチルジシロキサン（気体）の導入量に対して、体積比で２００倍以下が好ましく、１００倍以下又は５０倍以下であってもよい。 When the silicon oxycarbide layer 13 is formed by the CVD method using hexamethyldisiloxane and oxygen, the introduction amount (flow rate) of oxygen is set to the introduction amount (flow rate) of hexamethyldisiloxane (gas). The ratio is preferably 10 times or more, and may be 15 times or more or 20 times or more. From the viewpoint of appropriately maintaining the film formation rate, the amount of oxygen introduced is preferably 200 times or less, and preferably 100 times or less or 50 times or less, the volume ratio of the amount of hexamethyldisiloxane (gas) introduced. good too.
　ケイ素源に対する酸素源（又は酸素源及び炭素源）の導入量を変更することにより、酸炭化ケイ素層１３の組成を適宜に調整できる。 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.
　ＣＶＤ法により成膜する際の導入ガスとして、ケイ素源及び酸素源以外のガスを用いてもよい。例えば、液体のケイ素源を用いる場合は、液体を気化させてチャンバー（真空チャンバー）内に導入するためにキャリアガスを用いてもよい。また、酸素源を、キャリアガスと混合して真空チャンバー内に導入してもよく、プラズマ放電を安定させるために放電用ガスを用いてもよい。キャリアガス及び放電用ガスとしては、ヘリウム、アルゴン、ネオン、キセノン等の希ガスや水素が挙げられる。キャリアガス及び放電用ガスとしては、膜中に取り込まれる水素量を低減して透明性を高める観点から、希ガスが好ましい。 A gas other than the silicon source and the oxygen source may be used as the introduced gas when forming a film by the CVD method. For example, when using a liquid silicon source, a carrier gas may be used to vaporize the liquid and introduce it into the chamber (vacuum chamber). Also, an oxygen source may be mixed with a carrier gas and introduced into the vacuum chamber, and a discharge gas may be used to stabilize the plasma discharge. Carrier gas and discharge gas include rare gases such as helium, argon, neon, and xenon, and hydrogen. As the carrier gas and the discharge gas, rare gases are preferable from the viewpoint of reducing the amount of hydrogen taken into the film and increasing the transparency.
　プラズマＣＶＤ法における諸条件は、適宜設定すればよい。基材温度（成膜ロール表面の温度）は、例えば－２０℃以上５００℃以下の範囲内に設定される。フィルム基材上にガスバリア層（例えば、酸炭化ケイ素層１３）を成膜する場合の基材温度（フィルム基材温度）は、フィルム基材の耐熱性の観点から、１５０℃以下であることが好ましく、１００℃以下であることがより好ましい。成膜室（真空チャンバー内）の圧力は、例えば、０．００１Ｐａ以上５０Ｐａ以下である。プラズマ発生用電源としては、例えば、交流電源が用いられる。ロールトゥロール方式のＣＶＤ成膜における電源の周波数は、一般に５０ｋＨｚ以上５００ｋＨｚ以下の範囲内である。ロールトゥロール方式のＣＶＤ成膜における印加電力は、一般に０．１ｋＷ以上１０ｋＷ以下である。 Various conditions in the plasma CVD method can be set as appropriate. The substrate temperature (temperature of the surface of the film-forming roll) is set, for example, within the range of -20°C or higher and 500°C or lower. The substrate temperature (film substrate temperature) when forming a gas barrier layer (for example, silicon oxycarbide layer 13) on a film substrate is preferably 150° C. or less from the viewpoint of the heat resistance of the film substrate. The temperature is preferably 100° C. or lower, and more preferably 100° C. or lower. The pressure in the film forming chamber (inside the vacuum chamber) is, for example, 0.001 Pa or more and 50 Pa or less. An AC power supply, for example, is used as the power supply for plasma generation. The frequency of the power supply in roll-to-roll CVD film formation is generally in the range of 50 kHz to 500 kHz. The applied power in roll-to-roll CVD film formation is generally 0.1 kW or more and 10 kW or less.
　ガスバリア性により優れるガスバリアフィルムを得るためには、酸炭化ケイ素層１３の密度は、１．８０ｇ／ｃｍ３以上であることが好ましく、１．９０ｇ／ｃｍ３以上であることがより好ましく、２．００ｇ／ｃｍ３以上２．４０ｇ／ｃｍ３以下、２．０５ｇ／ｃｍ３以上２．３５ｇ／ｃｍ３以下、又は２．１０ｇ／ｃｍ３以上２．３０ｇ／ｃｍ３以下であってもよい。 In order to obtain a gas barrier film with better gas barrier properties, the silicon oxycarbide layer 13 preferably has a density of 1.80 g/cm 3 or more, more preferably 1.90 g/cm 3 or more. 00 g/cm 3 or more and 2.40 g/cm 3 or less, 2.05 g/cm 3 or more and 2.35 g/cm 3 or less, or 2.10 g/cm 3 or more and 2.30 g/cm 3 or less.
　高いガスバリア性と透明性とを両立させる観点から、酸炭化ケイ素層１３の厚みは、１０ｎｍ以上５００ｎｍ以下であることが好ましく、５０ｎｍ以上４００ｎｍ以下であることがより好ましく、８０ｎｍ以上３００ｎｍ以下であることが更に好ましい。また、ガスバリア層が酸炭化ケイ素層１３以外の層（上述したガスバリア性層等）を有する場合、高いガスバリア性と透明性とを両立させる観点から、ガスバリア層の合計厚みは、２０ｎｍ以上１０００ｎｍ以下であることが好ましく、５０ｎｍ以上８００ｎｍ以下であることがより好ましい。 From the viewpoint of achieving both high gas barrier properties and transparency, 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. Further, when the gas barrier layer has a layer other than the silicon oxycarbide layer 13 (such as the gas barrier layer described above), 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.
［ハードコート層３１］
　ハードコート層３１は、例えば、バインダー樹脂とナノ粒子とを含む。バインダー樹脂としては、熱硬化性樹脂、光硬化性樹脂、電子線硬化性樹脂等の硬化性樹脂が好ましく用いられる。硬化性樹脂の種類としては、ポリエステル系樹脂、アクリル系樹脂、ウレタン系樹脂、アクリルウレタン系樹脂、アミド系樹脂、シリコーン系樹脂、シリケート系樹脂、エポキシ系樹脂、メラミン系樹脂、オキセタン系樹脂等が挙げられる。硬化性樹脂は、一種又は二種以上を使用できる。これらの中でも、硬度が高く、光硬化が可能であることから、アクリル系樹脂、アクリルウレタン系樹脂及びエポキシ系樹脂からなる群より選択される一種以上が好ましく、アクリル系樹脂及びアクリルウレタン系樹脂からなる群より選択される一種以上がより好ましい。 [Hard coat layer 31]
The hard coat layer 31 contains, for example, a binder resin and nanoparticles. As the binder resin, curable resins such as thermosetting resins, photocurable resins and electron beam curable resins are preferably used. Types of 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. Among these, one or more selected from the group consisting of 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
　ハードコート層３１に含まれるナノ粒子の個数平均一次粒子径は、バインダー樹脂中での分散性を高める観点から、１５ｎｍ以上であることが好ましく、２０ｎｍ以上であることがより好ましい。密着性向上に寄与する微細な凹凸形状を形成する観点から、ハードコート層３１に含まれるナノ粒子の個数平均一次粒子径は、９０ｎｍ以下であることが好ましく、７０ｎｍ以下であることがより好ましく、５０ｎｍ以下であることが更に好ましい。 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.
　ナノ粒子の材料としては、無機酸化物が好ましい。無機酸化物としては、シリカ、酸化チタン、酸化アルミニウム、酸化ジルコニウム、酸化ニオブ、酸化亜鉛、酸化スズ、酸化セリウム、酸化マグネシウム等の金属（又は半金属）の酸化物が挙げられる。無機酸化物は、複数種の（半）金属の複合酸化物でもよい。例示の無機酸化物の中でも、密着性向上効果が高いことから、シリカが好ましい。つまり、ナノ粒子としては、シリカ粒子（ナノシリカ粒子）が好ましい。ナノ粒子としての無機酸化物粒子の表面には、樹脂との密着性や親和性を高める目的で、アクリル基、エポキシ基等の官能基が導入されていてもよい。 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. Among the exemplified inorganic oxides, 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.
　ハードコート層３１におけるナノ粒子の量は、バインダー樹脂とナノ粒子の合計量１００重量部に対して、５重量部以上であることが好ましく、１０重量部以上、２０重量部以上又は３０重量部以上であってもよい。ナノ粒子の量が５重量部以上であれば、ハードコート層３１上に形成されるガスバリア層との密着性を向上させることができる。ハードコート層３１におけるナノ粒子の量の上限は、バインダー樹脂とナノ粒子の合計量１００重量部に対して、例えば９０重量部であり、８０重量部であることが好ましく、７０重量部であってもよい。 The amount of the nanoparticles in the hard coat layer 31 is preferably 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, or 30 parts by weight or more with respect to 100 parts by weight of the total amount of the binder resin and the nanoparticles. may be If the amount of the nanoparticles is 5 parts by weight or more, the adhesion to the gas barrier layer formed on the hard coat layer 31 can be improved. The upper limit of the amount of nanoparticles in the hard coat layer 31 is, for example, 90 parts by weight, preferably 80 parts by weight, and preferably 70 parts by weight with respect to 100 parts by weight of the total amount of the binder resin and the nanoparticles. good too.
　ハードコート層３１の厚みは、特に限定されないが、高い硬度を実現しつつガスバリア層との密着性を向上させるためには、０．５μｍ以上であることが好ましく、１．０μｍ以上であることがより好ましく、２．０μｍ以上であることが更に好ましく、３．０μｍ以上であることが更により好ましい。一方、凝集破壊による強度の低下を抑制するためには、ハードコート層３１の厚みは、２０μｍ以下であることが好ましく、１５μｍ以下であることがより好ましく、１２μｍ以下であることが更に好ましい。 The thickness of the hard coat layer 31 is not particularly limited, but is preferably 0.5 μm or more, more preferably 1.0 μm or more, in order to improve the adhesion to the gas barrier layer while achieving high hardness. It is more preferably 2.0 μm or more, and even more preferably 3.0 μm or more. On the other hand, the thickness of the hard coat layer 31 is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 12 μm or less, in order to suppress a decrease in strength due to cohesive failure.
（ハードコート層３１の形成方法）
　透明フィルム基材１１上にハードコート組成物を塗布し、必要に応じて溶媒の除去及び樹脂の硬化を行うことにより、ハードコート層３１が形成される。ハードコート組成物は、例えば、上記のバインダー樹脂及びナノ粒子を含み、必要に応じてこれらの成分を溶解又は分散可能な溶媒を含む。ハードコート組成物中の樹脂成分が硬化性樹脂である場合は、ハードコート組成物中に、適宜の重合開始剤が含まれていることが好ましい。例えば、ハードコート組成物中の樹脂成分が光硬化型樹脂である場合には、ハードコート組成物中に光重合開始剤が含まれていることが好ましい。 (Method for Forming Hard Coat Layer 31)
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. When the resin component in the hard coat composition is a curable resin, the hard coat composition preferably contains an appropriate polymerization initiator. For example, when the resin component in the hard coat composition is a photocurable resin, the hard coat composition preferably contains a photopolymerization initiator.
　ハードコート組成物は、上記成分の他に、個数平均一次粒子径が１．０μｍ以上の粒子（マイクロ粒子）、レベリング剤、粘度調整剤（チクソトロピー剤、増粘剤等）、帯電防止剤、ブロッキング防止剤、分散剤、分散安定剤、酸化防止剤、紫外線吸収剤、消泡剤、界面活性剤、滑剤等の添加剤を含んでいてもよい。 In addition to the above components, the hard coat composition includes particles (microparticles) having a number average primary particle diameter of 1.0 μm or more, leveling agents, viscosity modifiers (thixotropic agents, thickeners, etc.), antistatic agents, blocking agents, Additives such as inhibitors, dispersants, dispersion stabilizers, antioxidants, UV absorbers, antifoaming agents, surfactants and lubricants may be included.
　ハードコート組成物の塗布方法としては、バーコート法、ロールコート法、グラビアコート法、ロッドコート法、スロットオリフィスコート法、カーテンコート法、ファウンテンコート法、コンマコート法等の任意の適切な方法を採用し得る。 As a method for applying the hard coat composition, 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.
［粘着剤層５１］
　粘着剤層５１の構成材料としては、可視光透過率が高い粘着剤が好適に用いられる。粘着剤層５１を構成する粘着剤としては、例えば、アクリル系ポリマー、シリコーン系ポリマー、ポリエステル、ポリウレタン、ポリアミド、ポリビニルエーテル、酢酸ビニル－塩化ビニル共重合体、変性ポリオレフィン、エポキシ系樹脂、フッ素系樹脂、天然ゴム、合成ゴム等のポリマーをベースポリマーとする透明な粘着剤を、適宜に選択して用いることができる。粘着剤層５１の厚みは、好ましくは５μｍ以上１００μｍ以下である。粘着剤層５１の屈折率は、例えば１．４以上１．５以下である。 [Adhesive layer 51]
As a constituent material of the adhesive layer 51, an adhesive having a high visible light transmittance is preferably used. Examples of 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 μm or more and 100 μm or less. The refractive index of the adhesive layer 51 is, for example, 1.4 or more and 1.5 or less.
［ガスバリアフィルムの特性］
　ガスバリアフィルムの水蒸気透過率は、厚み１００ｎｍのガスバリア層を有するガスバリアフィルムを基準に規格化した値として、０．１０ｇ／ｍ２・ｄａｙ以下であることが好ましく、０．０８ｇ／ｍ２・ｄａｙ以下であることがより好ましい。有機ＥＬ素子等の保護対象の劣化を抑制する観点からは、水蒸気透過率は小さいほど好ましい。ガスバリアフィルムの水蒸気透過率の下限は、特に限定されないが、上記規格化した値として、一般には１．０×１０－５ｇ／ｍ２・ｄａｙである。水蒸気透過率（ＷＶＴＲ）は、温度４０℃、相対湿度差９０％の条件下で、ＪＩＳ　Ｋ　７１２９：２００８の附属書Ｂ（モコン法）の記載に従って測定される。 [Characteristics of gas barrier film]
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. Although 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).
　ガスバリアフィルムの光透過率は、８０％以上であることが好ましく、９０％以上であることがより好ましい。光透過率は、ＪｌＳ　Ｚ８７８１－３：２０１６で規定されるＣＩＥ三刺激値のＹ値である。ガスバリアフィルムの光透過率は、例えば、第２層厚み比率を変更することにより調整できる。 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.
　ガスバリアフィルムの耐屈曲性は、後述する実施例に記載の屈曲試験により評価できる。例えば、後述する実施例に記載の屈曲試験と同じ方法又はそれに準ずる方法でガスバリアフィルムを評価した際に、屈曲直径６ｍｍの条件でクラックが発生しないことが好ましく、屈曲直径５ｍｍの条件でクラックが発生しないことがより好ましい。 The flex resistance of the gas barrier film can be evaluated by the flex test described in Examples below. For example, when the gas barrier film is evaluated by the same method as the bending test described in the examples described later or by a method equivalent thereto, it is preferable that cracks do not occur under the condition of a bending diameter of 6 mm, and cracks occur under the condition of a bending diameter of 5 mm. It is more preferable not to.
＜第２実施形態：ガスバリアフィルムの製造方法＞
　次に、本発明の第２実施形態に係るガスバリアフィルムの製造方法について説明する。第２実施形態に係るガスバリアフィルムの製造方法は、上述した第１実施形態に係るガスバリアフィルムの好適な製造方法である。よって、上述した第１実施形態と重複する構成要素については、その説明を省略する場合がある。第２実施形態に係るガスバリアフィルムの製造方法は、一対の対向電極として一対の成膜ロールを有する成膜装置のチャンバー（真空チャンバー）内に、有機ケイ素化合物（例えば、ヘキサメチルジシロキサン等）及び酸素を導入して、ＣＶＤ法により酸炭化ケイ素層を形成する工程を備える。 <Second Embodiment: Method for Producing Gas Barrier Film>
Next, a method for manufacturing a gas barrier film according to the second embodiment of the present invention will be described. 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. In the method for producing a gas barrier film according to the second embodiment, an organosilicon compound (eg, hexamethyldisiloxane) and A step of introducing oxygen and forming a silicon oxycarbide layer by a CVD method is provided.
　以下、第２実施形態に係るガスバリアフィルムの製造方法について、図６を参照しながら説明する。図６は、第２実施形態に係るガスバリアフィルムの製造方法に使用される成膜装置の一例を示す構成図である。 A method for manufacturing a gas barrier film according to the second embodiment will be described below with reference to FIG. 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.
　図６に示す成膜装置は、送り出しロール７１と、搬送ロール７２、７３、７４及び７５と、一対の対向電極としての成膜ロール７６及び７７と、巻取りロール７８と、成膜ガスを導入するためのガス供給口７９とを備えている。ガス供給口７９は、複数個設けられていてもよい。成膜ロール７６及び７７の各々の内部には、図示を省略した磁場発生装置が設置されている。また、図６に示す成膜装置では、少なくとも成膜ロール７６及び７７と、ガス供給口７９と、プラズマ発生用電源（不図示）とが図示を省略した真空チャンバー内に配置されている。更に、図６に示す成膜装置では、上記真空チャンバーが図示を省略した真空ポンプに接続されており、この真空ポンプにより真空チャンバー内の圧力を適宜調整することが可能となっている。 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 . Further, in the film forming apparatus shown in FIG. 6, at least the film forming rolls 76 and 77, the gas supply port 79, and the power source for plasma generation (not shown) are arranged in a vacuum chamber (not shown). Furthermore, in the film forming apparatus shown in FIG. 6, 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.
　図６に示す成膜装置では、一対の成膜ロール（成膜ロール７６及び７７）を一対の対向電極として機能させることが可能となるように、成膜ロール７６及び７７がそれぞれプラズマ発生用電源（不図示）に接続されている。そのため、図６に示す成膜装置では、プラズマ発生用電源により電力を供給することにより、成膜ロール７６と成膜ロール７７との間の空間に放電することが可能であり、これにより成膜ロール７６と成膜ロール７７との間の空間にプラズマを発生させることができる。図６に示す成膜装置において、高い成膜レートで成膜するためには、一対の成膜ロール（成膜ロール７６及び７７）は、その中心軸が同一平面上において略平行となるようにして配置されていることが好ましい。 In the film forming apparatus shown in FIG. 6, 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 . In the film forming apparatus shown in FIG. 6, in order to form a film at a high film forming rate, 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.
　このような図６に示す成膜装置を用いて、例えば、第１実施形態に係るガスバリアフィルムの説明において例示したプラズマＣＶＤ法における諸条件を採用し、第１実施形態に係るガスバリアフィルムを容易に製造することができる。例えば、上述したガスバリアフィルム１０（図１参照）を製造する場合は、成膜ガス（より具体的には、有機ケイ素化合物、酸素等）を真空チャンバー内に供給しつつ、一対の成膜ロール（成膜ロール７６及び７７）間にプラズマ放電を発生させることにより、上記成膜ガスがプラズマによって分解され、成膜ロール７６近傍の成膜領域及び成膜ロール７７近傍の成膜領域の双方において、透明フィルム基材１１（図１参照）上に酸炭化ケイ素層１３（図１参照）が形成される。例えば、成膜ロール７６近傍の成膜領域及び成膜ロール７７近傍の成膜領域の各々において、ガス供給口７９から比較的遠い箇所では、気化した有機ケイ素化合物の分解量が比較的多い。一方、成膜ロール７６近傍の成膜領域及び成膜ロール７７近傍の成膜領域の各々において、ガス供給口７９から比較的近い箇所では、気化した有機ケイ素化合物の分解量が比較的少ない。そのため、図６に示す成膜装置を用いて得られた酸炭化ケイ素層１３は、層の厚み方向の中央部分の炭素含有率が比較的高くなる。なお、酸炭化ケイ素層１３の成膜に際しては、透明フィルム基材１１が、送り出しロール７１、搬送ロール７２等により搬送され、ロールトゥロール方式の連続的な成膜プロセスにより、透明フィルム基材１１上に酸炭化ケイ素層１３が形成される。 Using such a film forming apparatus shown in FIG. 6, for example, 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. For example, when manufacturing the above-described gas barrier film 10 (see FIG. 1), 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). For example, in each of the film-forming region near the film-forming roll 76 and the film-forming region near the film-forming roll 77 , the decomposition amount of the vaporized organosilicon compound is relatively large at a location relatively far from the gas supply port 79 . On the other hand, in each of the film-forming region near the film-forming roll 76 and the film-forming region near the film-forming roll 77 , 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. In forming the silicon oxycarbide layer 13, 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.
　図６に示す成膜装置において、成膜ロール７６の中心軸と成膜ロール７７の中心軸とを含む仮想平面Ｐからのガス供給口７９の高さＨ、成膜ロール７６とガス供給口７９との最短距離Ｄ１、成膜ロール７７とガス供給口７９との最短距離Ｄ２、成膜ロール７６のロール径、成膜ロール７７のロール径、成膜ロール７６の抱き角度、及び成膜ロール７７の抱き角度（以下、これらをまとめて「成膜装置条件」と記載することがある）のうちの少なくとも１つを変更すると、成膜ロール７６近傍の成膜領域及び成膜ロール７７近傍の成膜領域の各々において、導入した成膜ガスの分布が成膜ロールの周方向に沿って変化する。よって、成膜装置条件のうちの少なくとも１つを変更することにより、酸炭化ケイ素層１３（図１参照）の炭素含有率を厚み方向で変化させることができる。なお、「抱き角度」とは、フィルムが成膜ロールの外周面に周方向において接触する角度範囲を成膜ロールの中心角で表したものをさす。 In the film forming apparatus shown in FIG. 6, the height H of the gas supply port 79 from the virtual plane P including the central axis of the film forming roll 76 and the central axis of the film forming roll 77, the film forming roll 76 and the gas supply port 79 , the shortest distance D2 between the film-forming roll 77 and the gas supply port 79, the roll diameter of the film-forming roll 76, the roll diameter of the film-forming roll 77, the holding angle of the film-forming roll 76, and the film-forming roll 77 When 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. In each of the film regions, 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.
　上記成膜装置条件のうち、ガス供給口７９の高さＨは、第２層厚み比率との相関性が高い。第２層厚み比率を第１実施形態で説明した特定範囲内に容易に調整するためには、ガス供給口７９の高さＨは、１００ｍｍ以上２００ｍｍ以下であることが好ましく、１５０ｍｍ以上１８０ｍｍ以下であることがより好ましい。なお、ガス供給口７９が複数個設けられている場合、複数個のガス供給口７９のそれぞれの高さＨは、同一でも異なっていてもよい。なお、第２層厚み比率は、図６に示す成膜装置を用いて酸炭化ケイ素層１３を成膜する際において、例えば、有機ケイ素化合物の導入量、酸素の導入量、及び印加電力のうちの少なくとも１つを変更することによっても調整できる。 　Among the above film forming apparatus conditions, the height H of the gas supply port 79 has a high correlation with the second layer thickness ratio. In order to easily adjust the second layer thickness ratio within the specific range described in the first embodiment, 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 In addition, when a plurality of gas supply ports 79 are provided, the height H of each of the plurality of gas supply ports 79 may be the same or different. In addition, when 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
　Ｃｍａｘ及びＣｍｉｎは、図６に示す成膜装置を用いて酸炭化ケイ素層１３を成膜する際において、例えば、有機ケイ素化合物の導入量、酸素の導入量、及び印加電力のうちの少なくとも１つを変更することにより調整できる。 When forming the silicon oxycarbide layer 13 using the film forming apparatus shown in FIG . It can be adjusted by changing one.
＜第３実施形態：ガスバリア層付き偏光板＞
　次に、本発明の第３実施形態に係るガスバリア層付き偏光板について説明する。第３実施形態に係るガスバリア層付き偏光板は、第１実施形態に係るガスバリアフィルムと、偏光子とを備える。図７は、第３実施形態に係るガスバリア層付き偏光板の一例を示す断面図である。図７に示すガスバリア層付き偏光板１００は、上述したガスバリアフィルム５０と、偏光板１０１とを有する。ガスバリア層付き偏光板１００では、粘着剤層５１の酸炭化ケイ素層１３側とは反対側の主面５１ａに偏光板１０１が配置されている。つまり、偏光板１０１と酸炭化ケイ素層１３とが、粘着剤層５１を介して貼り合わせられている。なお、図７に示すガスバリア層付き偏光板１００はガスバリアフィルム５０（ガスバリアフィルム４０）を有するが、第３実施形態に係るガスバリア層付き偏光板が有するガスバリアフィルムは、ガスバリアフィルム５０に限定されず、例えば、ガスバリアフィルム１０、ガスバリアフィルム２０又はガスバリアフィルム３０であってもよい。 <Third Embodiment: Polarizing Plate with Gas Barrier Layer>
Next, a polarizing plate with a gas barrier layer according to a third embodiment of the present invention will be described. 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 . In the polarizing plate 100 with a gas barrier layer, 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. Although 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. For example, it may be the gas barrier film 10, the gas barrier film 20, or the gas barrier film 30.
　偏光板１０１は、偏光子（不図示）を含み、一般には、偏光子の両主面に偏光子保護フィルムとしての透明保護フィルム（不図示）が積層されている。偏光子の一方の主面又は両主面の透明保護フィルムは、設けられていなくてもよい。偏光子としては、例えば、ポリビニルアルコール系フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料等の二色性物質を吸着させて一軸延伸したものが挙げられる。 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. As 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.
　透明保護フィルムとしては、セルロース系樹脂、環状ポリオレフィン系樹脂、アクリル系樹脂、フェニルマレイミド系樹脂、ポリカーボネート系樹脂等から構成された透明樹脂フィルムが好ましく用いられる。透明保護フィルムとしてガスバリアフィルムを用いてもよい。 As the transparent protective film, 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.
　偏光板１０１は、偏光子の一方又は両方の主面に、必要に応じて適宜の接着剤層や粘着剤層を介して積層された光学機能フィルムを備えていてもよい。光学機能フィルムとしては、位相差板、視野角拡大フィルム、視野角制限（覗き見防止）フィルム、輝度向上フィルム等が挙げられる。 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. Examples of the optical functional film include retardation plates, viewing angle widening films, viewing angle limiting (peep prevention) films, brightness improving films, and the like.
　なお、図７に示すガスバリア層付き偏光板１００では、偏光板１０１と酸炭化ケイ素層１３とが粘着剤層５１を介して貼り合わせられているが、本発明に係るガスバリア層付き偏光板は、図７に示す構成に限定されず、例えば、偏光子にガスバリア層が直接設けられていてもよい。また、本発明に係るガスバリア層付き偏光板は、偏光子に隣接して配置された透明保護フィルムにガスバリア層が直接設けられていてもよい。 In the gas barrier layer-attached polarizing plate 100 shown in FIG. 7, 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. In the polarizing plate with a gas barrier layer according to the present invention, the gas barrier layer may be directly provided on the transparent protective film arranged adjacent to the polarizer.
　第３実施形態に係るガスバリア層付き偏光板は、第１実施形態に係るガスバリアフィルムを備えるため、透明性、耐屈曲性及びガスバリア性に優れる。 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.
＜第４実施形態：画像表示装置＞
　次に、本発明の第４実施形態に係る画像表示装置について説明する。第４実施形態に係る画像表示装置は、第１実施形態に係るガスバリアフィルム又は第３実施形態に係るガスバリア層付き偏光板と、画像表示セルとを備える。 <Fourth Embodiment: Image Display Device>
Next, an image display device according to a fourth embodiment of the invention will be described. An image display device according to the fourth embodiment 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.
　図８は、第４実施形態に係る画像表示装置の一例を示す断面図である。図８に示す画像表示装置２００は、ガスバリアフィルム５０を有するガスバリア層付き偏光板１００と、画像表示セル２０２とを備える。画像表示セル２０２は、基板２０３と、基板２０３上に設けられた表示素子２０４とを備える。画像表示装置２００では、ガスバリア層４１と表示素子２０４とが、粘着剤層２０１を介して貼り合わせられている。なお、図８に示す画像表示装置２００はガスバリアフィルム５０（ガスバリアフィルム４０）を有するが、第４実施形態に係る画像表示装置が有するガスバリアフィルムは、ガスバリアフィルム５０に限定されず、例えば、ガスバリアフィルム１０、ガスバリアフィルム２０又はガスバリアフィルム３０であってもよい。 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 . In the image display device 200 , the gas barrier layer 41 and the display element 204 are bonded together with the adhesive layer 201 interposed therebetween. Although 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. For example, the gas barrier film 10, it may be the gas barrier film 20 or the gas barrier film 30;
　粘着剤層２０１を構成する粘着剤としては、例えば上述した粘着剤層５１を構成する粘着剤として例示したものと同じ粘着剤が挙げられる。粘着剤層２０１を構成する粘着剤と粘着剤層５１を構成する粘着剤とは、同種であってもよく、互いに異なる種類であってもよい。 As the adhesive constituting the adhesive layer 201, for example, 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.
　粘着剤層２０１の厚みの好ましい範囲は、例えば、上述した粘着剤層５１の厚みの好ましい範囲と同じである。粘着剤層２０１の厚み及び粘着剤層５１の厚みは、同一であっても異なっていてもよい。 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.
　基板２０３としては、ガラス基板又はプラスチック基板が用いられる。画像表示セル２０２がトップエミッション型である場合、基板２０３は透明である必要はなく、基板２０３としてポリイミドフィルム等の高耐熱性フィルムを用いてもよい。 A glass substrate or a plastic substrate is used as the substrate 203 . When the image display cell 202 is of the top emission type, 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 .
　表示素子２０４としては、有機ＥＬ素子、液晶素子、電気泳動方式の表示素子（電子ペーパー）等が挙げられる。画像表示セル２０２の視認側には、タッチパネルセンサー（不図示）が配置されていてもよい。 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 .
　表示素子２０４が有機ＥＬ素子である場合、画像表示セル２０２は、例えばトップエミッション型である。有機ＥＬ素子は、例えば、基板２０３側から、金属電極（不図示）、有機発光層（不図示）及び透明電極（不図示）をこの順に備える。 When the display element 204 is an organic EL element, 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.
　有機発光層は、それ自身が発光層として機能する有機層の他に、電子輸送層、正孔輸送層等を備えていてもよい。透明電極は、金属酸化物層又は金属薄膜であり、有機発光層からの光を透過する。基板２０３の裏面側には基板２０３の保護や補強を目的としてバックシート（不図示）が設けられていてもよい。 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 .
　有機ＥＬ素子の金属電極は光反射性である。そのため、外光が画像表示セル２０２の内部に入射すると、金属電極で光が反射し、外部からは反射光が鏡面のように視認される。画像表示セル２０２の視認側に、偏光板１０１として円偏光板を配置することにより、金属電極での反射光の外部への再出射を防止して、画像表示装置２００の画面の視認性及び意匠性を向上させることができる。 　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. By arranging 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.
　円偏光板は、例えば偏光子の画像表示セル２０２側の主面に位相差フィルムを備える。偏光子に隣接して配置された透明保護フィルムが位相差フィルムであってもよい。また、ガスバリアフィルム５０の透明フィルム基材１１が位相差フィルムであってもよい。位相差フィルムがλ／４のレターデーションを有し、位相差フィルムの遅相軸方向と偏光子の吸収軸方向とのなす角度が４５°である場合に、偏光子と位相差フィルムとの積層体が、金属電極での反射光の再出射を抑制するための円偏光板として機能する。円偏光板を構成する位相差フィルムは、２層以上のフィルムが積層されたものであってもよい。例えば、偏光子とλ／２板とλ／４板とを、それぞれの光学軸が所定の角度をなすように積層することにより、可視光の広帯域にわたって円偏光板として機能する広帯域円偏光板が得られる。 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. Further, 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 λ / 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. For example, by laminating a polarizer, a λ/2 plate, and a λ/4 plate so that their optical axes form a predetermined angle, a broadband circularly polarizing plate that functions as a circularly polarizing plate over a wide band of visible light is obtained. can get.
　画像表示セル２０２は、基板上に透明電極と有機発光層と金属電極とをこの順に積層したボトムエミッション型であってもよい。ボトムエミッション型の画像表示セル２０２では、透明基板が用いられ、透明基板が視認側に配置される。透明基板としてガスバリアフィルムを用いてもよい。 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. In the bottom emission type image display cell 202, 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.
　第４実施形態に係る画像表示装置は、第１実施形態に係るガスバリアフィルムを備えるため、ガス（例えば水蒸気）に起因する表示素子の劣化を抑制できる。 Since the image display device according to the fourth embodiment 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).
　以下、本発明の実施例について説明するが、本発明は以下の実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to the following examples.
＜ガスバリアフィルムの作製＞
　以下、実施例１及び２並びに比較例１～４のガスバリアフィルムの作製方法について、それぞれ説明する。実施例１及び２並びに比較例１～４のガスバリアフィルムの作製において、ガスバリア層の成膜には、いずれも、上述した図６に示す成膜装置と同じ構成を備えた成膜装置（詳しくは、ロールトゥロール方式のＣＶＤ成膜装置）を使用した。ガスバリア層の成膜に使用した上記成膜装置は、酸素を導入するためのガス供給口と、ヘキサメチルジシロキサンを導入するためのガス供給口とを備えていた。また、実施例１及び２並びに比較例１～４のガスバリアフィルムの作製では、酸素を導入するためのガス供給口の高さ（図６の高さＨ）を１７４ｍｍとし、かつヘキサメチルジシロキサンを導入するためのガス供給口の高さ（図６の高さＨ）を１５６ｍｍとした。 <Production of gas barrier film>
The methods for producing the gas barrier films of Examples 1 and 2 and Comparative Examples 1 to 4 are described below. In the production of the gas barrier films of Examples 1 and 2 and Comparative Examples 1 to 4, a film forming apparatus having the same configuration as the film forming apparatus shown in FIG. , a roll-to-roll type CVD film forming apparatus) was used. The film forming apparatus used for forming the gas barrier layer had a gas supply port for introducing oxygen and a gas supply port for introducing hexamethyldisiloxane. In the production of the gas barrier films of Examples 1 and 2 and Comparative Examples 1 to 4, the height of the gas supply port for introducing oxygen (height H in FIG. 6) was set to 174 mm, and hexamethyldisiloxane was used. The height of the gas supply port for introduction (height H in FIG. 6) was set to 156 mm.
［実施例１］
　透明フィルム基材としての厚み４０μｍの環状ポリオレフィンフィルム（日本ゼオン社製「ゼオノア（登録商標）フィルムＺＦ－１４」）を成膜装置にセットし、真空チャンバー内を１×１０－３Ｐａまで減圧した。次いで、フィルムを走行させながら、基材温度１２℃で、厚み１７６ｎｍの酸炭化ケイ素層（ガスバリア層）をＣＶＤ成膜し、実施例１のガスバリアフィルムを得た。実施例１のガスバリアフィルムを得る際のＣＶＤ成膜では、プラズマ発生用電源の周波数を８０ｋＨｚとし、印加電力１．０ｋＷの条件で放電してプラズマを発生させ、ヘキサメチルジシロキサン（ＨＭＤＳＯ）：２５ｓｃｃｍ、酸素：７００ｓｃｃｍの流量条件で、真空チャンバー内の成膜ロール間（電極間）にガスを導入し、圧力１．０Ｐａで成膜した。なお、ＨＭＤＳＯは加熱気化させて、真空チャンバー内に導入した。 [Example 1]
A 40 μm-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. In the CVD film formation for obtaining the 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.
［実施例２］
　印加電力を０．６ｋＷに変更し、ＨＭＤＳＯの流量条件を１５ｓｃｃｍに変更し、酸炭化ケイ素層の厚みを１８６ｎｍに変更したこと以外は、実施例１と同じ方法により実施例２のガスバリアフィルムを作製した。 [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.
［比較例１］
　ＨＭＤＳＯの流量条件を１５ｓｃｃｍに変更し、ガスバリア層の厚みを１９７ｎｍに変更したこと以外は、実施例１と同じ方法により比較例１のガスバリアフィルムを作製した。 [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.
［比較例２］
　ＨＭＤＳＯの流量条件を２０ｓｃｃｍに変更し、酸炭化ケイ素層の厚みを１７３ｎｍに変更したこと以外は、実施例１と同じ方法により比較例２のガスバリアフィルムを作製した。 [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.
［比較例３］
　印加電力を２．０ｋＷに変更し、ＨＭＤＳＯの流量条件を５０ｓｃｃｍに変更し、酸炭化ケイ素層の厚みを２０３ｎｍに変更し、成膜時の圧力を１．６Ｐａに変更したこと以外は、実施例１と同じ方法により比較例３のガスバリアフィルムを作製した。 [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.
［比較例４］
　印加電力を０．３ｋＷに変更し、ＨＭＤＳＯの流量条件を５０ｓｃｃｍに変更し、酸素の流量条件を１００ｓｃｃｍに変更し、酸炭化ケイ素層の厚みを２５０ｎｍに変更したこと以外は、実施例１と同じ方法により比較例４のガスバリアフィルムを作製した。 [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.
＜ガスバリア層の組成分析＞
　Ａｒイオン銃を備えるＸ線光電子分光装置（アルバック・ファイ社製「Ｑｕａｎｔｅｒａ　ＳＸＭ」）を用いて、ガスバリア層の透明フィルム基材側とは反対側の主面からガスバリア層を下記条件でエッチングしながら、ＸＰＳによりガスバリア層の厚み方向における組成分析を行い、厚み方向の各測定個所において各元素（Ｓｉ、Ｏ、Ｎ及びＣ）の含有率を算出した。各元素の含有率の算出には、ワイドスキャンスペクトルから得られるＳｉの２ｐ、Ｏの１ｓ、Ｎの１ｓ、及びＣの１ｓのそれぞれの結合エネルギーに相当するピークを用いた。また、厚み方向の各測定個所において算出された各元素の含有率から、第２層厚み比率を算出した。詳細な測定条件を以下に示す。なお、ガスバリア層の表層は、汚染の影響で炭素含有率が大きくなる傾向があるため、エッチング開始時点における測定箇所については、炭素含有率を０原子％として各元素の含有率を算出した。 <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. Also, 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.
［測定条件］
　Ｘ線源：モノクロＡｌＫα
　Ｘ線の焦点サイズ：１００μｍφ（１５ｋＶ、２５Ｗ）
　光電子取り出し角：試料表面に対して４５°
　結合エネルギーの補正：Ｃ－Ｃ結合由来のピークを２８５．０ｅＶに補正（最表面のみ）
　帯電中和条件：電子中和銃とＡｒイオン銃（中和モード）の併用
　Ａｒイオン銃の加速電圧：１ｋＶ
　Ａｒイオン銃のラスターサイズ：１ｍｍ×１ｍｍ
　Ａｒイオン銃のエッチング速度：５ｎｍ／分（ＳｉＯ２換算）
　元素組成の測定間隔：６０秒（５ｎｍ） [Measurement condition]
X-ray source: monochrome AlKα
X-ray focal size: 100 μmφ (15 kV, 25 W)
Photoelectron extraction angle: 45° with respect to the sample surface
Bond energy correction: CC bond derived peak corrected to 285.0 eV (top surface only)
Charge neutralization conditions: combined use of electron neutralization gun and Ar ion gun (neutralization mode) Acceleration voltage of Ar ion gun: 1 kV
Ar ion gun raster size: 1mm x 1mm
Etching rate of Ar ion gun: 5 nm/min (in terms of SiO2 )
Elemental composition measurement interval: 60 seconds (5 nm)
＜ガスバリアフィルムの評価方法＞
［水蒸気透過率］
　ＪＩＳ　Ｋ　７１２９：２００８の附属書Ｂ（モコン法）の記載に従って、温度４０℃、相対湿度差９０％の条件で、各ガスバリアフィルムの水蒸気透過率（ＷＶＴＲ）を測定した。そして、得られたＷＶＴＲを、厚み１００ｎｍのガスバリア層を基準に規格化した値（以下、「規格化ＷＶＴＲ」と記載することがある）に変換した。例えば、実施例１の規格化ＷＶＴＲは、上記測定方法で得られた測定値（ＷＶＴＲ）×１７６／１００で算出される値である。規格化ＷＶＴＲが０．１０ｇ／ｍ２・ｄａｙ以下である場合、「ガスバリア性に優れている」と評価した。一方、規格化ＷＶＴＲが０．１０ｇ／ｍ２・ｄａｙを超えている場合、「ガスバリア性に優れていない」と評価した。 <Method for evaluating gas barrier film>
[Water vapor transmission rate]
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. For example, 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. When the normalized WVTR was 0.10 g/m 2 ·day or less, it was evaluated as "excellent in gas barrier properties". On the other hand, when the normalized WVTR exceeded 0.10 g/m 2 ·day, it was evaluated as "not excellent in gas barrier properties".
［光透過率］
　分光光度計（日立ハイテクサイエンス社製「Ｕ４１００」）により、各ガスバリアフィルムの光透過率（Ｙ値）を測定した。光透過率が９０％以上である場合、「透明性に優れている」と評価した。一方、光透過率が９０％未満である場合、「透明性に優れていない」と評価した。 [Light transmittance]
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".
［耐屈曲性］
　各ガスバリアフィルムを、幅２５ｍｍ、長さ１５０ｍｍの短冊状に切り出して、耐屈曲性評価用の試験片を得た。次いで、屈曲試験機（ユアサシステム機器社製「ＤＬＤＭＬＨ－ＦＳ」）に試験片を設置し、屈曲直径：６ｍｍ又は５ｍｍ、屈曲速度：１回／秒の条件で屈曲試験を１０００回実施した。試験片を屈曲させる際は、ガスバリア層形成面が内側になるように屈曲させた。なお、上記「屈曲直径」とは、屈曲試験において、試験片が円弧状に屈曲された際の当該円弧状の屈曲部における内周の直径をさす。屈曲試験後、試験片の屈曲部分のクラックの有無を目視にて観察し、下記の基準で判定した。判定がＡ又はＢの場合、「耐屈曲性に優れている」と評価した。一方、判定がＣの場合、「耐屈曲性に優れていない」と評価した。
　Ａ：屈曲直径６ｍｍ及び屈曲直径５ｍｍのいずれの場合もクラックが発生しなかった。
　Ｂ：屈曲直径６ｍｍではクラックが発生しなかったが、屈曲直径５ｍｍではクラックが発生した。
　Ｃ：屈曲直径６ｍｍ及び屈曲直径５ｍｍのいずれの場合もクラックが発生した。 [Flexibility]
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. Next, 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. When bending the test piece, it was bent so that the gas barrier layer-formed surface was on the inside. The above-mentioned "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. After the bending test, the presence or absence of cracks in the bent portion of the test piece was visually observed and judged according to the following criteria. When the judgment was A or B, it was evaluated as "excellent in flex resistance". On the other hand, when the judgment was C, it was evaluated as "not excellent in flex resistance".
A: No cracks occurred in both cases of bending diameter 6 mm and bending diameter 5 mm.
B: No cracks occurred at a bending diameter of 6 mm, but cracks occurred at a bending diameter of 5 mm.
C: Cracks occurred both when the bending diameter was 6 mm and when the bending diameter was 5 mm.
＜評価結果＞
　実施例１及び２について、各元素（Ｓｉ、Ｏ、Ｎ及びＣ）の含有率、第１層の厚み、第２層の厚み、第３層の厚み、第２層厚み比率、Ｃｍａｘ、Ｃｍｉｎ、Ｃｍａｘ－Ｃｍｉｎ、規格化ＷＶＴＲ、光透過率、及び耐屈曲性の判定結果を、表１に示す。また、比較例１～４について、各元素（Ｓｉ、Ｏ、Ｎ及びＣ）の含有率、第１層の厚み、第２層の厚み、第３層の厚み、第２層厚み比率、Ｃｍａｘ、Ｃｍｉｎ、Ｃｍａｘ－Ｃｍｉｎ、規格化ＷＶＴＲ、光透過率、及び耐屈曲性の判定結果を、表２に示す。なお、実施例１及び２並びに比較例２～４のいずれについても、透過型電子顕微鏡（日本電子社製「ＪＥＭ－２８００」）により、加速電圧２００ｋＶかつ倍率２０万倍の条件でガスバリア層の断面を暗視野像で観察した際、ガスバリア層を構成する各層間に界面が存在していなかった。また、表１及び表２の各元素（Ｓｉ、Ｏ、Ｎ及びＣ）の含有率は、ガスバリア層の厚み方向の中央部（総エッチング時間の１／２が経過したとき）における含有率であり、Ｓｉ、Ｏ、Ｎ及びＣの合計を１００原子％として算出した。また、表２の「－」は、ガスバリア層が炭素を含んでいなかったため、測定（算出）しなかったことを意味する。 <Evaluation results>
For Examples 1 and 2, the content of each element (Si, O, N and C), the thickness of the first layer, the thickness of the second layer, the thickness of the third layer, the thickness ratio of the second layer, C max , C Table 1 shows the determination results of min , C max −C min , normalized WVTR, light transmittance, and flex resistance. Further, for Comparative Examples 1 to 4, the content of each element (Si, O, N and C), the thickness of the first layer, the thickness of the second layer, the thickness of the third layer, the thickness ratio of the second layer, C max , C min , C max −C min , normalized WVTR, light transmittance, and bending resistance are shown in Table 2. For both Examples 1 and 2 and Comparative Examples 2 to 4, the cross section of the gas barrier layer was observed with a transmission electron microscope ("JEM-2800" manufactured by JEOL Ltd.) at an acceleration voltage of 200 kV and a magnification of 200,000 times. was observed with a dark-field image, no interfaces existed between the layers constituting the gas barrier layer. In addition, the content of each element (Si, O, N, and C) in Tables 1 and 2 is the content in the central portion of the gas barrier layer in the thickness direction (when 1/2 of the total etching time has elapsed). , Si, O, N and C was calculated as 100 atomic %. In addition, "-" in Table 2 means that the gas barrier layer did not contain carbon and therefore was not measured (calculated).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１に示すように、実施例１及び２では、第２層厚み比率が２０％以上７０％以下であった。実施例１及び２では、Ｃｍａｘ－Ｃｍｉｎが６．０以下であった。 As shown in Table 1, in Examples 1 and 2, the second layer thickness ratio was 20% or more and 70% or less. In Examples 1 and 2, C max -C min was 6.0 or less.
　表１に示すように、実施例１及び２では、規格化ＷＶＴＲが０．１０ｇ／ｍ２・ｄａｙ以下であった。よって、実施例１及び２は、ガスバリア性に優れていた。実施例１及び２では、光透過率が９０％以上であった。よって、実施例１及び２は、透明性に優れていた。実施例１及び２では、耐屈曲性の判定がＡ又はＢであった。よって、実施例１及び２は、耐屈曲性に優れていた。 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.
　表２に示すように、比較例２では、第２層厚み比率が２０％未満であった。比較例３及び４では、第２層厚み比率が７０％を超えていた。比較例３では、Ｃｍａｘ－Ｃｍｉｎが６．０を超えていた。比較例１では、ガスバリア層が炭素を含んでいなかった。 As shown in Table 2, in Comparative Example 2, 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.
　表２に示すように、比較例１～３では、規格化ＷＶＴＲが０．１０ｇ／ｍ２・ｄａｙを超えていた。よって、比較例１～３は、ガスバリア性に優れていなかった。比較例１及び４では、光透過率が９０％未満であった。よって、比較例１及び４は、透明性に優れていなかった。比較例１、２及び４では、耐屈曲性の判定がＣであった。よって、比較例１、２及び４は、耐屈曲性に優れていなかった。 As shown in Table 2, in Comparative Examples 1 to 3, the normalized WVTR exceeded 0.10 g/m 2 ·day. Therefore, Comparative Examples 1 to 3 were not excellent in gas barrier properties. In Comparative Examples 1 and 4, the light transmittance was less than 90%. Therefore, Comparative Examples 1 and 4 were not excellent in transparency. In Comparative Examples 1, 2 and 4, the flex resistance was evaluated as C. Therefore, Comparative Examples 1, 2 and 4 were not excellent in bending resistance.
　以上の結果から、本発明によれば、透明性、耐屈曲性及びガスバリア性に優れるガスバリアフィルムを提供できることが示された。 From the above results, it was shown that the present invention can provide a gas barrier film with excellent transparency, flexibility and gas barrier properties.
１０、２０、３０、４０、５０　ガスバリアフィルム
１１　透明フィルム基材
１２、２１　ガスバリア層
１３　酸炭化ケイ素層
１４　第１層
１５　第２層
１６　第３層
３１　ハードコート層
５１　粘着剤層
１００　ガスバリア層付き偏光板
２００　画像表示装置
２０２　画像表示セル

  10, 20, 30, 40, 50 Gas barrier film 11 Transparent film substrate 12, 21 Gas barrier layer 13 Silicon oxycarbide layer 14 First layer 15 Second layer 16 Third layer 31 Hard coat layer 51 Adhesive layer 100 With gas barrier layer Polarizing plate 200 Image display device 202 Image display cell

Claims (12)

  1. 　透明フィルム基材と、前記透明フィルム基材の少なくとも一方の主面に直接的又は間接的に配置されたガスバリア層とを有するガスバリアフィルムであって、
    　前記ガスバリア層は、構成元素としてケイ素、酸素及び炭素を含む酸炭化ケイ素層を有し、
    　前記酸炭化ケイ素層は、前記透明フィルム基材側から第１層、第２層及び第３層をこの順に有し、
    　前記第１層中の炭素含有率、及び前記第３層中の炭素含有率が、ケイ素、酸素及び炭素の合計１００原子％に対して、いずれも０．１原子％未満であり、
    　前記第２層中の炭素含有率が、ケイ素、酸素及び炭素の合計１００原子％に対して、０．１原子％以上であり、
    　前記第２層の厚み比率が、前記第１層、前記第２層及び前記第３層の合計厚み１００％に対して、２０％以上７０％以下であり、
    　Ｘ線光電子分光法を用いて前記酸炭化ケイ素層の厚み方向における組成分析を行った際に、ケイ素、酸素及び炭素の合計１００原子％に対する炭素含有率が最大値を示す箇所の当該炭素含有率をＣｍａｘ原子％とし、ケイ素、酸素及び炭素の合計１００原子％に対する炭素含有率が最小値を示す箇所の当該炭素含有率をＣｍｉｎ原子％としたとき、ＣｍａｘからＣｍｉｎを引いた値が６．０以下である、ガスバリアフィルム。     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 thickness direction of the silicon oxycarbide layer is performed using X-ray photoelectron spectroscopy. is C max atomic %, and 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.
  2. 　前記Ｃｍａｘから前記Ｃｍｉｎを引いた値が２．０以上である、請求項１に記載のガスバリアフィルム。 The gas barrier film according to claim 1, wherein the value obtained by subtracting the Cmin from the Cmax is 2.0 or more.
  3. 　前記第２層の厚み比率が、前記第１層、前記第２層及び前記第３層の合計厚み１００％に対して、２０％以上５５％以下である、請求項１又は２に記載のガスバリアフィルム。 The gas barrier according to claim 1 or 2, wherein 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. film.
  4. 　前記酸炭化ケイ素層の厚みが、１０ｎｍ以上５００ｎｍ以下である、請求項１又は２に記載のガスバリアフィルム。 The gas barrier film according to claim 1 or 2, wherein the silicon oxycarbide layer has a thickness of 10 nm or more and 500 nm or less.
  5. 　ＪｌＳ　Ｚ８７８１－３：２０１６で規定されるＣＩＥ三刺激値のＹ値が、９０％以上である、請求項１又は２に記載のガスバリアフィルム。 The gas barrier film according to claim 1 or 2, wherein the Y value of the CIE tristimulus values defined in JlS Z8781-3:2016 is 90% or more.
  6. 　前記透明フィルム基材と前記ガスバリア層との間に配置された、個数平均一次粒子径１．０μｍ未満のシリカ粒子を含むハードコート層を更に有する、請求項１又は２に記載のガスバリアフィルム。 The gas barrier film according to claim 1 or 2, further comprising a hard coat layer containing silica particles having a number average primary particle diameter of less than 1.0 µm, disposed between the transparent film substrate and the gas barrier layer.
  7. 　前記ガスバリア層の前記透明フィルム基材側とは反対側に配置された粘着剤層を更に有する、請求項１又は２に記載のガスバリアフィルム。 The gas barrier film according to claim 1 or 2, further comprising an adhesive layer disposed on the side of the gas barrier layer opposite to the transparent film substrate side.
  8. 　請求項１又は２に記載のガスバリアフィルムの製造方法であって、
    　一対の対向電極として一対の成膜ロールを有する成膜装置のチャンバー内に、有機ケイ素化合物及び酸素を導入して、化学気相成長法により前記酸炭化ケイ素層を形成する、ガスバリアフィルムの製造方法。     A method for producing the gas barrier film according to claim 1 or 2,
    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. .
  9. 　請求項１に記載のガスバリアフィルムと、偏光子とを備える、ガスバリア層付き偏光板。 A polarizing plate with a gas barrier layer, comprising the gas barrier film according to claim 1 and a polarizer.
  10. 　請求項１に記載のガスバリアフィルムと、画像表示セルとを備える、画像表示装置。 An image display device comprising the gas barrier film according to claim 1 and an image display cell.
  11. 　請求項９に記載のガスバリア層付き偏光板と、画像表示セルとを備える、画像表示装置。 An image display device comprising the gas barrier layer-attached polarizing plate according to claim 9 and an image display cell.
  12. 　前記画像表示セルは、有機ＥＬ素子を含む、請求項１０又は１１に記載の画像表示装置。

          12. The image display device according to claim 10, wherein said image display cell includes an organic EL element.
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