WO2023054176A1 - Film formant barrière contre les gaz, son procédé de production, plaque de polarisation avec couche formant barrière contre les gaz et dispositif d'affichage d'image - Google Patents
Film formant barrière contre les gaz, son procédé de production, plaque de polarisation avec couche formant barrière contre les gaz et dispositif d'affichage d'image Download PDFInfo
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- WO2023054176A1 WO2023054176A1 PCT/JP2022/035425 JP2022035425W WO2023054176A1 WO 2023054176 A1 WO2023054176 A1 WO 2023054176A1 JP 2022035425 W JP2022035425 W JP 2022035425W WO 2023054176 A1 WO2023054176 A1 WO 2023054176A1
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- Prior art keywords
- layer
- gas barrier
- film
- oxygen
- barrier film
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Images
Classifications
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual 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 element deterioration 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.
- Patent Document 1 proposes a gas barrier film including a silicon nitride layer and a silicon oxide layer as a gas barrier film with excellent transparency and flexibility.
- Patent Document 1 leaves room for improvement in terms of enhancing transparency and gas barrier properties.
- the present invention has been made in view of the above problems, and aims to provide a gas barrier film having excellent transparency 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. to provide.
- 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 first layer containing silicon, oxygen and carbon as constituent elements, and a second layer containing silicon, oxygen and nitrogen as constituent elements,
- the first layer is a layer located farthest from the transparent film substrate in the gas barrier layer,
- the second layer is in contact with the main surface of the first layer on the transparent film substrate side,
- the thickness of the first layer is 80 nm or more and 700 nm or less
- the thickness of the second layer is 20 nm or more and 220 nm or less
- the gas barrier film, wherein the oxygen content in the second layer is 15 atomic % or more when the total of silicon, oxygen and nitrogen in the second layer is 100 atomic %.
- the gas barrier layer further has a third layer in contact with the main surface of the second layer on the transparent film substrate side,
- the gas barrier film according to any one of [1] to [3], wherein the third layer contains silicon, oxygen and carbon as constituent elements.
- a polarizing plate with a gas barrier layer comprising the gas barrier film according to any one of [1] to [5] above and a polarizer.
- An image display device comprising the gas barrier film according to any one of [1] to [5] and an image display cell.
- An image display device comprising the polarizing plate with a gas barrier layer according to [7] and an image display cell.
- the present invention it is possible to provide a gas barrier film excellent in transparency 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. 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
- 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 a 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 refers to a surface orthogonal to the thickness direction of the layered material.
- the numerical value for the "thickness" of the layered material 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 first layer containing silicon, oxygen and carbon as constituent elements and a second layer containing silicon, oxygen and nitrogen as constituent elements.
- a 1st layer is a layer arrange
- the second layer is in contact with the main surface of the first layer on the side of the transparent film substrate.
- the thickness of the first layer is 80 nm or more and 700 nm or less.
- the thickness of the second layer is 20 nm or more and 220 nm or less.
- the oxygen content in the second layer is 15 atomic % or more when the total of silicon, oxygen and nitrogen in the second layer is 100 atomic %.
- a layer containing silicon, oxygen and carbon as constituent elements may be referred to as a "silicon oxycarbide layer".
- a layer containing silicon, oxygen, and nitrogen as constituent elements is sometimes referred to as a "silicon oxynitride layer.”
- the content of oxygen in the second layer (or silicon oxynitride layer) when the total of silicon, oxygen and nitrogen in the second layer (or silicon oxynitride layer) is 100 atomic % is defined as "second content of oxygen in the layer (or silicon oxynitride layer)".
- the content of carbon in the first layer (or silicon oxycarbide layer) when the total of silicon, oxygen and carbon in the first layer (or silicon oxycarbide layer) is 100 atomic % is defined as "first The content of carbon in the layer (or silicon oxycarbide layer)".
- the elemental composition of the silicon oxycarbide layer is the elemental composition at the central portion in the thickness direction of the silicon oxycarbide layer (when 1/2 of the total etching time of the silicon oxycarbide layer, which will be described later, has elapsed). .
- the elemental composition of the silicon oxynitride layer is the elemental composition at the central portion in the thickness direction of the silicon oxynitride layer (when 1/2 of the total etching time of the silicon oxynitride layer, which will be described later, has elapsed).
- the method for measuring the elemental composition of the silicon oxycarbide layer and the method for measuring the elemental composition of the silicon oxynitride layer are both the same method as in Examples described later or a method based thereon.
- the gas barrier film according to the first embodiment has the above configuration, it is excellent in transparency and gas barrier properties. The reason is presumed as follows.
- silicon oxynitride layers tend to have higher gas barrier properties as the nitrogen ratio increases, and the higher the oxygen ratio, the less visible light is absorbed and the more transparent they tend to be.
- the silicon oxynitride layer which is the second layer, has an oxygen content of 15 atomic % or more, and the upper limit of the thickness of the first layer and the second layer is a predetermined value. Because it is set, it is excellent in transparency.
- the inventors' studies have revealed that if the silicon oxynitride layer is excessively thick, the gas barrier properties tend to deteriorate. It is presumed that this is because if the thickness of the silicon oxynitride layer is excessively large, irregularities on the surface of the silicon oxynitride layer become apparent, and minute defects tend to occur in the gas barrier layer.
- the thickness of the second layer which is a silicon oxynitride layer
- the gas barrier film according to the first embodiment has a silicon oxycarbide layer (first layer) outside the silicon oxynitride layer, the thickness of which is set within a predetermined range.
- the gas barrier film according to the first embodiment has excellent gas barrier properties even though the oxygen content in the silicon oxynitride layer (second layer) is 15 atomic % or more.
- the oxygen content in the second layer is preferably 18 atomic % or more, more preferably 19 atomic % or more, More preferably 20 atomic % or more, 21 atomic % or more, 22 atomic % or more, 23 atomic % or more, 24 atomic % or more, 25 atomic % or more, 26 atomic % or more, 27 atomic % or more, 28 atomic % or more , 29 atomic % or more, or 30 atomic % or more.
- the oxygen content in the second layer is preferably 50 atomic % or less, more preferably 47 atomic % or less, It is more preferably 45 atomic % or less, and even more preferably 43 atomic % or less.
- the thickness of the first layer is preferably 90 nm or more and 500 nm or less, more preferably 90 nm or more and 400 nm or less, and 90 nm. It is more preferably 350 nm or less, even more preferably 90 nm or more and 340 nm or less, and may be 100 nm or more and 340 nm or less, or 100 nm or more and 330 nm or less.
- the thickness of the second layer is preferably 20 nm or more and 200 nm or less, more preferably 25 nm or more and 190 nm or less, and 25 nm. It is more preferably 185 nm or less, and may be 30 nm or more and 185 nm or less, or 30 nm or more and 180 nm or less.
- the carbon content in the first layer is preferably 1 atomic % or more and 10 atomic % or less, and 2 atomic % or more. It is more preferably 7 atomic % or less, and still more preferably 3 atomic % or more and 5 atomic % or less.
- the carbon content (the total of silicon, oxygen and carbon is The carbon content at the point where the carbon content at 100 atomic %) is the maximum value is sometimes referred to as the "maximum carbon content.”
- the maximum carbon content is preferably 10 atomic % or less, more preferably 9 atomic % or less, and even more preferably 7 atomic % or less. It is even more preferably 5 atomic % or less, and particularly preferably 3 atomic % or more and 5 atomic % or less.
- the maximum carbon content is at least one of the introduction amount (flow rate) of the silicon source, the introduction amount (flow rate) of the oxygen source, and the applied power. can be adjusted by changing the
- Condition 1 In the first embodiment, in order to obtain a gas barrier film with even better gas barrier properties and transparency, it is preferable to satisfy Condition 1 below, more preferably Condition 2 below, and even more preferably Condition 3 below.
- Condition 1 The oxygen content in the second layer is 18 atomic % or more and 50 atomic % or less, and the thickness of the first layer is 90 nm or more and 340 nm or less.
- Condition 2 Condition 1 above is satisfied, and the thickness of the second layer is 25 nm or more and 185 nm or less.
- Condition 3 Condition 2 above is satisfied, and the maximum carbon content of the first layer is 5 atomic % 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 comprises a first layer 13 (silicon oxycarbide layer) containing silicon, oxygen and carbon as constituent elements, and a second layer 14 (silicon oxynitride layer) containing silicon, oxygen and nitrogen as constituent elements. and a third layer 15 (silicon oxycarbide layer) containing silicon, oxygen and carbon as elements.
- the first layer 13 is the layer located farthest from the transparent film substrate 11 in the gas barrier layer 12 .
- the second layer 14 is in contact with the main surface 13a of the first layer 13 on the transparent film substrate 11 side.
- the third layer 15 is in contact with the main surface 14a of the second layer 14 on the transparent film substrate 11 side.
- the oxygen content in the second layer 14 is 15 atomic % or more when the total of silicon, oxygen and nitrogen in the second layer 14 is 100 atomic %.
- the thickness of the first layer 13 is 80 nm or more and 700 nm or less.
- the thickness of the second layer 14 is 20 nm or more and 220 nm or less.
- the thickness of the third layer 15 is preferably 30 nm or more and 400 nm or less, more preferably 40 nm or more and 350 nm or less, and 50 nm or more and 340 nm or less, or 50 nm. It may be more than or equal to 330 nm or less.
- the carbon content in the third layer 15 should be 1 atom when the total of silicon, oxygen and carbon in the third layer 15 is 100 atom %. % or more and 10 atomic % or less, more preferably 2 atomic % or more and 7 atomic % or less, and even more preferably 3 atomic % or more and 5 atomic % or less.
- 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.
- the gas barrier film according to the first embodiment may not have the third layer. That is, the gas barrier film according to the first embodiment may be a gas barrier film in which the gas barrier layer is composed only of the first layer (silicon oxycarbide layer) and the second layer (silicon oxynitride layer).
- the gas barrier film according to the first embodiment should include a third layer (oxycarburization silicon layer).
- the gas barrier layer may include two or more silicon oxynitride layers, for example, two silicon oxynitride layers and three silicon oxycarbide 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 having a four-layer structure may be an alternate laminate in which silicon oxynitride layer/silicon oxycarbide layer/silicon oxynitride layer/silicon oxycarbide layer are arranged in this order from the transparent film substrate side.
- the gas barrier layer may be an alternately laminated body composed of 3 silicon oxynitride layers and 4 silicon oxycarbide layers, a total of 7 layers, or may be an alternately laminated body composed of 8 or more layers.
- the gas barrier layer preferably has a laminated structure of two to five layers, and a laminated structure of three layers like the gas barrier film 10 shown in FIG. It is more preferable to have
- the gas barrier layer may be indirectly arranged on the main surface of the transparent film substrate.
- the gas barrier film 20 shown in FIG. 2 has a hard coat layer 21 arranged between the transparent film substrate 11 and the gas barrier layer 12 (third layer 15).
- the gas barrier layer 12 is indirectly arranged on the main surface of the transparent film substrate 11 .
- the hard coat layer 21 is a layer that enhances mechanical properties such as hardness and elastic modulus of the gas barrier film 20 . If the main surface of the hard coat layer 21 on the side of the gas barrier layer 12 is smooth, the gas barrier properties of the gas barrier layer 12 formed thereon are enhanced, and the water vapor transmission rate tends to decrease.
- the arithmetic mean height Sa of the main surface of the hard coat layer 21 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 according to ISO 25178 from the three-dimensional surface profile of the range of 1 ⁇ m ⁇ 1 ⁇ m measured by an atomic force microscope (AFM).
- the hard coat layer 21 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 21 contains nanoparticles, fine irregularities are formed on the surface of the hard coat layer 21, and adhesion between the hard coat layer 21 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.
- the gas barrier film 30 shown in FIG. and a gas barrier layer having a laminated structure of two layers or four or more layers may be provided on each of both main surfaces of the transparent film substrate.
- the configuration of the gas barrier layer 31 may be the same as or different from the configuration of the gas barrier layer 12 . That is, the gas barrier layer 31 may have a silicon oxycarbide layer 34, a silicon oxynitride layer 33, and a silicon oxycarbide layer 32 in this order from the transparent film substrate 11 side. The content may be 15 atomic % or more. Moreover, the gas barrier layer 31 may have a structure of four or more layers, a two-layer structure, or a single-layer structure.
- the gas barrier layer 31 has a silicon oxycarbide layer 34, a silicon oxynitride layer 33 and a silicon oxycarbide layer 32 in this order from the transparent film substrate 11 side, and It is preferable that the oxygen content in the silicon oxynitride layer 33 is 15 atomic % or more.
- the silicon oxycarbide layer 32 should have a thickness of 80 nm or more and 700 nm or less, and the silicon oxynitride layer 33 should have a thickness of 20 nm or more and 220 nm or less.
- the thickness of the layer 34 is 30 nm or more and 400 nm or less.
- the carbon content in the silicon oxycarbide layer 32 and the carbon content in the silicon oxycarbide layer 34 should both be 1 atomic % or more and 10%. It is preferably atomic % or less.
- the gas barrier film according to the first embodiment may further have an adhesive layer.
- a gas barrier film 40 shown in FIG. 4 has an adhesive layer 41 in addition to the configuration of the gas barrier film 30 .
- the adhesive layer 41 is arranged on the main surface 13b of the first 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 41 opposite to the first layer 13 side.
- the release liner protects the surface of the pressure-sensitive adhesive layer 41, for example, until the gas barrier film 40 is attached to the polarizing plate 101 (see FIG. 5), 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 a layer that serves as a base for forming the 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 second layer 14 is a layer mainly having a gas barrier function in the gas barrier layer, and is a silicon oxynitride layer made of a material containing silicon, oxygen and nitrogen as main constituent elements.
- the second layer 14 may contain a small amount of elements such as hydrogen, carbon, etc. taken in from the raw material at the time of film formation, the transparent film substrate 11 and the external environment.
- the carbon content in the second layer 14 is preferably lower than that in the first layer 13 .
- the composition of silicon oxynitride contained in the second layer 14 is represented by the general formula SiO x N y .
- x in the general formula SiO x N y may be simply referred to as "x”.
- y in the general formula SiO x N y may be simply described as "y”.
- the silicon oxynitride contained in the second layer 14 may have a stoichiometric composition or may be a non-stoichiometric composition deficient in oxygen or nitrogen.
- the value of (x/2+3y/4) is preferably 0.70 or more and 1.10 or less.
- the upper limit of (x/2+3y/4) is 1, but it may show a value greater than 1 due to excessive intake of oxygen or nitrogen. If (x/2+3y/4) is 0.70 or more, transparency and gas barrier properties tend to be enhanced.
- x is preferably 0.3 or more. In order to obtain a gas barrier film with more excellent gas barrier properties, x is preferably 1.2 or less. In order to obtain a gas barrier film with more excellent gas barrier properties, y is preferably 0.4 or more. In order to obtain a gas barrier film with excellent transparency, y is preferably 0.8 or less.
- the content of elements other than silicon, oxygen, and nitrogen is preferably 5 atomic % or less, more preferably 3 atomic % or less, and 1 atomic % or less. More preferred.
- the total content of silicon, oxygen and nitrogen is preferably 90 atomic % or more, more preferably 95 atomic % or more, and 97 atomic % or more. is more preferable, and may be 99 atomic % or more, 99.5 atomic % or more, or 99.9 atomic % or more.
- the refractive index of the second layer 14 is generally 1.50 or more and 2.20 or less, preferably 1.55 or more and 2.00 or less, and may be 1.60 or more and 1.90 or less. 0.85 or less, 1.80 or less, 1.75 or less, or 1.70 or less.
- the second layer 14 having a refractive index within this range can achieve both excellent gas barrier properties and transparency. Further, when the refractive index is 2.00 or less, there is a tendency for the light transmittance to be improved. The second layer 14 tends to have a higher refractive index as the nitrogen ratio increases.
- the density of the second layer 14 is preferably 2.10 g/cm 3 or more.
- the second layer 14 tends to have a higher density as the nitrogen ratio increases.
- a method for forming the second layer 14 is not particularly limited, and may be a dry coating method or a wet coating method.
- a dry process such as a sputtering method, an ion plating method, a vacuum deposition method, or a chemical vapor deposition method (CVD method) is preferable because a film having a high film density and a high gas barrier property can be easily formed.
- a CVD method is preferable, and a plasma CVD method is more preferable, because a film having small film stress and excellent bending resistance can be easily formed.
- 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 roll. be.
- 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.
- 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”.
- Examples of the silicon supply source (silicon source) when forming the second layer 14 by the CVD method include silicon hydride (more specifically, silane, disilane, etc.) and silicon halide (more specifically, , dichlorosilane, etc.) Si-containing gas such as hexamethyldisilazane, hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, tetramethylsilane, vinyltrimethoxysilane, vinyltrimethylsilane, dimethyldimethoxy Silicon compounds such as silane, tetramethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, tetraethoxysilane, diethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysiloxane, monosilylamine, disilylamine, and trisilylamine is mentioned. Among these, tri
- Nitrogen sources include nitrogen and ammonia.
- Oxygen sources include oxygen, carbon monoxide, carbon dioxide, and the like. Nitrogen (nitrogen gas) is preferable as the nitrogen source, and oxygen (oxygen gas) is preferable as the oxygen source, from the viewpoint of reducing hydrogen and carbon taken into the film.
- a silicon nitride film formed by a CVD method by introducing a nitrogen source together with trisilylamine as a silicon source has a large amount of hydrogen in the film, and a wave number of 2140 cm ⁇ 1 (range of 2120 cm ⁇ 1 to 2150 cm ⁇ 1 ).
- a silicon oxynitride film formed by a CVD method by introducing nitrogen and oxygen together with trisilylamine as a silicon source shifts the infrared absorption peak to the high wave number side, and is 2160 cm ⁇ 1 to 2280 cm It exhibits an infrared absorption peak in the range of -1 or less, and exhibits transparency superior to that of silicon nitride films.
- Oxygen has a strong bonding force with silicon, so it is presumed that the introduction of oxygen suppresses the uptake of hydrogen into the film, which is one of the reasons for the improvement in transparency.
- the composition of the second layer 14 can be appropriately adjusted.
- the amount of oxygen to be introduced is set to 0.05 by volume with respect to the amount of nitrogen to be introduced. It is preferably 0.1 times or more and 5 times or less, more preferably 0.03 times or more and 2 times or less, further preferably 0.04 times or more and 1.5 times or less, and 0.04 times or more and 1 0 times or less, or 0.04 times or more and 0.5 times or less.
- the amount of oxygen introduced is excessively small, the amount of oxygen introduced into the film tends to be small and the light transmittance of the film tends to decrease. If the amount of oxygen introduced is excessively large, the amount of nitrogen incorporated into the film tends to be small, resulting in insufficient gas barrier properties.
- a gas other than the silicon source, the nitrogen source, and the oxygen source may be used as the introduced gas when forming the film by the CVD method.
- a carrier gas may be used to vaporize the liquid and introduce it into the chamber (vacuum chamber).
- a nitrogen source or an oxygen source may be mixed with a carrier gas and introduced into the vacuum chamber, or 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. A rare gas is preferable from the viewpoint of reducing the amount of hydrogen taken into the film and increasing the transparency.
- 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, the second layer 14) on the film substrate is preferably 150° C. or less from the viewpoint of the heat resistance of the film substrate. , 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.
- the density of the second layer 14 formed by the CVD method is, for example, 2.10 g/cm 3 or more and 2.50 g/cm 3 or less, 2.15 g/cm 3 or more and 2.45 g/cm 3 or less, or 2.20 g/cm 3 or more. /cm 3 or more and 2.40 g/cm 3 or less, or 2.25 g/cm 3 or more and 2.35 g/cm 3 or less.
- the first layer 13 is a layer having a gas barrier function together with the second layer 14, and is a silicon oxycarbide layer made of a material containing silicon, oxygen and carbon as main constituent elements.
- the first layer 13 may contain a small amount of elements such as hydrogen, nitrogen, etc. taken in from the raw material at the time of film formation, the transparent film substrate 11 and the external environment.
- the nitrogen content in the first layer 13 is preferably lower than that in the second layer 14 .
- 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. is more preferred.
- 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. is more preferable, and may be 99 atomic % or more, 99.5 atomic % or more, or 99.9 atomic % or more.
- the composition of silicon oxycarbide contained in the first layer 13 is represented by the general formula SiO a C b .
- a in the general formula SiO a C b may be simply referred to as "a”.
- b in the general formula SiOaCb may be simply described as "b”.
- a is 1.5 or more and 2.5 or less and b is 0.01 or more and 0.5 or less.
- a method for forming the first layer 13 is not particularly limited, and may be a dry coating method or a wet coating method.
- the first layer 13 is also preferably formed by the CVD method from the viewpoint of productivity.
- Examples of the silicon source and the oxygen source for forming the first layer 13 by the CVD method include those exemplified above regarding the formation of the second layer 14 .
- the silicon source organosilicon compounds are preferred because they have low toxicity and can suppress incorporation of nitrogen into the film. methylsilane, vinyltrimethoxysilane, vinyltrimethylsilane, dimethyldimethoxysilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, tetraethoxysilane, diethyldiethoxysilane, methyldimethoxysilane, and methyldimethoxysilane.
- organosilicon compounds More preferably, one or more selected from the group consisting of ethoxysiloxane.
- ethoxysiloxane 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.
- 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.
- Oxygen gas is preferable as the oxygen source from the viewpoint of reducing the amount of hydrogen in the film.
- the amount of oxygen introduced is preferably 10 times or more by volume the amount of hexamethyldisiloxane (gas) introduced. , 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.
- the composition of the first layer 13 can be appropriately adjusted by changing the introduction amount of the oxygen source (or the oxygen source and the carbon source) with respect to the silicon source.
- a carrier gas or a discharge gas may be introduced in the CVD film formation of the first layer 13 .
- Various conditions such as substrate temperature, pressure, power supply frequency, and applied power may be appropriately adjusted in the same manner as in the film formation of the second layer 14 .
- the density of the first layer 13 is preferably 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.
- a preferable range of the content of each element contained in the third layer 15 is the same as that of the first layer 13 described above, for example.
- the content of each element contained in the third layer 15 and the content of each element contained in the first layer 13 may be the same or different.
- the thickness of the third layer 15 and the thickness of the first layer 13 may be the same or different.
- the same method as the method described above as the film formation method of the first layer 13 can be adopted.
- the gas barrier layer may include layers (other layers) other than the first layer 13, the second layer 14 and the third layer 15.
- “other layers” include inorganic thin films made of ceramic materials such as metal or semi-metal oxides, nitrides or oxynitrides. Oxides, nitrides or oxynitrides of Si, Al, In, Sn, Zn, Ti, Nb, Ce or Zr are preferred because they have both low moisture permeability and transparency.
- the total thickness of the gas barrier layer is preferably 100 nm or more and 1000 nm or less, more preferably 100 nm or more and 900 nm or less.
- the hard coat layer 21 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 size of the nanoparticles contained in the hard coat layer 21 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 21 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 amount of nanoparticles in the hard coat layer 21 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 nanoparticles is 5 parts by weight or more, the adhesion to the gas barrier layer formed on the hard coat layer 21 can be improved.
- the upper limit of the amount of nanoparticles in the hard coat layer 21 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.
- the thickness of the hard coat layer 21 is not particularly limited, but is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, in order to improve the adhesion to the gas barrier layer while achieving high hardness. It is more preferably 2.0 ⁇ m or more, and even more preferably 3.0 ⁇ m or more. On the other hand, the thickness of the hard coat layer 21 is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and even more preferably 12 ⁇ m or less in order to suppress a decrease in strength due to cohesive failure.
- the hard coat layer 21 is formed by applying the hard coat composition onto the transparent film substrate 11 and, if necessary, 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.
- the hard coat composition includes particles (microparticles) having a number average primary particle diameter of 1.0 ⁇ m 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.
- 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 41 As a constituent material of the adhesive layer 41, an adhesive having a high visible light transmittance is preferably used.
- adhesives constituting the adhesive layer 41 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 41 is preferably 5 ⁇ m or more and 100 ⁇ m or less.
- the refractive index of the adhesive layer 41 is, for example, 1.4 or more and 1.5 or less.
- the water vapor transmission rate of the gas barrier film is preferably 3.0 ⁇ 10 ⁇ 2 g/m 2 ⁇ day or less, more preferably 2.0 ⁇ 10 ⁇ 2 g/m 2 ⁇ day or less. It is more preferably .0 ⁇ 10 ⁇ 2 g/m 2 ⁇ day or less, and even more preferably 7.0 ⁇ 10 ⁇ 3 g/m 2 ⁇ day or less. 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. Water vapor transmission rate (WVTR) is measured according to the differential pressure method (Pressure Sensor Method) described in ISO 15106-5 under conditions of a temperature of 40° C. and a relative humidity of 90%.
- WVTR Water vapor transmission rate
- the light transmittance of the gas barrier film is preferably 75% or higher, more preferably 80% or higher.
- Light transmittance is the Y value of the CIE tristimulus values specified in JlS Z8781-3:2016.
- 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.
- trisilylamine, nitrogen and oxygen are introduced into a chamber (vacuum chamber) of a film forming apparatus to form the second layer 14 by chemical vapor deposition. and a step of introducing an organosilicon compound and oxygen into a chamber of a film forming apparatus to form the first layer 13 by chemical vapor deposition.
- the second layer 14 is formed.
- a film-forming gas more specifically, trisilylamine, oxygen, nitrogen, etc.
- plasma discharge is generated between a pair of film-forming rolls, so that the film-forming gas is It is decomposed by plasma, and the second layer 14 is formed on the transparent film substrate 11, for example.
- plasma discharge is generated between a pair of film-forming rolls while supplying a film-forming gas (more specifically, an organic silicon compound, oxygen, etc.) for forming the first layer 13 into the vacuum chamber.
- a film-forming gas more specifically, an organic silicon compound, oxygen, etc.
- 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. 5 is a cross-sectional view showing an example of a polarizing plate with a gas barrier layer according to the third embodiment.
- the polarizing plate 100 with a gas barrier layer shown in FIG. 5 has the gas barrier film 40 and the polarizing plate 101 described above.
- the polarizing plate 101 is arranged on the main surface 41a of the adhesive layer 41 opposite to the first layer 13 side.
- the polarizing plate 101 and the first layer 13 are bonded together with the adhesive layer 41 interposed therebetween.
- the polarizing plate 100 with a gas barrier layer shown in FIG. 5 has a gas barrier film 40 (gas barrier film 30)
- 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 40.
- the gas barrier film included in the polarizing plate with a gas barrier layer according to the third embodiment is a gas barrier film in which the gas barrier layer is composed only of a first layer (silicon oxycarbide layer) and a second layer (silicon oxynitride layer), or A gas barrier film having a gas barrier layer having a laminated structure of four or more layers may also be used.
- the gas barrier film included in the polarizing plate with a gas barrier layer according to the third embodiment may be the gas barrier film 10 or the gas barrier film 20, for example.
- 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 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 gas barrier properties and transparency.
- 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. 6 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. 6 includes a gas barrier layer-attached polarizing plate 100 having a gas barrier film 40 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 31 and the display element 204 are bonded together with the adhesive layer 201 interposed therebetween.
- the image display device 200 shown in FIG. 6 has the gas barrier film 40 (gas barrier film 30)
- the gas barrier film of the image display device according to the fourth embodiment is not limited to the gas barrier film 40.
- the gas barrier film included in the image display device according to the fourth embodiment is a gas barrier film in which the gas barrier layer is composed only of the first layer (silicon oxycarbide layer) and the second layer (silicon oxynitride layer), or four layers.
- a gas barrier film having a gas barrier layer having the above laminated structure may also be used.
- the gas barrier film included in the image display device according to the fourth embodiment may be the gas barrier film 10 or the gas barrier film 20, for example.
- the same adhesives as those exemplified as the adhesive constituting the adhesive layer 41 described above can be used.
- the adhesive that forms the adhesive layer 201 and the adhesive that forms the adhesive layer 41 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 41 described above.
- the thickness of the adhesive layer 201 and the thickness of the adhesive layer 41 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 40 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
- the methods for producing the gas barrier films of Examples 1 to 14 and Comparative Examples 1 to 5 are described below.
- the "first layer” means the layer in the gas barrier layer that is the farthest from the transparent film substrate.
- “Second layer” means a layer in contact with the main surface of the first layer on the side of the transparent film substrate.
- “Third layer” means a layer in contact with the main surface of the second layer on the side of the transparent film substrate.
- the "fourth layer” means a layer in contact with the main surface of the third layer on the side of the transparent film substrate.
- the "fifth layer” means a layer in contact with the main surface of the fourth layer on the side of the transparent film substrate.
- 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 third layer (silicon oxycarbide layer) with a thickness of 200 nm was formed on the film by CVD, and then a second layer (silicon oxynitride layer) with a thickness of 30 nm was formed on the third layer by CVD.
- a first layer (silicon oxycarbide layer) having a thickness of 200 nm was formed on the second layer by CVD, and as a gas barrier film of Example 1, a silicon oxycarbide layer/silicon oxynitride layer/silicon oxycarbide layer was formed.
- a gas barrier film having a gas barrier layer having a layer structure was obtained.
- the temperature of the base material is set to 12° C.
- the frequency of the power source for plasma generation is set to 80 kHz
- the discharge is performed under the conditions of an applied power of 1.0 kW.
- Plasma was generated, a film forming gas was introduced between the film forming rolls (between the electrodes) in the vacuum chamber, and a film was formed at a pressure of 1.0 Pa.
- Hexamethyldisiloxane (HMDSO) (flow rate: 25 sccm) and oxygen (flow rate: 700 sccm) were used as deposition gases for both the first layer and the third layer.
- HMDSO Hexamethyldisiloxane
- oxygen flow rate: 700 sccm
- TSA trisilylamine
- nitrogen flow rate: 500 sccm
- oxygen flow rate: 100 sccm
- Example 2 A gas barrier film of Example 2 was produced in the same manner as in Example 1, except that the second layer was formed directly on the film without forming the third layer.
- Example 3 A gas barrier film of Example 3 was produced in the same manner as in Example 1, except that the thickness of the second layer was changed to 60 nm.
- Example 4 When forming the second layer, except that the flow rate of nitrogen was set to 550 sccm and the flow rate of oxygen was set to 50 sccm, and the thickness of the second layer was changed to 60 nm. A gas barrier film of Example 4 was prepared.
- Example 5 A gas barrier film of Example 5 was produced in the same manner as in Example 1, except that the thicknesses of the first layer and the third layer were both changed to 330 nm.
- Example 6 A gas barrier film of Example 6 was produced in the same manner as in Example 1, except that the thicknesses of the first layer and the third layer were both changed to 330 nm, and the thickness of the second layer was changed to 60 nm. .
- Example 7 A gas barrier film of Example 7 was produced in the same manner as in Example 1, except that the thickness of the second layer was changed to 120 nm.
- Example 8 A gas barrier film of Example 8 was produced in the same manner as in Example 1, except that the thickness of the second layer was changed to 180 nm.
- Example 9 A gas barrier film of Example 9 was produced in the same manner as in Example 1, except that the thickness of the first layer was changed to 150 nm.
- Example 10 A gas barrier film of Example 10 was produced in the same manner as in Example 1, except that the thickness of the first layer was changed to 100 nm.
- Example 11 A gas barrier film of Example 11 was produced in the same manner as in Example 1, except that the thickness of the third layer was changed to 50 nm.
- Example 12 A fifth layer (silicon oxycarbide layer) with a thickness of 200 nm and a fourth layer (silicon oxynitride layer) with a thickness of 30 nm were deposited by CVD between the transparent film substrate and the third layer in this order from the transparent film substrate side.
- a gas barrier film of Example 12 was produced in the same manner as in Example 1 except for the above.
- the deposition conditions for the fifth layer were the same as the deposition conditions for the third layer in Example 1.
- the deposition conditions for the fourth layer were the same as the deposition conditions for the second layer in Example 1.
- Example 13 When forming the first layer and the third layer, the flow rate of HMDSO was set to 15 sccm, the flow rate of oxygen was set to 420 sccm, the applied power was set to 0.6 kW, and the thickness of the second layer was changed to 60 nm.
- a gas barrier film of Example 13 was produced in the same manner as in Example 1, except for the above.
- Example 14 In forming the second layer, the same method as in Example 1 was used except that the flow rate of nitrogen was set to 575 sccm and the flow rate of oxygen was set to 25 sccm, and the thickness of the second layer was changed to 60 nm. A gas barrier film of Example 14 was made.
- Comparative Example 1 A gas barrier film of Comparative Example 1 was produced in the same manner as in Example 1, except that the thickness of the second layer was changed to 240 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 thickness of the first layer was changed to 50 nm.
- Comparative Example 3 A gas barrier film of Comparative Example 3 was produced in the same manner as in Example 1, except that the thicknesses of the first layer and the third layer were both changed to 50 nm.
- Comparative Example 4 A gas barrier film of Comparative Example 4 was produced in the same manner as in Example 1, except that the thicknesses of the first layer and the third layer were both changed to 330 nm, and the thickness of the second layer was changed to 230 nm. .
- a gas barrier film having a gas barrier layer having a layer structure of silicon oxycarbide layer/silicon oxynitride layer was obtained.
- the substrate temperature is set to 12 ° C.
- the frequency of the plasma generation power supply is set to 80 kHz
- the applied power is 1.0 kW to generate plasma.
- a film forming 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.
- HMDSO flow rate condition: 25 sccm
- oxygen flow rate condition: 700 sccm
- TSA flow rate: 30 sccm
- nitrogen flow rate: 500 sccm
- oxygen flow rate: 100 sccm
- total etching time of the silicon oxycarbide layer is the time from the start of etching when etching the silicon oxycarbide layer (each silicon oxycarbide layer when multiple silicon oxycarbide layers are provided). Means time to finish.
- Total etching time of a silicon oxynitride layer means the time from the start to the end of etching when etching a silicon oxynitride layer (each silicon oxynitride layer when multiple silicon oxynitride layers are provided). means the time of 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. Detailed measurement conditions are shown below.
- the light transmittance (Y value) of the gas barrier film was measured with a spectrophotometer ("U4100" manufactured by Hitachi High-Tech Science). When the light transmittance was 75% or more, it was evaluated as “excellent in transparency”. On the other hand, when the light transmittance was less than 75%, it was evaluated as "not excellent in transparency”.
- the gas barrier layer consisted of a first layer containing silicon, oxygen and carbon as constituent elements and a second layer containing silicon, oxygen and nitrogen as constituent elements. had In Examples 1 to 14, the thickness of the first layer was 80 nm or more and 700 nm or less. In Examples 1 to 14, the thickness of the second layer was 20 nm or more and 220 nm or less. In Examples 1 to 14, the oxygen content in the second layer was 15 atomic % or more when the total of silicon, oxygen and nitrogen in the second layer was 100 atomic %.
- Examples 1 to 14 the light transmittance was 75% or more. Therefore, the gas barrier films of Examples 1 to 14 were excellent in transparency. In Examples 1 to 14, WVTR was 7.0 ⁇ 10 ⁇ 3 g/m 2 ⁇ day or less. Therefore, the gas barrier films of Examples 1 to 14 were excellent in gas barrier properties.
- the thickness of the second layer exceeded 220 nm.
- the thickness of the first layer was less than 80 nm.
- the layer (first layer) located farthest from the transparent film substrate in the gas barrier layer was the silicon oxynitride layer.
- the present invention can provide a gas barrier film with excellent transparency and gas barrier properties.
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Abstract
L'invention concerne un film formant barrière contre les gaz (10) comprenant un matériau de base de film transparent (11) et une couche formant barrière contre les gaz (12). La couche formant barrière contre les gaz (12) comprend : une première couche (13) qui contient, en tant qu'éléments constitutifs, du silicium, de l'oxygène et du carbone ; et une seconde couche (14) qui contient, en tant qu'éléments constitutifs, du silicium, de l'oxygène et de l'azote. La première couche (13) est la couche la plus éloignée dans la couche formant barrière contre les gaz (12) à partir du matériau de base de film transparent (11). La seconde couche (14) est en contact avec une surface principale (13a) côté matériau de base de film transparent (11) de la première couche (13). Si la teneur totale en silicium, oxygène et azote dans la seconde couche (14) est prise en tant que 100 % par atome, le rapport de teneur en oxygène dans la seconde couche (14) est de 15 % par atome ou plus. L'épaisseur de la première couche (13) est de 80 nm à 700 nm. L'épaisseur de la seconde couche (14) est de 20 nm à 220 nm.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006263989A (ja) * | 2005-03-22 | 2006-10-05 | Fuji Photo Film Co Ltd | ガスバリア性フィルム、基材フィルムおよび有機エレクトロルミネッセンス素子 |
JP2007015350A (ja) * | 2005-07-11 | 2007-01-25 | Fujifilm Holdings Corp | ガスバリア性フィルム、基材フィルムおよび有機エレクトロルミネッセンス素子 |
JP2010064303A (ja) * | 2008-09-09 | 2010-03-25 | Gunze Ltd | 透明導電膜付ガスバリアフィルムとこれを用いたタッチパネル |
JP2012087326A (ja) * | 2010-10-15 | 2012-05-10 | Lintec Corp | 透明導電性フィルム、その製造方法、電子デバイス用部材及び電子デバイス |
JP2012086378A (ja) * | 2010-10-15 | 2012-05-10 | Lintec Corp | 透明導電性フィルム、その製造方法、電子デバイス用部材及び電子デバイス |
JP2013180473A (ja) * | 2012-03-01 | 2013-09-12 | Nitto Denko Corp | 透明ガスバリアフィルム、有機el素子、太陽電池および薄膜電池 |
JP2015131473A (ja) * | 2014-01-15 | 2015-07-23 | コニカミノルタ株式会社 | ガスバリア性フィルム、およびこれを用いた電子デバイス |
JP2017007310A (ja) * | 2015-06-26 | 2017-01-12 | 株式会社マテリアルデザインファクトリ− | ガスバリアフィルム、該ガスバリアフィルムを含む製品、および該ガスバリアフィルムの製造方法 |
-
2022
- 2022-09-22 WO PCT/JP2022/035425 patent/WO2023054176A1/fr unknown
- 2022-09-30 TW TW111137191A patent/TW202332583A/zh unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006263989A (ja) * | 2005-03-22 | 2006-10-05 | Fuji Photo Film Co Ltd | ガスバリア性フィルム、基材フィルムおよび有機エレクトロルミネッセンス素子 |
JP2007015350A (ja) * | 2005-07-11 | 2007-01-25 | Fujifilm Holdings Corp | ガスバリア性フィルム、基材フィルムおよび有機エレクトロルミネッセンス素子 |
JP2010064303A (ja) * | 2008-09-09 | 2010-03-25 | Gunze Ltd | 透明導電膜付ガスバリアフィルムとこれを用いたタッチパネル |
JP2012087326A (ja) * | 2010-10-15 | 2012-05-10 | Lintec Corp | 透明導電性フィルム、その製造方法、電子デバイス用部材及び電子デバイス |
JP2012086378A (ja) * | 2010-10-15 | 2012-05-10 | Lintec Corp | 透明導電性フィルム、その製造方法、電子デバイス用部材及び電子デバイス |
JP2013180473A (ja) * | 2012-03-01 | 2013-09-12 | Nitto Denko Corp | 透明ガスバリアフィルム、有機el素子、太陽電池および薄膜電池 |
JP2015131473A (ja) * | 2014-01-15 | 2015-07-23 | コニカミノルタ株式会社 | ガスバリア性フィルム、およびこれを用いた電子デバイス |
JP2017007310A (ja) * | 2015-06-26 | 2017-01-12 | 株式会社マテリアルデザインファクトリ− | ガスバリアフィルム、該ガスバリアフィルムを含む製品、および該ガスバリアフィルムの製造方法 |
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