TW202332582A - Gas barrier film and method for producing the same, and polarizing plate with gas barrier layer and image display device - Google Patents

Abstract

There is provided a gas barrier film 10 which has a transparent film base material 11 and a gas barrier layer 12. The gas barrier layer 12 has a silicon oxynitride layer 13. A composition of a silicon oxynitride contained in the silicon oxynitride layer 13 is expressed by the general formula SiOxNy. The x and y of the general formula SiOxNy satisfy a relation of 0.30 < x < 1.20, 0.40 < y < 0.80 and 0.50 < x/y < 2.30. In a Si2p spectrum of the silicon oxynitride layer 13, when the area of a region between a Si2p spectral curve and a baseline is defined as S1 and the area of a peak derived from Si-Si bonding is defined as S2, a relation 0.05 ≤ S2/S1 ≤ 0.30 is satisfied.

Description

Gas barrier film and manufacturing method thereof, as well as polarizing plate and image display device with gas barrier layer

The present invention relates to a gas barrier film and its manufacturing method, as well as a polarizing plate and an image display device with a gas barrier layer.

As image display devices become lighter, thinner and more flexible, resin film substrates are gradually used to replace glass substrates. Compared with glass, resin films have higher permeability to gases such as water vapor or oxygen. Therefore, it is proposed to use a gas barrier film with a gas barrier layer to suppress the deterioration of display elements caused by these gases.

Organic EL (Electroluminescence, electroluminescence) devices sometimes have defects called "dark spots" due to the penetration of trace amounts of moisture, and are required to have high gas barrier properties (water vapor barrier properties). As materials with excellent gas barrier properties, silicon nitride (SiN) and silicon oxynitride (SiON) are known.

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 excellent in transparency and flexibility. [Prior technical documents] [Patent documents]

[Patent Document 1] International Publication No. 2019/187978

[Problem to be solved by the invention]

Research by the present inventors has revealed that in a gas barrier film using a nitrogen-containing layer (more specifically, a silicon nitride layer, a silicon oxynitride layer, etc.) as a gas barrier layer, the gas barrier film may be deformed in a humidified environment. The nitrogen-containing layer produces ammonia (ammonia gas). Ammonia generated from the nitrogen-containing layer reacts with moisture in the air to produce ammonium ions and hydroxide ions. The plasma may corrode components.

It is difficult to obtain a gas barrier film that suppresses the generation of ammonia, ensures gas barrier properties even when exposed to high temperature and high humidity environments, and has excellent transparency using only the technology disclosed in Patent Document 1.

The present invention was completed in view of the above problems, and its object is to provide a gas barrier film that suppresses the generation of ammonia, ensures gas barrier properties even when exposed to a high temperature and high humidity environment, and has excellent transparency, and a method for manufacturing the same. A polarizing plate and an image display device with a gas barrier layer using the gas barrier film. [Technical means to solve problems]

<Aspects of the present invention> The present invention includes the following aspects.

[1] A gas barrier film having a transparent film base material and a gas barrier layer directly or indirectly disposed on at least one main surface of the transparent film base material, and the gas barrier layer has a gas barrier layer containing oxygen, nitrogen and silicon. The composition of the silicon oxynitride layer of the constituent elements is represented by the general formula SiO _x N _y . The composition of the silicon oxynitride contained in the silicon oxynitride layer is represented by the general formula SiO _x N _y . The relationship between 0.40＜y＜0.80 and 0.50＜x/y＜2.30, in the Si2p spectrum of the above-mentioned silicon oxynitride layer obtained by X-ray photoelectron spectroscopy, combines Si2p with a binding energy in the range of 95 eV to 110 eV When the area of the region between the spectral curve and the baseline is set to S1, and the area of the peak derived from the Si-Si bond separated from the above-mentioned Si2p spectrum by waveform analysis is set to S2, 0.05≦S2/S1≦0.30 is satisfied. relation.

[2] The gas barrier film according to the above [1], wherein the S2/S1 is 0.15 or more and 0.30 or less.

[3] The gas barrier film according to the above [1] or [2], wherein the x/y is 2.00 or less.

[4] The gas barrier film according to any one of the above [1] to [3], wherein the thickness of the silicon oxynitride layer is from 10 nm to 200 nm.

[5] The gas barrier film according to any one of [1] to [4] above, further comprising a hard coat layer disposed between the transparent film base material and the gas barrier layer.

[6] The gas barrier film according to any one of the above [1] to [5], further comprising an adhesive layer disposed on the side of the gas barrier layer opposite to the side of the transparent film substrate.

[7] A method for manufacturing a gas barrier film, which is a method for manufacturing a gas barrier film as described in any one of the above [1] to [6], and includes introducing trisilylamine, a nitrogen source and an oxygen source The step of forming the silicon oxynitride layer by chemical vapor phase growth in a chamber of a film forming device.

[8] A polarizing plate with a gas barrier layer, including the gas barrier film according to any one of the above [1] to [6], and a polarizing element.

[9] An image display device including the gas barrier film according to any one of [1] to [6] above, and an image display unit.

[10] An image display device including the polarizing plate with a gas barrier layer as described in the above [8], and an image display unit.

[11] The image display device according to the above [9] or [10], wherein the image display unit includes an organic EL element. [The effect of the invention]

According to the present invention, it is possible to provide a gas barrier film that suppresses the generation of ammonia, ensures gas barrier properties even when exposed to a high temperature and high humidity environment, and has excellent transparency, a manufacturing method thereof, and a gas barrier film using the gas barrier film. layer of polarizing plates and image display devices.

Preferred embodiments of the present invention will be described below. First, the terms used in this manual will be explained. Regarding the number-average primary particle diameter of particles, unless there is any specification, it refers to 100 primary particles measured using a scanning electron microscope and image processing software (for example, "ImageJ" manufactured by the National Institutes of Health). The numerical average value of the circle equivalent diameter (projected area circle equivalent diameter: the diameter of a circle with the same area as the projected area of the primary particle).

The "main surface" of a layered object (more specifically, a transparent film base material, a gas barrier layer, a silicon nitride oxide layer, a hard coat layer, an adhesive layer, a polarizing element, etc.) refers to the direction of the thickness of the layered object. Meet each other. The value of "thickness" of a layered material is the "average thickness". The average thickness of the layered material is obtained by observing a cross-section of the layered material along the thickness direction using an electron microscope, randomly selecting 10 measurement positions from the cross-sectional image, and measuring the thickness of the selected 10 measurement positions. The arithmetic mean of the measured values.

"Refractive index" refers to the refractive index of light with a wavelength of 550 nm at a temperature of 23°C.

The unit of flow rate "sccm (Standard Cubic Centimeter per Minute, standard condition milliliters per minute)" refers to the unit of flow rate "mL/minute" under standard conditions (temperature: 0℃, pressure: 101.3 kPa).

Hereinafter, X-ray photoelectron spectroscopy is sometimes referred to as "XPS". In addition, the spectrum obtained by XPS is sometimes referred to as "XPS spectrum". Hereinafter, unless otherwise specified, the "XPS spectrum" refers to the XPS spectrum after removing the background by the Shirley method. "Si2p spectrum" refers to the XPS spectrum of the 2p orbit of Si (silicon). "Baseline" refers to the XPS spectral line (or XPS spectral curve) extrapolated from the XPS spectrum as the photoelectrons originating from the 2p orbit of silicon are not emitted. That is, the baseline is assumed to be the XPS spectral line (or XPS spectral curve) that does not emit photoelectrons originating from the 2p orbit of silicon. The "peak" in the XPS spectrum refers to the part of the curve from the baseline on the low energy side until it returns to the same baseline again. The "peak area" in the XPS spectrum refers to the area between the curve constituting the peak and the baseline.

In the following, "system" may be appended to the compound name to collectively refer to the compound and its derivatives. When "system" is appended to the compound name to represent the polymer name, it means that the repeating units of the polymer are derived from the compound or its derivatives. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth)acrylic acid".

The drawings referred to in the following description are schematically shown with each constituent element as the main body in order to facilitate understanding. In order to facilitate the preparation of the drawings, the size, number, and shape of each constituent element in the illustration may be changed. etc. are different from reality. In addition, for the sake of convenience of description, in the drawings described below, the same components as those in the drawings described above are denoted by the same symbols, and their descriptions may be omitted.

<First Embodiment: Gas Barrier Film> A gas barrier film according to the first embodiment of the present invention has a transparent film base material, and a gas barrier layer directly or indirectly arranged on at least one main surface of the transparent film base material. The gas barrier layer has a silicon oxynitride layer containing oxygen, nitrogen and silicon as constituent elements. The composition of silicon oxynitride contained in the silicon oxynitride layer is represented by the general formula SiO _x N _y . In the general formula SiO _x N _y , x and y satisfy the relationships of 0.30<x<1.20, 0.40<y<0.80 and 0.50<x/y<2.30. In the Si2p spectrum of the silicon oxynitride layer obtained by When the area of the peak derived from the Si-Si bond separated by the spectrum is set to S2, the relationship of 0.05≦S2/S1≦0.30 is satisfied.

Hereinafter, x in the general formula SiO _x N _y may be simply referred to as "x". In addition, y in the general formula SiO _x N _y may be simply written as "y". In addition, in the Si2p spectrum of the silicon oxynitride layer obtained by XPS, the area between the Si2p spectrum curve and the baseline in the range of the binding energy of 95 eV to 110 eV is sometimes expressed as "area S1" or "S1". In addition, the area of the peak derived from the Si-Si bond separated from the Si2p spectrum by waveform analysis is sometimes referred to as "area S2" or "S2". The measurement methods of x, y, and the area ratio of S1 and S2 (S2/S1) are all the same as the examples described below or methods based on them.

The gas barrier film of the first embodiment has the above-mentioned structure, so it suppresses the generation of ammonia (especially the generation of ammonia in a humidified environment), and ensures gas barrier properties and transparency even if it is exposed to a high temperature and high humidity environment. Excellent. Hereinafter, the gas barrier properties after exposure to high temperature and high humidity environments are sometimes referred to as "gas barrier properties after high temperature and high humidity".

In the first embodiment, the gas barrier property tends to be higher as the ratio of x to y, that is, x/y, is smaller (i.e., the ratio of nitrogen is higher), and the larger x/y is (i.e., The higher the oxygen ratio), the less visible light is absorbed and the transparency tends to be improved.

In the first embodiment, the silicon oxynitride layer included in the silicon oxynitride layer may have a stoichiometric composition, or may have a non-stoichiometric composition lacking oxygen or nitrogen. The stoichiometric composition of silicon oxynitride satisfies x/2+3y/4=1. The value of (x/2+3y/4) is preferably from 0.70 to 1.10. The upper limit of (x/2+3y/4) is theoretically 1, but sometimes a value greater than 1 occurs due to excessive inclusion of oxygen or nitrogen. If (x/2+3y/4) is 0.70 or more, the transparency and gas barrier properties tend to be improved.

In the first embodiment, the greater the number of Si-Si bonds in the silicon oxynitride layer, the greater the area ratio between S1 and S2, that is, S2/S1. Furthermore, in the first embodiment, the larger S2/S1 is, the higher the gas barrier property is after high temperature and high humidity, and the tendency is to suppress the generation of ammonia (especially the generation of ammonia in a humidified environment). . It can be speculated that the reason is that the larger S2/S1 (the greater the number of Si-Si bonds in the silicon oxynitride layer), the more it can inhibit the Si-O bonds in the silicon oxynitride layer from being broken due to hydrolysis. As a result The better it can suppress the deterioration of the silicon oxynitride layer due to humidification.

In the first embodiment, in order to obtain a gas barrier film with more excellent transparency, x is preferably 0.33 or more, more preferably 0.35 or more, and further preferably 0.38 or more. In the first embodiment, in order to obtain a gas barrier film with better gas barrier properties after high temperature and high humidity, x is preferably 1.18 or less, more preferably 1.15 or less, and even more preferably 1.12 or less.

In the first embodiment, in order to obtain a gas barrier film with better gas barrier properties after high temperature and high humidity, y is preferably 0.43 or more, more preferably 0.45 or more, and further preferably 0.48 or more. In the first embodiment, in order to obtain a gas barrier film that further suppresses the generation of ammonia and has better transparency, y is preferably 0.78 or less, more preferably 0.77 or less, and still more preferably 0.76 or less.

In the first embodiment, in order to obtain a gas barrier film that further suppresses the generation of ammonia and has better transparency, x/y is preferably 0.52 or more, more preferably 0.53 or more, and still more preferably 0.54 or more. In the first embodiment, in order to obtain a gas barrier film with better gas barrier properties after exposure to high temperature and high humidity, x/y is preferably 2.25 or less, more preferably 2.20 or less, further preferably 2.10 or less, especially 2.00 or less. , it can also be below 1.90, below 1.80 or below 1.70.

In the first embodiment, in order to obtain a gas barrier film that further suppresses the generation of ammonia and has better gas barrier properties after exposure to high temperatures and high humidity, S2/S1 is preferably 0.06 or more, more preferably 0.08 or more, and still more preferably 0.10. Above, preferably above 0.15. In the first embodiment, in order to obtain a gas barrier film with better transparency, S2/S1 is preferably 0.29 or less, more preferably 0.28 or less. In the first embodiment, in order to obtain a gas barrier film that further suppresses the generation of ammonia and has better gas barrier properties and transparency after exposure to high temperatures and high humidity, S2/S1 is preferably 0.06 or more and 0.30 or less, more preferably 0.08 or more and 0.30. or less, more preferably 0.10 or more and 0.30 or less, particularly preferably 0.15 or more and 0.30 or less, and may also be 0.15 or more and 0.29 or less, or 0.15 or more and 0.28 or less.

In the first embodiment, in order to obtain a gas barrier film that further suppresses the generation of ammonia and has better gas barrier properties and transparency after exposure to high temperatures and high humidity, it is preferable to satisfy the following condition 1, and more preferably to satisfy the following condition 2. , and more preferably satisfies the following condition 3. Condition 1: x is above 0.38 and below 1.12, and y is above 0.48 and below 0.76. Condition 2: The above condition 1 is met, and x/y is above 0.54 and below 2.00. Condition 3: The above condition 2 is met, and S2/S1 is above 0.15 and below 0.30.

Hereinafter, the first embodiment will be described in detail 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. The gas barrier film 10 shown in FIG. 1 is a laminated body including a transparent film base 11 and a gas barrier layer 12 directly disposed on one main surface 11 a of the transparent film base 11 . The gas barrier layer 12 has a single-layer structure composed of a silicon oxynitride layer 13 containing oxygen, nitrogen and silicon as constituent elements. The composition of silicon oxynitride contained in the silicon oxynitride layer 13 is represented by the general formula SiO _x N _y . In the general formula SiO _x N _y , x and y satisfy the relationships of 0.30<x<1.20, 0.40<y<0.80 and 0.50<x/y<2.30. In the Si2p spectrum of the silicon oxynitride layer 13 obtained by When the area of the peak derived from the Si-Si bond separated by the Si2p spectrum is set to S2, it satisfies the relationship of 0.05≦S2/S1≦0.30.

FIG. 2 is a diagram showing an example of the results (ie, XPS spectrum) of the silicon oxynitride layer 13 analyzed by XPS. The XPS spectrum in Figure 2 has the background removed by the Shirley method. In Figure 2, the vertical axis represents intensity (counts per second, abbreviated as c/s in Figure 2), and the horizontal axis represents binding energy. In addition, in FIG. 2 , the Si2p spectrum curve SP is drawn as a solid line, the curve P1 constituting the peak derived from the Si-Si bond is drawn as a dotted line, and the base line BL is drawn as a single-dot chain line. The peaks originating from Si-Si bonds are peaks separated from the Si2p spectrum by waveform analysis. An example of a method of separating the Si2p spectrum by waveform analysis is a method of processing using a composite function of a Gaussian function and a Lorentz function (Gaussian-Lorentz function). Specifically, by using waveform analysis software (for example, "PHI MultiPak" manufactured by ULVAC-PHI Co., Ltd.) and processing the Si2p spectrum using the Gauss-Lorentz function, it is possible to separate the Si-Si bonds from the spectrum. Peak (peak with maximum value in the range of binding energy above 99 eV and below 101 eV). In Figure 2, area S1 refers to the area between the Si2p spectrum curve SP and the baseline BL in the range of binding energy 95 eV to 110 eV. In FIG. 2 , the area S2 refers to the area constituting the area between the curve P1 of the separated peak derived from the Si-Si bond and the baseline BL. Furthermore, although not shown in the figure, the XPS spectrum in Figure 2 also includes peaks derived from Si—O bonds and peaks derived from Si—N bonds.

The structure of the gas barrier film of the first embodiment is not limited to the structure of the gas barrier film 10 shown in FIG. 1 . For example, the gas barrier film of the first embodiment may have a laminated structure in which the gas barrier layer is composed of a plurality of thin films like the gas barrier film 20 shown in FIG. 3 . In the gas barrier film 20 , the gas barrier layer 21 has a silicon oxynitride layer 13 and a low refractive index layer 22 disposed on the main surface 13 a of the silicon oxynitride layer 13 opposite to the transparent film substrate 11 side. The low refractive index layer 22 has a lower refractive index than the silicon oxynitride layer 13 . The low refractive index layer 22 has the following functions: together with the silicon oxynitride layer 13, it improves the gas barrier property, and functions as an optical interference layer to reduce light reflection caused by the gas barrier layer 21 and increase the light transmittance. The gas barrier film of the first embodiment may also include low refractive index layers on both main surfaces of the silicon oxynitride layer.

Furthermore, in the gas barrier film of the first embodiment, the gas barrier layer may include two or more silicon oxynitride layers, for example, it may be an alternating laminate of two silicon oxynitride layers and three low refractive index layers. . The gas barrier layer may also be a laminated structure of 4 layers or a laminated structure of more than 6 layers. For example, the gas barrier layer having a four-layer structure may be an alternating laminated body in which a silicon oxynitride layer/low refractive index layer/silicon oxynitride layer/low refractive index layer are arranged in order from the transparent film substrate side. In an alternating laminated body in which the total number of layers is an even number, the outermost layer is preferably a low refractive index layer. The gas barrier layer containing a total of 4 or more layers may also include a refractive index layer with a refractive index intermediate between the silicon oxynitride layer and the low refractive index layer, or be composed of a material with a higher refractive index than silicon oxynitride layer. high refractive index layer. The gas barrier layer may be an alternating laminated body including 3 silicon oxynitride layers and 4 low refractive index layers, a total of 7 layers, or may be an alternating laminated body including 8 or more layers.

Furthermore, the gas barrier film of the first embodiment can have the gas barrier layer indirectly disposed on the main surface of the transparent film base material. For example, the gas barrier film 30 shown in FIG. 4 has a hard coat layer 31 disposed between the transparent film base material 11 and the gas barrier layer 12 (silicon oxynitride layer 13). In the gas barrier film 30 , the gas barrier layer 12 is indirectly disposed on the main surface of the transparent film base 11 . The hard coat layer 31 is a layer that improves mechanical properties such as hardness or elastic modulus of the gas barrier film 30 . If the main surface of the hard coat layer 31 on the gas barrier layer 12 side is smooth, the gas barrier properties of the gas barrier layer 12 formed thereon will increase, and the water vapor transmittance will tend to decrease. The arithmetic mean height Sa of the main surface on the gas barrier layer 12 side of the hard coating layer 31 may be 1.5 nm or less or 1.0 nm or less. The arithmetic mean height Sa is calculated according to ISO 25178 based on the three-dimensional surface shape in the range of 1 μm × 1 μm measured using an atomic force microscope (AFM).

The hard coat layer 31 may contain particles whose number average primary particle size is less than 1.0 μm (hereinafter, sometimes referred to as "nanoparticles"). For example, by making the hard coat layer 31 contain nanoparticles and forming fine unevenness on the surface of the hard coat layer 31, the adhesion between the hard coat layer 31 and the gas barrier layer 12 tends to be improved.

In addition, in order to further improve the gas barrier properties of the gas barrier film of the first embodiment, gas barrier layers may be provided on both main surfaces of the transparent film base material. For example, the gas barrier film 40 shown in FIG. 5 has a gas barrier layer 12 (silicon oxynitride layer 13) disposed on one main surface 11a of the transparent film base material 11, and a gas barrier layer 12 (silicon oxynitride layer 13) disposed on the other main surface of the transparent film base material 11. 11b gas barrier layer 41. In the gas barrier film of the first embodiment, gas barrier layers having a laminated structure may be provided on both main surfaces of the transparent film base material.

The composition of the gas barrier layer 41 may be the same as that of the gas barrier layer 12 , or may be different. That is, the gas barrier layer 41 may or may not have a silicon oxynitride layer in which x, y, x/y, and S2/S1 are within the above-mentioned specific ranges. In order to obtain a gas barrier film with further improved gas barrier properties and excellent transparency, it is preferred that the gas barrier layer 41 has a silicon oxynitride layer, and the silicon oxynitride layer of the gas barrier layer 41 satisfies 0.30<x<1.20, 0.40 The relationships of <y<0.80, 0.50<x/y<2.30, and 0.05≦S2/S1≦0.30.

Furthermore, the gas barrier film of the first embodiment may further include an adhesive layer. For example, the gas barrier film 50 shown in FIG. 6 has an adhesive layer 51 in addition to the structure of the gas barrier film 40 . In the gas barrier film 50 , an adhesive layer 51 is disposed on the main surface 13 a of the gas barrier layer 12 (silicon oxynitride layer 13 ) opposite to the transparent film base material 11 side.

A release liner (not shown) may be temporarily adhered to the main surface of the adhesive layer 51 opposite to the side of the silicon oxynitride layer 13 . The release liner protects the surface of the adhesive layer 51 before, for example, the gas barrier film 50 is bonded to the polarizing plate 101 (see FIG. 7 ) described below. As a material constituting the release liner, a plastic film made of acrylic, polyolefin, cyclic polyolefin, polyester, etc. can be preferably used. The thickness of the release liner is, for example, 5 μm or more and 200 μm or less. It is preferable to perform a release treatment on the surface of the release liner. Examples of the material of the release agent used in the release treatment include: silicone-based materials, fluorine-based materials, long-chain alkyl-based materials, fatty acid amide-based materials, etc.

The structure of the gas barrier film according to the first embodiment has been described above with reference to the drawings. Next, the elements of the gas barrier film of the first embodiment will be described.

[Transparent film base material 11] The transparent film base material 11 is the base layer that forms the gas barrier layer. The transparent film base 11 may have flexibility. By using a flexible film as the base material, the gas barrier layer can be formed in a roll-to-roll manner, thereby improving the productivity of the gas barrier layer. In addition, a gas barrier film formed by providing a gas barrier layer on a flexible film has the advantage that it can also be applied to soft devices or foldable devices.

The visible light transmittance of the transparent film base material 11 is preferably above 80%, more preferably above 90%. The thickness of the transparent film base material 11 is not particularly limited, but from the viewpoint of strength or handleability, it is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 150 μm or less, and still more preferably 30 μm or more. Below 100 μm.

As the resin material constituting the transparent film base material 11, a resin material excellent in transparency, mechanical strength, and thermal stability is preferred. Specific examples of the resin material include cellulose-based resins such as triacetyl cellulose, polyester-based resins, polyether-based resins, polyurethane-based resins, polycarbonate-based resins, and polyamide-based resins. Polyimide resin, polyolefin resin, (meth)acrylic resin, cyclic polyolefin resin (more specifically, norvinyl resin, etc.), polyarylate resin, polystyrene resin Resin, polyvinyl alcohol resin, and mixtures thereof.

In order to improve the adhesion with the gas barrier layer on the main surface of the transparent film base material 11 on which the gas barrier layer is formed, corona treatment, plasma treatment, flame treatment, ozone treatment, glow treatment, saponification treatment, etc. can also be performed. Coupling agent treatment and other surface modification treatments.

The surface layer of the transparent film substrate 11 on the side forming the gas barrier layer may be a primer layer (not shown). When the surface layer on the side where the gas barrier layer is formed is a primer layer, the adhesion between the transparent film base material 11 and the gas barrier layer tends to be improved. Examples of materials constituting the undercoat layer include silicon, nickel, chromium, tin, gold, silver, platinum, zinc, indium, titanium, tungsten, aluminum, zirconium, palladium and other metals (or semi-metals); Alloys of metals (or semimetals); oxides, fluorides, sulfides or nitrides of these metals (or semimetals), etc. The thickness of the undercoat layer is, for example, 1 nm or more and 20 nm or less, preferably 1 nm or more and 15 nm or less, more preferably 1 nm or more and 10 nm or less.

[Silicon nitride oxide layer 13] The silicon nitride oxide layer 13 is the layer mainly responsible for the gas barrier function in the gas barrier layer, and is a layer composed of materials with silicon, oxygen and nitrogen as the main constituent elements. The silicon oxynitride layer 13 may also include a small amount of hydrogen, carbon and other elements incorporated into the raw material during self-film formation, the transparent film substrate 11 and the external environment.

In the silicon oxynitride layer 13 , the content rates of elements other than silicon, oxygen, and nitrogen are each preferably 5 atomic % or less, more preferably 3 atomic % or less, and still more preferably 1 atomic % or less. The total content of silicon, oxygen, and nitrogen among the elements constituting the silicon oxynitride layer 13 is preferably 90 atomic % or more, more preferably 95 atomic % or more, further preferably 97 atomic % or more, and may also be 99 atomic %. More than 99.5 atomic % or more or 99.9 atomic % or more.

The refractive index of the silicon oxynitride layer 13 is usually 1.50 or more and 2.20 or less, preferably 1.55 or more and 2.00 or less. It can also be 1.60 or more and 1.90 or less, or it can be 1.85 or less, 1.80 or less, 1.75 or less, or 1.70 or less. The silicon oxynitride layer 13 with a refractive index in this range can have both excellent gas barrier properties and transparency. In addition, when the refractive index is 2.00 or less, the light transmittance tends to be improved. The silicon oxynitride layer 13 shows a tendency that the higher the ratio of nitrogen, the higher the refractive index.

The density of the silicon oxynitride layer 13 is preferably 2.10 g/cm ³ or more. The greater the density of the silicon oxynitride layer 13, the higher the gas barrier property is. The silicon oxynitride layer 13 shows a tendency that the higher the ratio of nitrogen, the higher the density.

In order to obtain a gas barrier film with better gas barrier properties, the thickness of the silicon oxynitride layer 13 is preferably 5 nm or more, and more preferably 10 nm or more. In order to obtain a gas barrier film with better transparency, the thickness of the silicon oxynitride layer 13 is preferably 200 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less. In order to obtain a gas barrier film with better gas barrier properties and transparency, the thickness of the silicon oxynitride layer 13 is preferably from 5 nm to 200 nm, more preferably from 10 nm to 200 nm, and further preferably from 10 nm to 100 nm. nm or less.

The method of forming the silicon oxynitride layer 13 is not particularly limited, and may be a dry coating method or a wet coating method. Since it is easy to form a film with high film density and high gas barrier properties, dry processes such as sputtering, ion plating, vacuum evaporation, and chemical vapor deposition (CVD) are preferred. Since it is easy to form a film with low film stress and excellent bending resistance, the CVD method is preferred, and the plasma CVD method is more preferred.

When a flexible film is used as the transparent film base material 11 and a gas barrier layer (for example, a silicon oxynitride layer 13) is formed (film-formed) on the flexible film, the CVD layer is formed by performing CVD in a roll-to-roll manner. membrane can improve productivity. In a roll-to-roll CVD film forming device, the film forming roller forms one or both electrodes in a pair of counter electrodes. When the film moves on the film forming roller, a thin film is formed on the film. When two film-forming rollers form a pair of counter electrodes, a thin film is formed on each film-forming roller, so the film-forming speed can be doubled. Furthermore, the expression "on" when describing the film forming method using the CVD method has nothing to do with the direction within the CVD film forming device, and is synonymous with "connected to".

As a silicon supply source (silicon source) when forming the silicon oxynitride layer 13 by the CVD method, for example, hydrogenated silicon (more specifically, silane, ethylsilane, etc.) or silicon halide (more specifically, , dichlorosilane, etc.) and other Si-containing gases; hexamethyldisilazane, hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, tetramethylsilane, vinyl Trimethoxysilane, vinyltrimethylsilane, dimethyldimethoxysilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane , tetraethoxysilane, diethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysiloxane, monosilylamine, disilylamine, trisilylamine and other silicas compound. Among these, trisilylamine is preferred in that it can form a film with low toxicity, low boiling point, high transparency, and high density. Furthermore, if trisilylamine is used as the silicon source, the number of Si-Si bonds in the silicon oxynitride layer 13 tends to increase. Therefore, if trisilylamine is used as the silicon source, adjustment of S2/S1 becomes easy.

In order to form the silicon oxynitride layer 13, gases that are nitrogen sources and oxygen sources are usually introduced in addition to the silicon source. Examples of the nitrogen source include nitrogen, ammonia, and the like. Examples of the oxygen source include oxygen, carbon monoxide, carbon dioxide, and the like. From the viewpoint of reducing hydrogen or carbon incorporated into the film, the nitrogen source is preferably nitrogen (nitrogen gas), and the oxygen source is preferably oxygen (oxygen).

Generally speaking, for a silicon nitride film formed by a CVD method in which a nitrogen source is introduced together with trisilylamine as a silicon source, the amount of hydrogen in the film is relatively large, indicating that it is derived from hydrogenated silicon such as Si-H ₃ Infrared absorption peak near wave number 2140 cm ^-1 (range above 2120 cm ^-1 and below 2150 cm ^-1 ). In addition, generally speaking, for a silicon oxynitride film formed by a CVD method by introducing nitrogen and oxygen together with trisilylamine as a silicon source, the infrared absorption peak is shifted to the high wave number side and is above 2160 cm ^-1 The infrared absorption peak is shown in the range below 2280 cm ^-1 , showing better transparency than silicon nitride film. One of the reasons for the improvement in transparency is presumed to be that since the binding force between oxygen and silicon is strong, the introduction of oxygen can inhibit the incorporation of hydrogen into the film.

By changing the introduction amount (flow rate) of at least one of the nitrogen source and the oxygen source relative to the silicon source, the composition of the silicon oxynitride layer 13 can be appropriately adjusted. When nitrogen is used as the nitrogen source and oxygen is used as the oxygen source, from the viewpoint of both transparency and gas barrier properties, the amount of oxygen introduced relative to the amount of nitrogen introduced is preferably 0.01 in terms of volume ratio. More than 5 times and not more than 5 times, more preferably not less than 0.03 times and not more than 2 times, further preferably not less than 0.04 times and not more than 1.5 times, it can also be not less than 0.04 times and not more than 1.0 times, or not less than 0.04 times and not more than 0.5 times. When the amount of oxygen introduced is too small, the amount of oxygen introduced into the film tends to be small, and the light transmittance of the film tends to become smaller. When the amount of oxygen introduced is too large, the amount of nitrogen incorporated into the membrane tends to be less, resulting in insufficient gas barrier properties.

S2/S1 can be adjusted, for example, by changing at least one of the introduction amount of the nitrogen source (preferably nitrogen gas) relative to the silicon source and the type of the silicon source. In order to easily adjust S2/S1, the silicon source is preferably a silicon compound having two or more silicon atoms in one molecule and having a Si-N bond, and more preferably trisilylamine.

As the introduced gas when forming a film by the CVD method, gases other than a silicon source, a nitrogen source, and an oxygen source can also be used. For example, when using a liquid such as trisilylamine, a carrier gas may be used in order to vaporize the liquid and introduce it into a chamber (vacuum chamber). Alternatively, a nitrogen source or an oxygen source may be mixed with a carrier gas and then introduced into the vacuum chamber. In order to stabilize the plasma discharge, a discharge gas may also be used. Examples of carrier gas and discharge gas include rare gases such as helium, argon, neon, and xenon; or hydrogen. From the viewpoint of reducing the amount of hydrogen incorporated into the film and improving transparency, a rare gas is preferred.

Various conditions in the plasma CVD method only need to be set appropriately. The base material temperature (temperature of the surface of the film forming roller) is set within a range of -20°C or more and 500°C or less, for example. The base material temperature (film base material temperature) when forming a gas barrier layer (for example, silicon oxynitride layer 13) on the film base material is preferably 150°C or less from the viewpoint of the heat resistance of the film base material. , preferably below 100℃. The pressure of the film forming chamber (inside the vacuum chamber) is, for example, 0.001 Pa or more and 50 Pa or less. As a power source for generating plasma, for example, an alternating current power source is used. 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 between 0.1 kW and 10 kW.

The density of the silicon oxynitride layer 13 formed by the CVD method is, for example, 2.10 g/cm ³ or more and 2.50 g/cm ³ or less, or it can be 2.15 g/cm ³ or more, 2.45 g/cm ³ or less, or 2.20 g/cm ³ Above 2.40 g/ ^cm3 and below or above 2.25 g/ ^cm3 and below 2.35 g/ ^cm3 .

[Low refractive index layer 22] As long as the refractive index of the low refractive index layer 22 is lower than that of the silicon oxynitride layer 13, its material is not particularly limited and can be an organic layer or an inorganic layer. Examples of the inorganic material constituting the low refractive index layer 22 include silicon oxide, magnesium fluoride, and the like. The refractive index difference between the silicon oxynitride layer 13 and the low refractive index layer 22 is preferably above 0.10, and may be above 0.13 or above 0.15. The above-mentioned refractive index difference is generally 1.0 or less, and may be 0.5 or less, 0.4 or less, or 0.3 or less. The refractive index of the low refractive index layer 22 may be 1.30 or more and 1.55 or less, or may be 1.40 or more and 1.52 or less.

The low refractive index layer 22 is preferably a silicon oxide layer. The silicon oxide layer may also include a small amount of hydrogen, carbon, nitrogen and other elements incorporated into the raw material during self-film formation, the transparent film substrate 11 and the external environment. When the silicon oxide layer contains nitrogen, the nitrogen content is preferably less than the silicon oxynitride layer 13 . In the silicon oxide layer, the content rates of elements other than silicon and oxygen are each preferably 5 atomic % or less.

The method of forming the low refractive index layer 22 is not particularly limited, and may be a dry coating method or a wet coating method. When the silicon oxynitride layer 13 is formed by the CVD method, from the viewpoint of productivity, the low refractive index layer 22 is preferably formed by the CVD method.

As a silicon source and an oxygen source when forming a silicon oxide layer (specifically, the silicon oxide layer serving as the low refractive index layer 22 ) by the CVD method, those described above for the film formation of the silicon oxynitride layer 13 can be exemplified. By. As a silicon source, an organic silicon compound is preferred because it has low toxicity and can inhibit the incorporation of nitrogen into the film. It can inhibit the incorporation of impurities into the film and can form a film with high transparency and gas barrier properties. In terms of film, hexamethyldisiloxane is more preferred. When an organic silicon compound such as hexamethyldisiloxane is used as the silicon source, carbon may be incorporated into the film. However, as mentioned above, carbon may be included in the oxidized silicon layer as long as it is a small amount. From the viewpoint of reducing the amount of carbon in the film, the oxygen source is preferably oxygen.

It appears that the greater the introduction amount of the oxygen source relative to the silicon source, the lower the carbon content in the film and the higher the film density. When using hexamethyldisiloxane and oxygen to form an oxide silicon layer by the CVD method, the volume ratio of the introduction amount of oxygen to the introduction amount of hexamethyldisiloxane (gas) is preferably: More than 10 times, it can also be more than 15 times or more than 20 times. From the viewpoint of appropriately maintaining the film formation speed, the volume ratio of the introduction amount of oxygen to the introduction amount of hexamethyldisiloxane (gas) is preferably 200 times or less, and may also be 100 times or less or 50 times. times or less.

During the CVD film formation of the silicon oxide layer, carrier gas or discharge gas can also be introduced. Various conditions such as substrate temperature, pressure, power supply frequency, applied power, etc. are the same as those for the film formation of the silicon oxynitride layer 13 and can be adjusted appropriately.

From the viewpoint that the silicon oxide layer as the low refractive index layer 22 contributes to improving gas barrier properties, the density of the silicon oxide layer is preferably 1.80 g/cm ³ or more, more preferably 1.90 g/cm ³ or more. It can be 2.00 g/ ^cm3 or more and 2.40 g/ ^cm3 or less, 2.05 g/ ^cm3 or more and 2.35 g/ ^cm3 or less, or 2.10 g/cm3 ^or more and 2.30 g/ ^cm3 or less.

From the viewpoint of making the low refractive index layer 22 function appropriately as an optical interference layer, the thickness of the low refractive index layer 22 is preferably 3 nm or more and 250 nm or less, and may be 5 nm or more and 200 nm or less, or 10 nm or more. Below 150 nm. The thickness of the low refractive index layer 22 is preferably set in such a way that the light reflectivity of the gas barrier layer is reduced and the coloring of the reflected light is suppressed. The characteristics (spectrum) of reflected light can be accurately evaluated through optical model calculations. Known methods for obtaining the reflection spectrum of a multilayer optical film through optical calculations include repeatedly applying the thin film interference formula to the interface of each film, adding all the multiple reflection waves, and applying the boundary conditions of Maxwell's equations. Taking it into consideration, the method of calculating the reflection spectrum using the transfer matrix, etc.

The gas barrier layer may also include layers other than the silicon oxynitride layer 13 and the low refractive index layer 22 (other layers). Examples of "other layers" include inorganic thin films made of ceramic materials such as metal or semimetal oxides, nitrides, or oxynitrides. In terms of having both low moisture permeability and transparency, oxides, nitrides or oxynitrides of Si, Al, In, Sn, Zn, Ti, Nb, Ce or Zr are preferred.

From the viewpoint of achieving both high gas barrier properties and transparency, the total thickness of the gas barrier layer is preferably 30 nm or more and 1000 nm or less, and more preferably 40 nm or more and 500 nm or less.

[Hard Coat 31] The hard coat layer 31 includes, for example, a binder resin and nanoparticles. As the binder resin, curable resins such as thermosetting resin, photocurable resin, and electron beam curable resin can be preferably used. Examples of types of curable resin include polyester resin, acrylic resin, polyurethane resin, acrylic polyurethane resin, amide resin, silicone resin, silicate resin, and epoxy resin. Resin, melamine-based resin, oxetane-based resin, etc. One type or two or more types of curable resins may be used. Among these, in terms of having high hardness and being capable of photocuring, it is preferable to select at least one type from the group consisting of acrylic resin, acrylic polyurethane resin, and epoxy resin, and more preferably It is one or more selected from the group consisting of acrylic resin and acrylic polyurethane resin.

The number average primary particle diameter of the nanoparticles included in the hard coat layer 31 is preferably 15 nm or more, and more preferably 20 nm or more from the viewpoint of improving dispersibility in the binder resin. From the viewpoint of forming fine uneven shapes that contribute to improving adhesion, the number average primary particle diameter of the nanoparticles included in the hard coat layer 31 is preferably 90 nm or less, more preferably 70 nm or less, and further Preferably it is 50 nm or less.

The material of nanoparticles is preferably inorganic oxide. Examples of the inorganic oxide include metal (or semimetal) oxides such as silicon dioxide, titanium oxide, aluminum oxide, zirconium oxide, niobium oxide, zinc oxide, tin oxide, cerium oxide, and magnesium oxide. Inorganic oxides can also be composite oxides of multiple (semi-) metals. Among the exemplified inorganic oxides, silicon dioxide is preferred because of its high adhesion-improving effect. That is, the nanoparticles are preferably silica particles (silica nanoparticles). On the surface of the inorganic oxide particles as nanoparticles, functional groups such as acryl groups and epoxy groups can also be introduced in order to improve the adhesion or affinity with the resin.

The amount of nanoparticles in the hard coat layer 31 is 100 parts by weight relative to the total amount of the binder resin and nanoparticles, preferably 5 parts by weight or more, and may also be 10 parts by weight or more, 20 parts by weight or 30 parts by weight. parts by weight or more. If the amount of the nanoparticles is 5 parts by weight or more, the adhesion with 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 100 parts by weight relative to the total amount of the binder resin and nanoparticles, such as 90 parts by weight, preferably 80 parts by weight, and may also be 70 parts by weight.

The thickness of the hard coat layer 31 is not particularly limited, but in order to achieve higher hardness and improve adhesion with the gas barrier layer, it is preferably 0.5 μm or more, more preferably 1.0 μm or more, and further preferably 2.0 μm or more. Furthermore, it is more preferably 3.0 μm or more. On the other hand, in order to suppress a decrease in strength due to cohesive failure, the thickness of the hard coat layer 31 is preferably 20 μm or less, more preferably 15 μm or less, and further preferably 12 μm or less.

(Method for forming hard coat layer 31) The hard coat layer 31 is formed by applying the hard coat composition on the transparent film base material 11 and removing the solvent and hardening the resin if necessary. The hard coat composition contains, for example, the above-mentioned binder resin and nanoparticles, and optionally a solvent capable of dissolving or dispersing these components. When the resin component in the hard coat composition is a curable resin, it is preferable to include an appropriate polymerization initiator in the hard coat composition. For example, when the resin component in the hard coat composition is a photocurable resin, it is preferable to include a photopolymerization initiator in the hard coat composition.

In addition to the above ingredients, the hard coat composition may also contain particles (fine particles) with a number average primary particle diameter of 1.0 μm or more, a leveling agent, a viscosity adjuster (thixotropic agent, tackifier, etc.), an antistatic agent Agents, anti-caking agents, dispersants, dispersion stabilizers, antioxidants, UV absorbers, defoaming agents, surfactants, lubricants and other additives.

As the coating method of the hard coat composition, rod coating, roll coating, gravure coating, rod coating, slot coating, curtain coating, Any appropriate method such as spray coating method, notch wheel coating method, etc.

[Adhesive layer 51] As a constituent material of the adhesive layer 51, an adhesive with a high visible light transmittance can preferably be used. As the adhesive constituting the adhesive layer 51, for example, acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyvinyl ether, vinyl acetate-vinyl chloride copolymer can be appropriately selected and used. , modified polyolefin, epoxy resin, fluorine resin, natural rubber, synthetic rubber and other polymers are transparent adhesives based on polymers. The thickness of the adhesive layer 51 is preferably not less than 5 μm and not more than 100 μm. The refractive index of the adhesive layer 51 is, for example, 1.4 or more and 1.5 or less.

[Characteristics of the gas barrier film] 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, and still more preferably It is 1.0×10 ^-2 g/m ² ·day or less. From the viewpoint of suppressing the deterioration of objects to be protected such as organic EL elements, the smaller 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, but is generally 1.0×10 ^-5 g/m ² ·day. Water vapor transmission rate (WVTR) is measured under the conditions of a temperature of 40°C and a relative humidity of 90%, according to the differential pressure method (Pressure Sensor Method) described in ISO 15106-5.

The light transmittance of the gas barrier film is preferably above 75%, more preferably above 80%. The light transmittance refers to the Y value of the CIE tristimulus value specified in JIS Z8781-3:2016.

The extraction amount of ammonium ions per 1 cm ² of the gas barrier film is preferably less than 0.30 μg. In addition, the method for measuring the extracted amount of ammonium ions is the same method as the Example described below or a method based on it.

<Second Embodiment: Manufacturing Method of Gas Barrier Film> Next, a method of manufacturing a gas barrier film according to the second embodiment of the present invention will be described. The manufacturing method of the gas barrier film of the second embodiment is a preferable manufacturing method of the gas barrier film of the above-mentioned first embodiment. Therefore, descriptions of components that are overlapping with those of the first embodiment may be omitted. The manufacturing method of the gas barrier film according to the second embodiment includes introducing trisilylamine, a nitrogen source (for example, nitrogen gas, etc.), and an oxygen source (for example, oxygen gas, etc.) into a chamber (vacuum chamber) of a film forming device, The step of forming a silicon oxynitride layer by CVD method.

In the second embodiment, for example, it can be easily formed by using a CVD film forming apparatus (not shown) and adopting various conditions in the plasma CVD method illustrated in the description of the gas barrier film of the first embodiment. The gas barrier film of the first embodiment is produced. For example, when the gas barrier film of the first embodiment is manufactured using a CVD film forming apparatus (not shown) using a pair of film forming rollers to form a pair of counter electrodes, the film forming gas (more specifically, the film forming gas (more specifically, That is, trisilylamine, oxygen source, nitrogen source, etc.) are supplied into the vacuum chamber, while causing plasma discharge between a pair of film-forming rollers, and using the plasma to decompose the above-mentioned film-forming gas, so as to form a transparent film base, for example A silicon oxynitride layer 13 is formed on the material 11. The values of x, y and x/y can be adjusted, for example, by changing the introduction amount of at least one of the nitrogen source and the oxygen source relative to trisilylamine. Moreover, S2/S1 can be adjusted, for example, by changing the introduction amount of a nitrogen source (preferably nitrogen gas) with respect to trisilylamine.

<Third Embodiment: Polarizing Plate with a Gas Barrier Layer> Next, a polarizing plate with a gas barrier layer according to the third embodiment of the present invention will be described. A polarizing plate with a gas barrier layer according to a third embodiment includes the gas barrier film according to the first embodiment and a polarizing element. 7 is a cross-sectional view showing an example of the polarizing plate with a gas barrier layer according to the third embodiment. The polarizing plate 100 with a gas barrier layer shown in FIG. 7 has the above-mentioned gas barrier film 50 and the polarizing plate 101. In the polarizing plate 100 with a gas barrier layer, the polarizing plate 101 is disposed on the main surface 51 a of the adhesive layer 51 opposite to the silicon oxynitride layer 13 side. That is, the polarizing plate 101 and the silicon oxynitride layer 13 are bonded together via the adhesive layer 51 . Furthermore, the polarizing plate with a gas barrier layer 100 shown in FIG. 7 has a gas barrier film 50 (gas barrier film 40 ), but the gas barrier film of the polarizing plate with a gas barrier layer of the third embodiment is not limited. The gas barrier film 50 may be, for example, the gas barrier film 10 , the gas barrier film 20 or the gas barrier film 30 .

The polarizing plate 101 includes a polarizing element (not shown). Generally speaking, a transparent protective film (not shown) serving as a polarizing element protective film is layered on both main areas of the polarizing element. It is also not necessary to provide a transparent protective film on one or both main surfaces of the polarizing element. As a polarizing element, for example, a hydrophilic polymer film such as a polyvinyl alcohol-based film is adsorbed with a dichroic substance such as iodine or a dichroic dye and uniaxially stretched.

As the transparent protective film, a transparent resin film composed of a cellulose-based resin, a cyclic polyolefin-based resin, an acrylic resin, a phenylmaleimide-based resin, a polycarbonate-based resin, or the like can be preferably used. A gas barrier film can also be used for the transparent protective film.

The polarizing plate 101 may also have an optically functional film laminated on one or both main surfaces of the polarizing element via an appropriate adhesive layer or adhesive layer as needed. Examples of the optical functional film include a phase difference plate, a viewing angle expansion film, a viewing angle limiting (peep prevention) film, a brightness improvement film, and the like.

The polarizing plate with a gas barrier layer according to the third embodiment includes the gas barrier film according to the first embodiment, thereby suppressing the generation of ammonia, ensuring gas barrier properties even when exposed to a high temperature and high humidity environment, and having excellent transparency.

<4th Embodiment: Image display device> Next, an image display device according to a fourth embodiment of the present invention will be described. An image display device according to a fourth embodiment includes the gas barrier film of the first embodiment or the polarizing plate with a gas barrier layer according to the third embodiment, and an image display unit.

FIG. 8 is a cross-sectional view showing an example of the image display device according to the fourth embodiment. The 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 unit 202. The image display unit 202 includes a substrate 203 and a display element 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 through the adhesive layer 201 . Furthermore, the image display device 200 shown in FIG. 8 has the gas barrier film 50 (the gas barrier film 40 ), but the gas barrier film included in the image display device of the fourth 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.

Examples of the adhesive constituting the adhesive layer 201 include the same adhesives as those exemplified above as the adhesive constituting the adhesive layer 51 . The adhesive constituting the adhesive layer 201 and the adhesive constituting the adhesive layer 51 may be of the same type, or may be of different types.

The preferred range of the thickness of the adhesive layer 201 is, for example, the same as the preferred range of the thickness of the adhesive layer 51 mentioned above. The thickness of the adhesive layer 201 and the thickness of the adhesive layer 51 may be the same or different.

The substrate 203 may use a glass substrate or a plastic substrate. When the image display unit 202 is a top-emitting type, the substrate 203 does not need to be transparent, and a highly heat-resistant film such as a polyimide film can also be used as the substrate 203 .

Examples of the display element 204 include organic EL elements, liquid crystal elements, electrophoretic display elements (electronic paper), and the like. A touch panel sensor (not shown) may also be disposed on the viewing side of the image display unit 202 .

When the display element 204 is an organic EL element, the image display unit 202 is, for example, a top-emission type. For example, the organic EL element includes a metal electrode (not shown), an organic light-emitting layer (not shown), and a transparent electrode (not shown) in order from the substrate 203 side.

The organic light-emitting layer may also have an electron transport layer, a hole transport layer, etc., in addition to the organic layer itself functioning as a light-emitting layer. The transparent electrode is a metal oxide layer or metal film that allows light from the organic light-emitting layer to pass through. On the back side of the substrate 203, in order to protect or reinforce the substrate 203, a bottom sheet (not shown) may also be provided.

The metal electrode of the organic EL element is light reflective. Therefore, when external light is incident into the interior of the image display unit 202, the light is reflected by the metal electrode, and the reflected light is seen from the outside like a mirror. By arranging a circular polarizing plate as the polarizing plate 101 on the viewing side of the image display unit 202, the reflected light at the metal electrode can be prevented from being emitted to the outside again, thereby improving the visibility and design of the image display device 200.

For example, the circularly polarizing plate has a retardation film on the main surface of the polarizing element on the image display unit 202 side. The transparent protective film disposed adjacent to the polarizing element may also be a retardation film. In addition, the transparent film base 11 of the gas barrier film 50 may be a retardation film. When the retardation film has a phase retardation of λ/4, and the angle between the slow axis direction of the retardation film and the absorption axis direction of the polarizing element is 45°, a laminate of the polarizing element and the retardation film is used. It functions as a circular polarizing plate that suppresses re-emission of reflected light from metal electrodes. The retardation film constituting the circularly polarizing plate may be a lamination of two or more films. For example, by laminating a polarizing element, a λ/2 plate, and a λ/4 plate so that their optical axes form a specific angle, it is possible to obtain broadband circularly polarized light that functions as a circularly polarizing plate in a broad band of visible light. plate.

The image display unit 202 may also be a bottom-emitting type in which a transparent electrode, an organic light-emitting layer and a metal electrode are sequentially stacked on a substrate. In the bottom-emission type image display unit 202, a transparent substrate is used, and the transparent substrate is arranged on the viewing side. A gas barrier film can also be used for the transparent substrate.

The image display device according to the fourth embodiment includes the gas barrier film according to the first embodiment, and therefore can suppress deterioration of the display element caused by gas (for example, water vapor). [Example]

Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples.

<Preparation of Gas Barrier Film> The following describes the production methods of the gas barrier films of Examples 1 to 3 and Comparative Examples 1 to 7 respectively. Furthermore, when producing the gas barrier films of Examples 1 to 3 and Comparative Examples 1 to 5 and 7, roll-to-roll CVD was used in the film formation of the gas barrier layer (silicon oxynitride layer or silicon oxide layer). Film forming device. Furthermore, when producing the gas barrier film of Comparative Example 6, a roll-to-roll sputtering film forming device was used to form the silicon oxynitride layer.

[Example 1] A cyclic polyolefin film with a thickness of 40 μm ("ZEONOR (registered trademark) film ZF-14" manufactured by Japan Zeon Corporation) as a transparent film base material was placed in a film forming device, and placed in a vacuum chamber Reduce the pressure to 1×10 ^-3 Pa. Then, while the film was moving, a silicon oxynitride layer (gas barrier layer) with a thickness of 60 nm was formed by CVD at a substrate temperature of 12° C. to obtain the gas barrier film of Example 1. In the CVD film formation when obtaining the gas barrier film of Example 1, the frequency of the plasma generation power supply was set to 80 kHz, and plasma was generated by discharging under the conditions of applying power of 1.0 kW. Trisilylamine (TSA) was used. ) (flow condition: 30 sccm), nitrogen (flow condition: 575 sccm) and oxygen (flow condition: 25 sccm) are used as film-forming gases, and the above-mentioned film-forming gases are introduced into the film-forming roller room (between electrodes) in the vacuum chamber , film formation was carried out under a pressure of 1.0 Pa. Furthermore, TSA is heated and vaporized, and introduced into the vacuum chamber.

[Example 2] The gas barrier film of Example 2 was produced in the same manner as in Example 1, except that the flow rate condition of nitrogen was set to 550 sccm and the flow rate condition of oxygen was set to 50 sccm.

[Example 3] The gas barrier film of Example 3 was produced in the same manner as in Example 1, except that the flow rate condition of nitrogen was set to 525 sccm and the flow rate condition of oxygen was set to 75 sccm.

[Comparative Example 1] The gas barrier film of Comparative Example 1 was produced in the same manner as Example 1, except that the flow rate of nitrogen was set to 600 sccm and oxygen was not introduced.

[Comparative Example 2] The gas barrier film of Comparative Example 2 was produced in the same manner as in Example 1, except that the flow rate condition of nitrogen was set to 300 sccm and the flow rate condition of oxygen was set to 300 sccm.

[Comparative Example 3] The gas barrier film of Comparative Example 3 was produced in the same manner as Example 1, except that the flow rate of oxygen was set to 600 sccm and nitrogen was not introduced.

[Comparative Example 4] Except for the changes shown below, the gas barrier film of Comparative Example 4 was produced in the same manner as in Example 1.

(Change point) In Comparative Example 4, hexamethyldisiloxane (HMDSO) (flow condition: 20 sccm), nitrogen (flow condition: 300 sccm), and oxygen (flow condition: 400 sccm) were used as film-forming gases , CVD forms a silicon oxynitride layer (gas barrier layer) with a thickness of 150 nm. Furthermore, HMDSO is heated and vaporized, and introduced into the vacuum chamber.

[Comparative Example 5] Except for the changes shown below, the gas barrier film of Comparative Example 5 was produced in the same manner as in Example 1.

(Change point) In Comparative Example 5, HMDSO (flow condition: 25 sccm) and oxygen (flow condition: 700 sccm) were used as film-forming gases, and a silicon oxide layer (gas barrier layer) with a thickness of 180 nm was formed by CVD. Furthermore, HMDSO is heated and vaporized, and introduced into the vacuum chamber.

[Comparative Example 6] A cyclic polyolefin film with a thickness of 40 μm ("ZEONOR (registered trademark) film ZF-14" manufactured by Japan Zeon Co., Ltd.) as a transparent film base was placed in a film forming device, and the vacuum chamber was Reduce the pressure to 1×10 ^-4 Pa. Then, while the film is moving, the substrate temperature is set to -8°C, and a silicon nitride oxide layer (gas barrier layer) with a thickness of 220 nm is sputtered by DC (Direct Current, DC) magnetron sputtering. The gas barrier film of Comparative Example 6 was obtained. In the sputtering film formation when obtaining the gas barrier film of Comparative Example 6, a pure Si target was used as the target, and Ar/O ₂ /N ₂ was introduced as the sputtering gas at a volume ratio of 23.5/1.0/23.5. Sputtering was performed under the conditions of 2.23 W/cm ² and pressure 0.15 Pa.

[Comparative Example 7] The gas barrier film of Comparative Example 7 was produced in the same manner as in Example 1, except that the flow rate condition of nitrogen was set to 400 sccm and the flow rate condition of oxygen was set to 200 sccm.

<Composition analysis of the gas barrier layer> Using an X-ray photoelectron spectrometer equipped with an Ar ion gun ("Quantera SXM" manufactured by ULVAC-PHI), one side of the self-barrier gas layer (silicon oxynitride layer or silicon oxide layer) and a transparent The gas barrier layer was etched under the following conditions on the main surface opposite to the film substrate side, and the composition of the gas barrier layer in the thickness direction was analyzed by XPS on one side. Then, the content ratio of each element (Si, O, N, and C) in the center part of the thickness direction of the gas barrier layer (when 1/2 of the total etching time has passed) is calculated, and the general formula SiO representing the composition of the gas barrier layer is obtained. _x N The value of x and y in _y . Furthermore, the "total etching time" refers to the time from the beginning to the end of etching of the gas barrier layer. When calculating the content rate of each element, the peak corresponding to the binding energy of 2p of Si, 1s of O, 1s of N, and 1s of C obtained from the wide scan spectrum is used. Detailed measurement conditions are shown below. Furthermore, in the gas barrier layers of Examples 1 to 3, the content of C with respect to 100 atomic % in total of Si, O, N, and C was all 0 atomic %.

[Measurement conditions] X-ray source: Monochromatic AlKα X-ray focus size: 100 μm (15 kV, 25 W) Photoelectron extraction angle: 45° relative to the sample surface Correction of binding energy: Correction of the peak originating from the CC bond to 285.0 eV (only the most surface) Charged neutralization conditions: Electron neutralization gun and Combination of Ar ion gun (neutralization mode) Ar ion gun acceleration voltage: 1 kV Ar ion gun grating size: 1 mm × 1 mm Ar ion gun etching speed: 5 nm/min (SiO ₂ conversion)

<Measurement of S2/S1 of the gas barrier layer> Analyze by XPS under the same conditions as the above <Composition analysis of the gas barrier layer>, and obtain the central part of the gas barrier layer in the thickness direction (1/1 of the total etching time) 2 o'clock) Si2p spectrum. For the obtained Si2p spectrum, waveform analysis software ("PHI MultiPak" manufactured by ULVAC-PHI Co., Ltd.) was used to perform waveform analysis to obtain S2/S1 of the gas barrier layer. Specifically, by using the above-mentioned waveform analysis software, the background of the Si2p spectrum is removed using the Shirley method, and the spectrum is processed using the Gauss-Lorentz function, and the peak originating from the Si-Si bond is isolated from the spectrum ( There is a peak with a maximum value in the range of binding energy above 99 eV and below 101 eV). Then, using the above-mentioned waveform analysis software, the area S1 (the area between the Si2p spectrum curve and the baseline in the range of binding energy 95 eV to 110 eV and below) and the area S2 (the separated Si-Si bond derived from Peak area), calculate their equal area ratio (S2/S1).

<Measurement of infrared spectroscopy of the gas barrier layer> Using FT-IR (Fourier Transform Infrared Radiation, Fourier Transform Infrared Spectroscopy) device ("Frontier" manufactured by PerkinElmer), the wave of the gas barrier layer was measured by the reflection method (ATR method) Take the infrared absorption spectrum in the range from 2160 cm ^-1 to 2280 cm ^-1 to confirm the wave number of the absorption peak.

<Evaluation method of gas barrier film> [Light transmittance] Use a spectrophotometer ("U4100" manufactured by Hitachi High-Tech Science Co., Ltd.) to measure the light transmittance (Y value) of the gas barrier film. When the light transmittance is 75% or more, it is evaluated as "excellent transparency". On the other hand, when the light transmittance is less than 75%, it is evaluated as "poor transparency".

[Water vapor transmission rate] According to the differential pressure method (Pressure Sensor Method) recorded in ISO 15106-5, use the water vapor transmission rate measuring device "Deltaperm (registered trademark)" manufactured by Technolox Company at a temperature of 40°C and a relative humidity of 90 Under the condition of %, measure the water vapor transmission rate (WVTR) of the gas barrier film. Hereinafter, the WVTR obtained here is recorded as "initial WVTR". In addition, the initial WVTR of Comparative Examples 4 to 6 is a value normalized based on a gas barrier layer with a thickness of 60 nm. For example, the initial WVTR of Comparative Example 4 is a value calculated using the measured value obtained by the above-mentioned measurement method × 150/60.

Using a gas barrier film (sample) prepared separately from the gas barrier film for which the initial WVTR was measured, the WVTR after exposure to a high temperature and high humidity environment was measured. Specifically, first, the above-mentioned sample was put into an oven set at a temperature of 85° C. and a relative humidity of 85% for 240 hours. Then, the sample was taken out of the oven, and the WVTR of the sample after being exposed to a high temperature and high humidity environment was measured using the same method as the initial WVTR measurement method described above. Hereinafter, the WVTR obtained here is referred to as "high temperature and high humidity WVTR". In addition, the high-temperature and high-humidity WVTR of Comparative Examples 4 to 6 is a value standardized based on a gas barrier layer with a thickness of 60 nm. For example, the high-temperature and high-humidity WVTR of Comparative Example 4 is a value calculated using the measured value obtained by the above-mentioned measurement method × 150/60. When the high-temperature and high-humidity WVTR is 0.10 g/m ² ·day or less, the evaluation is that "gas barrier properties can be ensured even when exposed to high-temperature and high-humidity environments." On the other hand, when the high-temperature and high-humidity WVTR exceeds 0.10 g/m ² ·day, it is evaluated that "gas barrier properties cannot be ensured after being exposed to a high-temperature and high-humidity environment."

[Extracted amount of ammonium ions] First, cut the gas barrier film into a size of 60 mm × 60 mm to obtain a sample for measurement. Next, the obtained sample was placed in a polypropylene container, and 100 mL of ultrapure water was added to the container. Then, the container with the sample and ultrapure water added was put into a dryer with a temperature set to 120°C for 1 hour, and then the liquid (extract liquid) in the container was filtered using a membrane filter with a pore size of 0.2 μm. Then, the amount of ammonium ions (extraction amount) in the obtained filtrate was quantified using ion chromatography (IC method) under the following conditions. For quantification, a commercially available ammonium ion standard solution (manufactured by Kanto Chemical Co., Ltd.) was used. When the extraction amount of ammonium ions per 1 cm ² of the sample is 0.30 μg or less, it is evaluated as "capable of inhibiting the generation of ammonia." On the other hand, when the extracted amount of ammonium ions per 1 cm ² of the sample exceeds 0.30 μg, it is evaluated as "unable to suppress the generation of ammonia."

(Measurement conditions of IC method) Analytical device: "Dionex (registered trademark) ICS-6000" manufactured by Thermo Fisher Scientific Separation column: "Dionex (registered trademark) IonPac CS16 (3 mm × 250 mm)" manufactured by Thermo Fisher Scientific Guard column: "Dionex (registered trademark) IonPac CG16 (3 mm × 50 mm)" manufactured by Thermo Fisher Scientific Suppressor: "Dionex (registered trademark) CDRS 600 (external mode)" manufactured by Thermo Fisher Scientific Detector: Conductivity detector Eluent: methanesulfonic acid aqueous solution (concentration of methanesulfonic acid: 25 mmоl/L) Eluate flow: 0.36 mL/min Injection volume of sample (filtrate): 5 μL

<Analysis results and evaluation results> Regarding Examples 1 to 3 and Comparative Examples 1 to 7, the value of x, the value of y, the value of x/y, S2/S1, and the wave number of 2160 cm in SiO _x N _y The wave numbers of the absorption peaks of the infrared absorption spectrum in the range from ^-1 to 2280 cm ^-1 are shown in Table 1. In addition, regarding Examples 1 to 3 and Comparative Examples 1 to 7, Table 2 shows the light transmittance, initial WVTR, high temperature and high humidity WVTR, and the amount of ammonium ions extracted per 1 cm ² of the sample.

Furthermore, the "wave number of the absorption peak" in Table 1 refers to the wave number of the absorption peak of the infrared absorption spectrum in the range of wave number 2160 cm ^-1 to 2280 cm ^-1 . In the "Wavenumber of Absorption Peak" column in Table 1, "-" means that there is no absorption peak in the range of wavenumbers above 2160 cm ^-1 and below 2280 cm ^-1 . In addition, the "NH ₄ ⁺ extraction amount" in Table 2 refers to the amount of ammonium ions extracted per 1 cm ² of the sample. In the column of "NH ₄ ⁺ extraction amount" in Table 2, "-" refers to the extraction amount of ammonium ions that was not measured.

[Table 1] The values of x and y and the value of x/y in SiO _x N _y S2/S1 Wave number of absorption peak [cm ^-1 ] x y x/y Example 1 0.41 0.74 0.55 0.27 2170 Example 2 0.72 0.66 1.09 0.18 2190 Example 3 0.97 0.58 1.67 0.08 2200 Comparative example 1 0.05 0.77 0.06 0.40 2140 Comparative example 2 1.70 0.22 7.73 0.00 2240 Comparative example 3 1.99 0.03 66.33 0.00 - Comparative example 4 1.99 0.09 22.11 0.00 - Comparative example 5 1.93 0.00 - 0.00 - Comparative example 6 1.07 0.63 1.70 0.00 - Comparative example 7 1.63 0.30 5.43 0.04 2240

[Table 2] Transmittance[%] Initial WVTR [g/m ² ･day] High temperature and high humidity WVTR [g/m ² ･day] NH ₄ ⁺ extraction amount [μg] Example 1 80 0.0071 0.02 0.12 Example 2 85 0.01 0.02 0.14 Example 3 87 0.0083 0.04 0.20 Comparative example 1 70 0.01 0.01 0.80 Comparative example 2 91 0.01 0.83 0.81 Comparative example 3 92 0.30 0.48 0.10 Comparative example 4 91 0.03 3.85 - Comparative example 5 91 0.15 0.69 - Comparative example 6 87 0.01 0.11 0.00 Comparative example 7 90 0.01 0.35 -

As shown in Table 1, in Examples 1 to 3, x and y satisfy the relationships of 0.30<x<1.20, 0.40<y<0.80, and 0.50<x/y<2.30. In Examples 1 to 3, S2/S1 is 0.05 or more and 0.30 or less.

As shown in Table 2, in Examples 1 to 3, the light transmittance was 75% or more. Therefore, the gas barrier films of Examples 1 to 3 have excellent transparency. In Examples 1 to 3, the high temperature and high humidity WVTR is 0.10 g/m ² ·day or less. Therefore, the gas barrier films of Examples 1 to 3 can ensure gas barrier properties even when exposed to high temperature and high humidity environments. In Examples 1 to 3, the amount of ammonium ions extracted per 1 cm ² of the sample was 0.30 μg or less. Therefore, the gas barrier films of Examples 1 to 3 can inhibit the generation of ammonia.

As shown in Table 1, in Comparative Example 1, x is 0.30 or less. In Comparative Examples 2 to 5 and 7, x is 1.20 or more. In Comparative Examples 2 to 5 and 7, y is 0.40 or less. In Comparative Example 1, x/y is 0.50 or less. In Comparative Examples 2 to 4 and 7, x/y is 2.30 or more. In Comparative Example 1, S2/S1 exceeded 0.30. In Comparative Examples 2 to 7, S2/S1 did not reach 0.05.

As shown in Table 2, in Comparative Example 1, the light transmittance did not reach 75%. Therefore, the gas barrier film of Comparative Example 1 had poor transparency. In Comparative Examples 2 to 7, the high temperature and high humidity WVTR exceeded 0.10 g/m ² ·day. Therefore, the gas barrier films of Comparative Examples 2 to 7 cannot ensure gas barrier properties after being exposed to high temperature and high humidity environments. In Comparative Examples 1 and 2, the extracted amount of ammonium ions per 1 cm ² of the sample exceeded 0.30 μg. Therefore, the gas barrier films of Comparative Examples 1 and 2 were unable to inhibit the generation of ammonia.

The above results show that according to the present invention, it is possible to provide a gas barrier film that suppresses the generation of ammonia, ensures gas barrier properties even when exposed to a high temperature and high humidity environment, and has excellent transparency.

10: Gas barrier film 11: Transparent film substrate 11a: Main surface 11b: Main surface 12: Gas barrier layer 13: Silicon oxynitride layer 13a: Main surface 20: Gas barrier film 21: Gas barrier layer 22: Low refractive index layer 30: Gas barrier film 31: Hard coating 40: Gas barrier film 41: Gas barrier layer 50: Gas barrier film 51: Adhesive layer 51a: Main surface 100: Polarizing plate with gas barrier layer 101: Polarizing plate 200: Figure Image display device 201: Adhesive layer 202: Image display unit 203: Substrate 204: Display element BL: Baseline P1: Curve SP: Si2p spectrum curve

FIG. 1 is a cross-sectional view showing an example of the gas barrier film of the present invention. 2 is a diagram showing an example of the results obtained by analyzing the silicon oxynitride layer of the gas barrier film of the present invention by X-ray photoelectron spectroscopy. Figure 3 is a cross-sectional view showing another example of the gas barrier film of the present invention. Figure 4 is a cross-sectional view showing another example of the gas barrier film of the present invention. Figure 5 is a cross-sectional view showing another example of the gas barrier film of the present invention. 6 is a cross-sectional view showing another example of the gas barrier film of the present invention. 7 is a cross-sectional view showing an example of the polarizing plate with a gas barrier layer of the present invention. 8 is a cross-sectional view showing an example of the image display device of the present invention.

10:Gas barrier film

11:Transparent film substrate

11a: Main side

12:Gas barrier layer

13:Silicone oxynitride layer

Claims (11)

A gas barrier film having a transparent film base material and a gas barrier layer directly or indirectly disposed on at least one main surface of the transparent film base material, and the gas barrier layer has a gas barrier layer containing oxygen, nitrogen and silicon as constituent elements. Silicon oxynitride layer, _the composition of silicon oxynitride contained in the silicon oxynitride layer is represented by the general formula SiO _{x N y ,} x and y in the above general formula SiO < 0.80 and 0.50 < When the area of the region between the baselines is set to S1 and the area of the peak derived from the Si-Si bond separated from the Si2p spectrum by waveform analysis is set to S2, the relationship of 0.05≦S2/S1≦0.30 is satisfied. Such as the gas barrier film of claim 1, wherein the above-mentioned S2/S1 is 0.15 or more and 0.30 or less. For example, the gas barrier film of claim 1 or 2, wherein the above x/y is 2.00 or less. The gas barrier film of claim 1 or 2, wherein the thickness of the silicon oxynitride layer is 10 nm or more and 200 nm or less. The gas barrier film according to claim 1 or 2, further having a hard coat layer disposed between the transparent film base material and the gas barrier layer. The gas barrier film of claim 1 or 2 further has an adhesive layer disposed on the side of the gas barrier layer opposite to the side of the transparent film substrate. A method for manufacturing a gas barrier film, which is the method for manufacturing a gas barrier film as claimed in claim 1 or 2, and includes introducing trisilylamine, a nitrogen source and an oxygen source into the chamber of a film forming device, and using chemical gases to The step of forming the above-mentioned silicon nitride oxide layer by phase growth method. A polarizing plate with a gas barrier layer, which is provided with the gas barrier film of claim 1 and a polarizing element. An image display device provided with the gas barrier film according to claim 1 and an image display unit. An image display device provided with a polarizing plate with a gas barrier layer according to claim 8, and an image display unit. The image display device according to claim 9 or 10, wherein the image display unit includes an organic EL element.