gas barrier film

Abstract

This invention provides a gas barrier film with high substrate adhesion and high ultraviolet (UV) barrier properties, which also suppresses the decrease in substrate adhesion even when exposed to UV light in a high-temperature and high-humidity environment. The gas barrier film comprises a substrate, an intermediate layer, and a gas barrier layer stacked sequentially. The gas barrier film has a first surface and a second surface opposite to the first surface. The first surface is the exposed surface of the gas barrier layer. Furthermore, the gas barrier film satisfies the following conditions (i) and (ii): (i) in a micro-scratch test on the first surface, the critical load value at the peel point is 65 mN or more; (ii) the light transmittance at a wavelength of 380 nm is less than 8.0%.

Description

Technical Field

[0001] This invention relates to gas barrier membranes. Background Technology

[0002] For the purpose of reducing the degradation of functional components constituting electronic devices due to ultraviolet radiation, it has been proposed to use a resin film with ultraviolet blocking properties as the substrate of a gas barrier film (see, for example, Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2015 / 152075 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] With the increasing popularity of gas barrier films, for example, their application in outdoor devices such as flexible solar cells and electronic paper, there is a demand for gas barrier films with higher UV blocking properties.

[0008] However, according to the inventors' research, it is clear that there is still room for improvement in the conventional gas barrier film in terms of maintaining substrate adhesion even when it has high gas barrier properties, high UV barrier properties, and is exposed to strong UV radiation for a long time in a high-temperature environment.

[0009] In view of the above problems, the objective of the present invention is to provide a gas barrier film that has high substrate adhesion and high ultraviolet barrier properties, and can suppress the reduction of substrate adhesion even when exposed to ultraviolet light in a high temperature and high humidity environment.

[0010] Problem Solving Methods

[0011] In order to solve the above problems, the inventors conducted repeated in-depth research and found that by setting the critical load value of the peeling point above a given value and the light transmittance at a wavelength of 380nm below a given value in the micro-scratch test of the gas barrier film, the above problems can be solved, and the present invention is completed.

[0012] That is, the present invention provides the following [1] to

[10] .

[0013] [1] A gas barrier film comprising a substrate, an intermediate layer and a gas barrier layer stacked sequentially, the gas barrier film having a first surface and a second surface opposite to the first surface, the first surface being the exposed surface side of the gas barrier layer, and the gas barrier film satisfying the following conditions (i) and (ii):

[0014] (i) In the micro-scratch test on the first surface, the critical load value at the peeling point is 65 mN or more;

[0015] (ii) The light transmittance at a wavelength of 380 nm is less than 8.0%.

[0016] [2] According to the gas barrier membrane described in [1] above, wherein,

[0017] The intermediate layer contains a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2).

[0018] The critical load value when the intermediate layer contains only the first ultraviolet absorber (B1) as an ultraviolet absorber is greater than the critical load value when the intermediate layer contains only the second ultraviolet absorber (B2) as an ultraviolet absorber.

[0019] [3] According to the gas barrier membrane described in [1] or [2] above, wherein,

[0020] The intermediate layer contains a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2), wherein the first ultraviolet absorber (B1) is a triazine ultraviolet absorber and the second ultraviolet absorber (B2) is a benzotriazole ultraviolet absorber.

[0021] [3-1] According to the gas barrier membrane described in [2] or [3] above, wherein,

[0022] The ratio of the mass MB1 of the first ultraviolet absorber (B1) to the mass MB2 of the second ultraviolet absorber (B2) in the intermediate layer is 1 / 0.1 to 1 / 10.

[0023] [4] The gas barrier membrane according to any one of [1] to [3-1], wherein,

[0024] The substrate is an ultraviolet-absorbing substrate.

[0025] [5] The gas barrier membrane according to any one of [1] to [4] above, wherein,

[0026] The thickness of the intermediate layer is 0.5~20μm.

[0027] [6] The gas barrier membrane according to any one of [1] to [5], wherein,

[0028] The water vapor transmission rate is less than 1.0 × 10⁻⁶ at 40℃ and 90% relative humidity. -3 g / (m 2 ·day).

[0029] [7] The gas barrier membrane according to any one of [1] to [6] above, wherein,

[0030] The haze value is below 10%.

[0031] [8] The gas barrier membrane according to any one of [1] to [7] above, wherein,

[0032] The total light transmittance is over 80%.

[0033] [9] The gas barrier membrane according to any one of [1] to [8] above, wherein,

[0034] L * a * b * L color system * A value of 93 or higher, a * Values ​​below 0.3, b * The value is below 1.

[0035]

[10] A gas barrier membrane comprising a substrate, an intermediate layer and a gas barrier layer stacked sequentially,

[0036] Weather resistance tests were conducted under the following conditions (1) to (4): 100 square cuts of 1 mm each were formed in the gas barrier layer. After adhesive tape was pressed onto the cuts, the ends of the adhesive tape were kept at right angles to the gas barrier layer and peeled off. The ratio of the number of unpeeled squares to the total number of squares in the cuts was more than 50%, and the light transmittance at a wavelength of 380 nm was less than 8.0%.

[0037] The conditions (1) to (4) are:

[0038] (1) In an environment with a temperature of 60℃ and a relative humidity of 70%RH, with an illuminance of 100mW / cm 2 Expose the patient to ultraviolet light for 5 hours.

[0039] (2) Let stand at 70℃ for 5 hours;

[0040] (3) Let it stand for 5 hours at a temperature of 70℃ and a relative humidity of 90%RH;

[0041] (4) Take (1) to (3) as one loop and execute a total of 8 loops.

[0042] The effects of the invention

[0043] According to the present invention, a gas barrier film can be provided that has high substrate adhesion, high ultraviolet barrier properties, high gas barrier properties and high transparency, and can suppress the reduction of substrate adhesion even when exposed to ultraviolet light in a high temperature and high humidity environment. Attached Figure Description

[0044] Figure 1 This is a cross-sectional view showing an example of a gas barrier membrane.

[0045] Symbol Explanation

[0046] 10: Substrate

[0047] 20: Intermediate layer

[0048] 30: Gas barrier layer

[0049] 100: Gas barrier membrane Detailed Implementation

[0050] In this specification, the preferred limitations can be arbitrarily selected, and the combination of preferred limitations can be considered to be more preferred.

[0051] In this specification, “XX~YY” means “XX and above and YY and below”.

[0052] In this specification, for preferred numerical ranges (e.g., ranges of content), the lower and upper limits recorded in stages can be combined independently. For example, based on the description "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit (10)" and the "more preferably upper limit (60)" can be combined and set to "10 to 60".

[0053] In this specification, for example, "(meth)acrylate" means both "acrylate" and "methacrylate", and other similar terms are used in the same way.

[0054] In this specification, the property of inhibiting the permeation of water vapor and oxygen is referred to as "gas barrier property", and the membrane with gas barrier property is referred to as "gas barrier membrane".

[0055] It should be noted that, for ease of understanding, accompanying drawings are used in various places for illustration, but the present invention is not limited to the contents shown in the drawings. Furthermore, the drawings are schematic diagrams and have been exaggerated compared to actual dimensions for ease of understanding.

[0056] Hereinafter, a gas barrier membrane of one or more embodiments of the present invention (hereinafter sometimes referred to as "this embodiment") will be described.

[0057] 1. Gas barrier membrane

[0058] The gas barrier film of the present invention comprises a substrate, an intermediate layer and a gas barrier layer stacked sequentially, the gas barrier layer having a first surface and a second surface opposite to the first surface, the first surface being the exposed surface side, and satisfying the following conditions (i) and (ii).

[0059] (i) In the micro-scratch test on the first surface mentioned above, the critical load value at the peeling point is 65 mN or more.

[0060] (ii) The light transmittance at a wavelength of 380 nm is less than 8.0%.

[0061] Hereinafter, the gas barrier membrane having the above-described structure will also be referred to as the "first gas barrier membrane".

[0062] The inventors conducted various studies and found that a gas barrier film having a structure comprising a substrate, an intermediate layer, and a gas barrier layer stacked sequentially can achieve a light transmittance of less than a given value at a wavelength of 380 nm, and can achieve a critical load value at the peel point greater than or equal to a given value in a micro-scratch test on the exposed surface of the gas barrier layer. The wavelength around 380 nm is the boundary between the ultraviolet and visible light regions; by sufficiently reducing the light transmittance at this wavelength, high ultraviolet blocking performance can be obtained. Furthermore, by setting the aforementioned critical load value above a given value, the substrate adhesion of the intermediate layer is increased. Moreover, the inventors discovered that for a gas barrier film having this structure, even when exposed to ultraviolet light under high temperature and high humidity conditions, the decrease in substrate adhesion can be suppressed, thus completing the present invention.

[0063] In condition (i) above, from the viewpoint of further improving the substrate adhesion of the intermediate layer, the critical load value is preferably 67 mN or more, more preferably 69 mN or more, and even more preferably 70 mN or more. There is no particular limitation on the upper limit of the critical load value.

[0064] For condition (i) above, for example, as described below, it can be achieved by the following method: the intermediate layer is composed of a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2), and the critical load value when the intermediate layer contains only the first ultraviolet absorber (B1) as an ultraviolet absorber is greater than the critical load value when the intermediate layer contains only the second ultraviolet absorber (B2) as an ultraviolet absorber. Hereinafter, such a combination of ultraviolet absorbers is sometimes referred to as "combination 1".

[0065] In condition (ii) above, from the viewpoint of further improving ultraviolet absorption, the light transmittance at a wavelength of 380 nm is preferably 6% or less, more preferably 5% or less. There is no lower limit; it can be 0%, but from the viewpoint of preventing a decrease in sealing performance, it can be, for example, 1%.

[0066] The above condition (ii) can be achieved, for example, by using a structure having a substrate with UV blocking properties and an intermediate layer containing a UV absorber, and setting the content of the UV absorber in the intermediate layer to an appropriate range.

[0067] 1-1. Example of the composition of a gas barrier membrane

[0068] Figure 1An example of the specific structure of the gas barrier membrane according to an embodiment of the present invention is shown.

[0069] Figure 1 The gas barrier film 100 shown has a substrate 10, an intermediate layer 20 formed on the substrate 10, and a gas barrier layer 30 formed on the intermediate layer 20.

[0070] The thickness of the aforementioned gas barrier film can be appropriately determined according to the intended use of the object to which it is applied (e.g., electronic equipment). From a processability point of view, the thickness of the aforementioned gas barrier film is preferably 5 to 500 μm, more preferably 10 to 200 μm, and even more preferably 30 to 90 μm.

[0071] From the perspective of ensuring high gas barrier properties, the water vapor permeability of the aforementioned gas barrier membrane in a gas atmosphere of 40°C and 90% relative humidity is preferably less than 1.0 × 10⁻⁶. -3 g / (m 2 ·day).

[0072] For example, by obtaining a gas barrier membrane that satisfies conditions (1) and (2) as described below by the method for manufacturing the gas barrier membrane, the water vapor permeability of the gas barrier membrane can be set to the above-described numerical range.

[0073] The water vapor transmission rate mentioned above can be determined by known methods.

[0074] From the viewpoint of ensuring the transparency of the gas barrier film, the haze value of the gas barrier film is preferably 10% or less, more preferably 1% or less, and even more preferably 0.7% or less.

[0075] To set the haze value within the aforementioned range, for example, as described below, the intermediate layer may be composed of a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2), and these may be configured as combination 1. It should be noted that the lower limit is not particularly limited and can be 0%.

[0076] From the viewpoint of ensuring the transparency of the gas barrier film, the total light transmittance (TT) of the aforementioned gas barrier film is preferably 80% or more, more preferably 85% or more, and even more preferably 88% or more. There is no particular upper limit to the aforementioned TT, and the higher the better. From the viewpoint of ease of manufacturing, for example, it is 99% or less.

[0077] To set the aforementioned TT to the aforementioned numerical range, for example, the aforementioned intermediate layer may include a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2) having an ultraviolet absorption capacity higher than that of the first ultraviolet absorber (B1), and preferably further uses a substrate with ultraviolet blocking properties. Hereinafter, such a combination of ultraviolet absorbers is sometimes referred to as "combination 2".

[0078] Among the aforementioned gas-barrier films, from the viewpoint of suppressing staining and improving transparency, L is preferred. * a * b * L color system * A value of 93 or higher, a * Values ​​(absolute values, others are treated the same way) below 0.3, b * Values ​​(absolute values, others are treated similarly) of 1 or less, preferably L. * A value above 94, a * Values ​​below 0.2, b * Values ​​below 0.9 are further optimized for L. * A value of 95 or above, a * Values ​​below 0.1, b * The value is below 0.8.

[0079] In order to make the above L * value, a * value and b * The value is set to the above-mentioned range. For example, the ultraviolet absorber contained in the intermediate layer is set to the above-mentioned combination 2, and it is preferable to further use a substrate with ultraviolet blocking properties.

[0080] The present invention also provides a barrier membrane having the following configuration (hereinafter also referred to as "second barrier membrane").

[0081] A gas barrier film comprising a substrate, an intermediate layer and a gas barrier layer stacked sequentially, subjected to a weather resistance test under the following conditions (1) to (4): 100 square cuts of 1 mm each are formed in the gas barrier layer, and after an adhesive tape is pressed onto the cuts, the ends of the adhesive tape are held at right angles relative to the gas barrier layer and peeled off from the gas barrier layer. At this time, the number of unpeeled squares is more than 50% of the total number of squares in the cuts, and the light transmittance at a wavelength of 380 nm is less than 8.0%.

[0082] (1) In an environment with a temperature of 60℃ and a relative humidity of 70%RH, with an illuminance of 100mW / cm 2 Expose to ultraviolet light for 5 hours.

[0083] (2) Let it stand at 70℃ for 5 hours.

[0084] (3) Let it stand for 5 hours at a temperature of 70℃ and a relative humidity of 90%RH.

[0085] (4) Take (1) to (3) above as one loop, and execute a total of 8 loops.

[0086] The aforementioned second gas barrier film has high UV blocking properties and high substrate adhesion to the intermediate layer under high temperature and high humidity conditions.

[0087] From the viewpoint of further improving the substrate adhesion of the intermediate layer to ultraviolet irradiation under high temperature and high humidity environments, the proportion of the number of unpeeled squares is more preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. There is no particular upper limit to the above proportion, and it can be 100%, but from the viewpoint of ease of manufacturing, it can be, for example, 98%.

[0088] In order to set the number of the above-mentioned unpeeled squares to the above-mentioned ratio, it is preferable that the intermediate layer has a variety of ultraviolet absorbers. For example, as described below, the intermediate layer adopts a structure containing a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2), and the ultraviolet absorbers are set to the above-mentioned combination 1. It is preferable to further use a substrate with ultraviolet blocking properties.

[0089] It should be noted that the matters described in “1-1. Example of the composition of the gas barrier membrane” also apply to the second gas barrier membrane mentioned above.

[0090] Furthermore, the matters described in “1-2. Substrate” to “1-5. Other configuration examples of gas barrier film” and “2. Method of manufacturing gas barrier film” below apply to both the first gas barrier film and the second gas barrier film.

[0091] 1-2. Substrate

[0092] As the substrate for the gas barrier film constituting the above embodiments, various conventionally known resin films were used, but the substrate is preferably an ultraviolet-absorbing substrate that absorbs ultraviolet light and exhibits high ultraviolet blocking properties. This ultraviolet-absorbing substrate is preferably a resin film with a light transmittance of 3.0% or less at a wavelength of 360 nm.

[0093] From the viewpoint of further improving ultraviolet blocking properties, the light transmittance of the above-mentioned resin film at a wavelength of 360nm is preferably 2.5% or less, and more preferably 2.0% or less.

[0094] The transmittance of light at a wavelength of 360 nm can be measured using an ultraviolet spectrophotometer.

[0095] Examples of resin films include those containing resin components and ultraviolet absorbers.

[0096] Examples of resin components for the aforementioned resin films include, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylates, as well as polyesters, polyimides, polyamides, polyamide-imides, polyphenylene ethers, polyetherketones, polyetheretherketones, polyolefins, polyesters, polycarbonates, polysulfones, polyethersulfones, polyphenylene sulfides, acrylic resins, cyclic olefin polymers, and aromatic polymers.

[0097] These resin components can be used alone or in combination of two or more.

[0098] For ultraviolet absorbers, there are no special limitations as long as a resin film with a light transmittance of less than 3.0% at a wavelength of 360nm can be obtained.

[0099] Examples of UV absorbers include: salicylic acid-based UV absorbers such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate; and benzophenone-based UV absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and bis(2-methoxy-4-hydroxy-5-benzoylphenyl)methane; 2- Benzotriazole UV absorbers such as (2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol]; cyanoacrylate UV absorbers such as 2-cyano-3,3'-diphenylacrylate; 2-p-nitrophenyl-3,1-benzotriazole... Azine-4-one, 2-(p-benzoylphenyl)-3,1-benzo[ Azine-4-one, 2-(2-naphthyl)-3,1-benzo[a] Azin-4-one, 2,2'-p-phenylenebis(3,1-benzo[]] 2,2'-(2,6-naphthylene)bis(3,1-benzo[a]one), 2,2'-(2,6-naphthylene)bis(3,1-benzo[a]one) Benzene (4-azinone) and other benzo[ Phosphine-ketone UV absorbers; inorganic UV absorbers such as titanium dioxide, cerium oxide, zinc oxide, iron oxide, and barium sulfate.

[0100] These UV absorbers can be used alone or in combination of two or more.

[0101] The content of ultraviolet absorber in the above resin film is preferably 0.1 to 10 parts by weight relative to 100 parts by weight of resin components.

[0102] In the above-mentioned resin film, when the total mass of the resin film is set to 100% by mass, the content of the above-mentioned resin component is preferably 50 to 99.9% by mass, more preferably 70 to 99.9% by mass, and even more preferably 90 to 99.9% by mass.

[0103] To the extent that it does not impair the effects of the present invention, the resin film described above may contain various additives. Examples of additives include: antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, fillers, and coloring pigments. The content of these additives may be appropriately determined according to the intended purpose.

[0104] The aforementioned resin film can be obtained by preparing a resin composition comprising resin components, ultraviolet absorbers, and various additives to be added as desired, and then molding it into a film. The molding method is not particularly limited, and known film-forming methods (e.g., casting, melt extrusion) can be used.

[0105] The aforementioned resin film can have various layers such as an anti-oligomer exudation layer, a slip-resistant layer, an antistatic layer, and a hard coating layer. It can also undergo easy-bonding treatments (e.g., corona treatment, flame treatment).

[0106] The resin film described above may or may not undergo heat-resistant treatment such as annealing.

[0107] From the viewpoint of ultraviolet blocking and light transmittance, the thickness of the above-mentioned resin film is preferably 5 to 500 μm, more preferably 10 to 250 μm, and even more preferably 20 to 100 μm.

[0108] As the aforementioned UV-absorbing substrate, commercially available UV-absorbing resin films can be used. Examples of such commercially available products include: Toyobo Co., Ltd.'s UV-absorbing PET film "HB3", DuPont Teijin Films Co., Ltd.'s UV-absorbing PET film "HBF8W", JSR Co., Ltd.'s UV-absorbing film "Arton R5300U", and Fujifilm Co., Ltd.'s UV-absorbing film "UV Guard".

[0109] 1-3. Intermediate Layer

[0110] From the viewpoint of substrate adhesion, the intermediate layer constituting the gas barrier film of this embodiment is preferably a cured product of a hard coating agent. Furthermore, from the viewpoint of easily exhibiting high ultraviolet absorption, the intermediate layer preferably contains at least two ultraviolet absorbers. For example, as such ultraviolet absorbers, it is more preferable to include a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2) different from the first ultraviolet absorber (B1). That is, the intermediate layer is more preferably a cured product of a hard coating agent comprising a hard coating agent, and the first ultraviolet absorber (B1) and the second ultraviolet absorber (B2).

[0111] From the viewpoint of sealing and ultraviolet blocking, the thickness of the above-mentioned intermediate layer is preferably 0.5~20μm, more preferably 0.6~15μm, even more preferably 0.7~10μm, even more preferably 0.8~8μm, and particularly preferably 0.9~4μm.

[0112] The components of the curable composition constituting the intermediate layer are described below.

[0113] (1) Hard coating agent

[0114] As the aforementioned hard coating agent, various commercially available hard coating agents can be used, as long as the critical load value obtained through the micro-scratch test meets the above-mentioned range; there are no particular limitations. The aforementioned hard coating agent may contain polymeric monomers, prepolymers, etc., that form a cured product through triggering, such as active energy rays, heat, etc.

[0115] As polymerizable monomers, from the viewpoint of forming a three-dimensional cross-linked structure and exhibiting hard coating properties, polyfunctional acrylates having more than three (meth)acryloyl groups in the molecule can be cited.

[0116] Examples of multifunctional acrylates include: 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate with hydroxypentanoic acid, dicyclopentyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified di(meth)acrylate phosphate, allylated cyclohexyl di(meth)acrylate, isocyanate di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. The following are esters: dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol penta(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tri(acryloyloxyethyl)isocyanurate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, and caprolactone modified dipentaerythritol hexa(meth)acrylate.

[0117] These can be used individually or in combination.

[0118] On the other hand, examples of prepolymers, specifically (meth)acrylate prepolymers, include prepolymers of polyester acrylates, epoxy acrylates, urethane acrylates, and polyol acrylates.

[0119] Furthermore, the aforementioned hard coating agent may contain monofunctional or difunctional polymerizable monomers and resins, etc., within a range that does not impair the aforementioned physical properties. Examples of resins include: polyethylene resins, polypropylene resins, polystyrene resins, polycarbonate resins, polyester resins, acrylic resins, phenolic resins, urea resins, epoxy resins, silicone resins, etc.

[0120] From the viewpoint of the UV-absorbing substrate and the adhesion to the gas barrier layer, the content of the hard coating agent in the curable composition for forming the interlayer is preferably 90.0% by mass or more, more preferably 95.0% by mass or more, and even more preferably 97.0% by mass or more, relative to the total mass of the solid components in the curable composition for forming the interlayer. In addition, from the viewpoint of easily ensuring weather-resistant adhesion, it is preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and even more preferably 99.7% by mass or less.

[0121] (2) Ultraviolet absorber (B)

[0122] In the gas barrier film of the embodiments of the present invention, the intermediate layer preferably includes an ultraviolet absorber (B). The ultraviolet absorber (B) is used to absorb ultraviolet rays entering from the outside, preventing the resin components constituting the intermediate layer from deteriorating or deteriorating.

[0123] Examples of ultraviolet absorbers (B) include: triazine compounds, benzophenone compounds, benzotriazole compounds, benzoic acid esters, and benzo[…]. Phosphine ketone compounds, phenyl salicylate compounds, cyanoacrylate compounds, and nickel complex salt compounds. These can be used individually or in combination. From the viewpoint of achieving both good adhesion to the substrate and high UV shielding of the interlayer, it is preferable to use a combination of two or more.

[0124] In the gas barrier membrane of the present invention, it is preferable that the intermediate layer contains a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2) as ultraviolet absorber (B). The critical load value when the intermediate layer contains only the first ultraviolet absorber (B1) as ultraviolet absorber is greater than the critical load value when the intermediate layer contains only the second ultraviolet absorber (B2) as ultraviolet absorber (i.e., the ultraviolet absorber is set as the above combination 1).

[0125] In the gas barrier membrane of the embodiments of the present invention, it is preferable that the above-mentioned intermediate layer includes a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2) having an ultraviolet absorption capacity higher than that of the first ultraviolet absorber (B1) as ultraviolet absorber (B) (that is, set as the above combination 2), more preferably the first ultraviolet absorber (B1) is a triazine ultraviolet absorber and the second ultraviolet absorber (B2) is a benzotriazole ultraviolet absorber.

[0126] Compared to benzotriazole UV absorbers, triazine-based UV absorbers tend to exhibit better substrate adhesion in the intermediate layer. Furthermore, benzotriazole-based UV absorbers have lower light transmittance at 380 nm compared to triazine-based UV absorbers. Therefore, by combining triazine-based and benzotriazole-based UV absorbers, both combinations 1 and 2 of the aforementioned UV absorbers can be achieved simultaneously, making it easier for the gas barrier film to meet the aforementioned conditions (i) and (ii). Additionally, it is easier to achieve a light transmittance of less than 8.0% at 380 nm, and it is easier to achieve a proportion of uncracked squares of 50% or more in the weather resistance tests according to conditions (1) to (4) above.

[0127] Examples of triazine compounds used as the aforementioned triazine ultraviolet absorbers include: 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine and 2-[4,6-bis(2,4-dimethylyl)-1,3,5-triazine-2-yl]-5-octyloxyphenol.

[0128] Examples of benzotriazole compounds used as the aforementioned benzotriazole ultraviolet absorbers include: 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate.

[0129] Relative to 100 parts by weight of the hard coating agent (A), the total content of ultraviolet absorber (B) in the curable composition for forming the intermediate layer is preferably greater than 2.0 parts by weight, more preferably 2.3 parts by weight or more, even more preferably 2.5 parts by weight or more, and even more preferably 3.5 parts by weight or more. It is also preferably less than 10 parts by weight, more preferably 7 parts by weight or less, even more preferably 5 parts by weight or less, and particularly preferably 4.4 parts by weight or less. By setting the total content of ultraviolet absorber (B) within the above range, it is easy to improve the adhesion of the formed intermediate layer to the substrate, and it is also easy to make the coatability of the curable composition for forming the intermediate layer good.

[0130] From the viewpoint of easily improving the substrate adhesion of the intermediate layer and the light transmittance at 380nm, the ratio of the mass MB1 of the first ultraviolet absorber (B1) to the mass MB2 of the second ultraviolet absorber (B2) in the above-mentioned intermediate layer, MB1 / MB2, is preferably 1 / 0.1 to 1 / 10, more preferably 1 / 0.5 to 1 / 3, and even more preferably 1 / 1 to 1 / 2.2.

[0131] (3) Additives (C)

[0132] To the extent that it does not impair the effects of the present invention, the curable composition for forming the intermediate layer may contain additives (C) as other components.

[0133] Other components may include, for example, photopolymerization initiators, antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, fillers, inorganic fillers, coloring pigments, and silane coupling agents. The content of these additives can be appropriately determined according to the intended purpose. The amount of photopolymerization initiator added will be discussed later.

[0134] By including a photopolymerization initiator in the curable composition for forming the intermediate layer, the amount of light irradiation can be reduced, and the polymerization and curing time can be shortened. In particular, the presence of a photopolymerization initiator is preferred when crosslinking is carried out by irradiation with active light such as ultraviolet light as an active energy ray.

[0135] There are no particular limitations on the photopolymerization initiator used; conventionally known photopolymerization initiators can be used. Examples include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl benzophenone, benzophenone, p-phenylbenzophenone, 2-methylanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, benzyl dimethyl ketal, p-dimethylaminobenzoate, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one. A single photopolymerization initiator can be used, or two or more can be used in combination.

[0136] When the curable composition for forming the intermediate layer contains a photopolymerization initiator, from the viewpoint of improving the efficiency of intermediate layer formation and preventing a decrease in adhesion, the content of the photopolymerization initiator in the curable composition for forming the intermediate layer is preferably 0.05 to 5.0 parts by weight, more preferably 0.1 to 3.0 parts by weight, and even more preferably 0.15 to 1.0 parts by weight, relative to 100 parts by weight of the hard coating agent (A).

[0137] 1-4. Gas barrier layer

[0138] From the viewpoint of low cost and ensuring high gas barrier properties, the aforementioned gas barrier film is preferably a gas barrier layer containing silicon and oxygen as main components. Here, "containing silicon and oxygen as main components" means that the combined mass of silicon and oxygen is 50% or more relative to the total mass of the gas barrier layer.

[0139] As described below, the aforementioned gas barrier layer is preferably formed by a coating of a composition comprising a polysilazane compound. Moreover, it is preferable to have a first region (high nitrogen content region) in the thickness direction of the gas barrier layer, which comprises silicon, oxygen, and nitrogen, and in which the nitrogen content is greater than that of other regions.

[0140] As described below, the first region was formed through a modification process, and compared to the second region, which is a region other than the first region, the nitrogen content is relatively higher. Therefore, in the following description, the first region is sometimes referred to as the "modified region" or "high-nitrogen region." The second region is sometimes referred to as the "unmodified region" or "low-nitrogen region." It should be noted that a "high-nitrogen region" refers to a region whose thickness does not decrease over time and is in a time-stable state.

[0141] The aforementioned gas barrier layer has a first region comprising silicon, oxygen, and nitrogen in its thickness direction, preferably satisfying the following conditions (1) and (2):

[0142] • Condition (1): The composition of the first region mentioned above is SiO x N y express.

[0143] x: 0.1~1.5

[0144] y: 0.2~0.7

[0145] • Condition (2): The thickness d of the first region mentioned above M It is 10nm or larger.

[0146] It can be assumed that the first region, which satisfies the above condition (1), reflects a high-density structure of silicon-nitrogen bonding, which is conducive to exhibiting high gas barrier performance.

[0147] From the perspective of improving air barrier properties, the aforementioned thickness d M Preferably, the nanometer diameter is 12 nm or more, more preferably 30 nm or more, and from the viewpoint of increasing the strength of the gas barrier layer, it is even more preferably 50 nm or more, and even more preferably 60 nm or more. There is no particular upper limit, but from the viewpoint of ease of manufacturing, it is preferably 300 nm or less, more preferably 150 nm or less, and particularly preferably 90 nm or less.

[0148] The aforementioned high-nitrogen-content region can be located on the outermost surface of the gas barrier layer or inside the gas barrier layer. From the viewpoints of achieving good gas barrier properties and ease of manufacturing, it is preferable that it is located on the outermost surface of the gas barrier layer.

[0149] Multiple high-nitrogen-content regions can exist in the depth direction. When multiple high-nitrogen-content regions are included, their combined thickness should be 10 nm or more.

[0150] From the viewpoint of preventing water vapor from passing through the ends, it is preferable that one of the multiple high nitrogen content regions is located at the outermost surface of the gas barrier membrane.

[0151] It should be noted that a gas barrier layer with multiple high nitrogen-containing regions in the depth direction can be obtained, for example, by repeatedly forming a gas barrier precursor layer for forming the gas barrier layer and the modification treatment described later.

[0152] In the depth direction of the aforementioned barrier layer, as described later, the nitrogen atom ratio can be gradually and continuously varied from the outermost surface by using modification treatment to form a high nitrogen content region.

[0153] In addition, in the variation of the element ratios of silicon, oxygen and nitrogen in the thickness direction of the barrier layer, there are sometimes regions where the nitrogen element ratio is higher than that in the deeper layers.

[0154] In the aforementioned gas barrier film, from the viewpoints of easily ensuring high gas barrier performance and light transmittance, as well as ease of manufacturing, the thickness d of the gas barrier layer is preferred. G And the thickness d of the first region mentioned above M Satisfying 1.00≥d M / d G A relationship ≥ 0.01 is preferred, and more preferably, 0.80 ≥ d is preferred. M / d G The relationship ≥0.02 is further optimized to satisfy 0.60≥d. M / d G A relationship ≥0.03.

[0155] From the perspectives of easily ensuring gas barrier properties, light transmittance, and flexibility, as well as ease of manufacturing, the thickness d of the gas barrier layer... G Preferably, the wavelength is 30~1500nm, more preferably 100~400nm.

[0156] Even if the thickness d of the gas barrier layer G At the nanoscale, by setting up high nitrogen-containing regions, it is also possible to obtain a barrier film with sufficient gas barrier performance.

[0157] By manufacturing the gas barrier film according to the method described later, and adjusting the composition of the coating solution and the conditions of the modification treatment at this time, the aforementioned thicknesses d can be achieved.G d M Set to the numerical range mentioned above.

[0158] The aforementioned gas barrier layer is formed from a gas barrier precursor layer, preferably a layer formed by drying a coating film containing a polysilazane compound (hereinafter also referred to as "coating liquid for gas barrier precursor layer"), which serves as the aforementioned gas barrier precursor layer. Then, the aforementioned high nitrogen content region can be formed by the modification treatment described later.

[0159] By providing a high-nitrogen-content region obtained by applying the modification treatment described later in the gas barrier precursor layer, a gas barrier layer with excellent gas barrier properties can be formed efficiently. The gas barrier precursor layer is a layer obtained by drying the above-mentioned gas barrier precursor layer with a coating liquid.

[0160] Examples of polysilazane compounds include inorganic polysilazanes and organic polysilazanes. Examples of inorganic polysilazanes include, for instance, perhydropolysilazanes, and examples of organic polysilazanes include compounds formed by replacing some or all of the hydrogen atoms in perhydropolysilazanes with organic groups such as alkyl groups. From the viewpoint of ease of acquisition and the ability to form a gas barrier layer with excellent gas barrier properties, inorganic polysilazanes are more preferred.

[0161] In addition, polysilazane compounds can also be used directly as commercially available products such as glass coating materials.

[0162] Polysilazane compounds can be used alone or in combination of two or more.

[0163] As a method for forming a layer by coating a coating liquid for coating a gas barrier precursor layer and drying it, an example is: coating a gas barrier precursor layer containing a polysilazane compound, other components (e.g., polysilane compound, curing agent, other polymer, antioxidant, light stabilizer, flame retardant) and solvent onto an ultraviolet-absorbing substrate by coating liquid using a known method, and then drying the resulting coating film appropriately.

[0164] Since the aforementioned polysilazane compounds are contained in the coating liquid for the gas barrier precursor layer, the polysilazane undergoes a conversion reaction through heating after coating, resulting in a coating film (gas barrier precursor layer) with gas barrier properties.

[0165] The thickness of the barrier layer is preferably 30~1500nm, more preferably 40~1000nm, and even more preferably 100~400nm.

[0166] Even if the thickness of the gas barrier precursor layer is in the nanometer range, a gas barrier film with sufficient gas barrier performance can be obtained through subsequent modification treatment.

[0167] Examples of modification treatments mentioned above include ion implantation and vacuum ultraviolet irradiation (irradiation by excimer laser, etc.). Among these, ion implantation is preferred from the viewpoint of obtaining high gas barrier properties.

[0168] Examples of ions that can be implanted include ions of rare gases such as argon, helium, neon, krypton, and xenon; and ions of fluorocarbons, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur. These ions can be used individually or in combination of two or more.

[0169] There are no particular limitations on the method of ion implantation, and examples include: irradiating ions accelerated by an electric field (ion beam) and implanting ions into plasma. Among these, the latter method of implanting plasma ions is preferred from the perspective of easily obtaining a membrane with gas barrier properties.

[0170] As for the types of ions that are injected into the plasma, the same ions as those exemplified above as the injected ions can be cited.

[0171] 1-5. Other examples of gas barrier membrane construction

[0172] The gas barrier membrane in the embodiments of the present invention is not limited to Figure 1 The gas barrier film shown may include one or more other layers in one or more portions selected from the substrate, between the substrate and the intermediate layer, between the intermediate layer and the gas barrier layer, and on the gas barrier layer, without prejudice to the purpose of the present invention.

[0173] Other layers mentioned above could include other gas barrier layers or protective layers. Furthermore, the placement of these other layers is not limited to the positions described above.

[0174] Alternatively, the aforementioned gas barrier film can be a long strip of gas barrier film. In this case, the aforementioned gas barrier film can be a roll-shaped gas barrier film wound around the core material.

[0175] 2. Manufacturing method of gas barrier membrane

[0176] The method for manufacturing the gas barrier membrane according to embodiments of the present invention includes the following steps.

[0177] • Process 1: Intermediate Layer Formation Process

[0178] • Process 2: Gas barrier layer formation process

[0179] The above-mentioned process 1 further includes the following processes.

[0180] • Process 1-1: Preparation of substrate

[0181] Process 1-2: Formation of the intermediate layer

[0182] 2-1. Preparation of the substrate (Step 1-1)

[0183] Prepare a substrate (preferably a UV-absorbing substrate).

[0184] 2-2. Formation of the intermediate layer (process 1-2)

[0185] In the formation of the intermediate layer, a coating liquid containing a curable composition for intermediate layer formation and a solvent added as needed is prepared. Then, the coating liquid is applied to a substrate using a known method, and the resulting coating film is cured to form an intermediate layer formed from the cured product of the curable composition for intermediate layer formation. If necessary, a drying process can be performed before curing the coating film.

[0186] Examples of solvents used in coating solutions include: aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; and alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane.

[0187] These solvents can be used alone or in combination of two or more.

[0188] Examples of coating methods include: bar coating, spin coating, dip coating, roller coating, gravure coating, doctor blade coating, air knife coating, roller knife coating, mold coating, screen printing, spray coating, and gravure offset printing.

[0189] When drying the coating, conventionally known drying methods such as hot air drying, hot roller drying, and infrared irradiation can be used. The drying temperature is typically in the range of 60–130°C. The drying time is typically from a few seconds to several tens of minutes.

[0190] The coating can be cured by irradiating the surface of the coating (the side without a substrate) with active energy rays. Ultraviolet light emitted from an ultraviolet source is preferably used as the active energy ray.

[0191] As a source of ultraviolet light, various light sources can be used, including ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light lamps, and metal halide lamps. There are no particular limitations on the amount of ultraviolet light emitted, typically around 100 mJ / cm². 2 ~1000mJ / cm 2 The irradiation time is usually from a few seconds to several hours, and the irradiation temperature is usually from room temperature (20°C) to 100°C.

[0192] 2-3. Formation of the gas barrier layer (Step 2)

[0193] In step 2, following the steps described in the “1-4. Gas Barrier Layer” section above, a gas barrier layer is formed on the intermediate layer.

[0194] 3. Methods for evaluating the sealing performance of gas barrier membranes

[0195] For any of the aforementioned gas barrier films, the adhesion evaluation method of the gas barrier film according to the embodiments of the present invention is performed in accordance with JIS R 3255 (1997). Specifically, the indenter of a micro-scratch tester is brought into contact with a first surface, and a micro-scratch test is performed while increasing the load value at a given load loading rate according to the aforementioned standard. The first surface is the surface of the exposed side of the gas barrier layer of the aforementioned gas barrier film. Then, the load value at the location where the gas barrier layer peels off is taken as the critical load value, and the adhesion of the gas barrier layer to the substrate is evaluated based on this critical load value. The larger the critical load value, the higher the adhesion of the intermediate layer to the substrate.

[0196] The micro-scratch test described above was conducted under the conditions detailed in the examples.

[0197] Micro-scratch tests are mostly applicable to evaluating the adhesion of films formed on glass materials. However, as in this embodiment, it is also suitable for evaluating the substrate adhesion of the intermediate layer to a gas barrier film on which an intermediate layer and a gas barrier layer are formed.

[0198] Example

[0199] The following describes specific embodiments of the present invention, but the present invention is not limited to these examples.

[0200] The following steps were used to determine and evaluate the sealing properties, gas barrier properties, ultraviolet absorption properties, and turbidity after weathering tests in the examples and comparative examples described below.

[0201] [Substrate Adhesion]

[0202] For the first surface of the gas barrier membrane prepared in the examples and comparative examples, which serves as the exposed side of the gas barrier layer, a micro-scratch test was performed using an ultra-thin film scratch tester (Rhesca CSR-2000) according to JIS R 3255 (1997) under the following conditions.

[0203] • Stylus diameter of the pressure head: 25μm

[0204] • Spring constant of the indenter: 100g / m 2

[0205] • Scratch speed: 20μm / sec

[0206] • Loading speed: 0.83 mN / sec

[0207] • Excitation amplitude: 100μm

[0208] • Excitation vibration frequency: 45Hz

[0209] The scratches after the experiment were observed using a digital microscope to determine the peeling point, and the load value at this point was recorded as the critical load value, which served as an indicator for evaluating the film's adhesion. Then, cases with a critical load value above 65 mN were rated "G", and cases below 65 mN were rated "NG". "G" was deemed acceptable, and "NG" was deemed unacceptable.

[0210] [Gas barrier properties]

[0211] After forming an intermediate layer and a gas barrier layer sequentially on an ultraviolet-absorbing substrate according to the steps of the examples or comparative examples, the water vapor transmission rate (WVTR) was measured to evaluate the gas barrier properties. A WVTR value less than 1.0 × 10⁻⁶ was considered acceptable. -3 [g / (m 2 The evaluation of the case of [day] is "G", and the value will be 1.0 × 10. -3 [g / (m 2 The above situation is evaluated as "NG". "G" is judged as qualified, and "NG" is judged as unqualified.

[0212] WVTR was measured using a water vapor transmission rate measuring device (MOCON, AQUATRAN-2 (AQUATRAN is a registered trademark)) at a relative humidity of 90% and a temperature of 40°C.

[0213] [UV blocking properties]

[0214] After forming an intermediate layer and a barrier layer sequentially on an ultraviolet-absorbing substrate according to the steps of the examples or comparative examples, the light transmittance at a wavelength of 380 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by Shimadzu Corporation).

[0215] [Seam tightness after weathering test]

[0216] After forming an intermediate layer and a gas barrier layer on a UV-absorbing substrate according to the steps of the examples or comparative examples, the substrate was subjected to UV irradiation at high temperature using a QUV accelerated weathering tester (manufactured by Sanyo Trading Co., Ltd.) (UV lamp: UVA-340+, 60°C, 1.15W / m²). 2(400h). Then, by forming 10×10 cuts at 1mm intervals in the gas barrier layer, 100 square cuts of 1mm each were formed. Adhesive tape (Cellotape (registered trademark), manufactured by Nichiban Co., Ltd.) was tightly pressed onto the cuts. After 1 minute, the adhesive tape was peeled off in one go while holding the end at a right angle relative to the gas barrier layer. The ratio of the number of unpeeled squares to the total number of squares in the cuts was investigated. Cases with more than 50% were rated as "G", and cases with less than 50% were rated as "NG". "G" was considered acceptable, and "NG" was considered unacceptable.

[0217] [Optical property evaluation]

[0218] After the gas barrier layer was formed, turbidity (haze) and total light transmittance (TT) were measured using a haze meter (NDH-5000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). Additionally, brightness (L) was measured using a UV-Vis-NIR spectrophotometer (manufactured by Shimadzu Corporation). * and chromaticity a * b * Evaluation.

[0219] [Example 1]

[0220] A composition for forming an intermediate layer was prepared by mixing 100 parts by weight of UV-5501 (manufactured by Mitsubishi Chemical Corporation) as a hard coating agent (A), 0.2 parts by weight of 1-hydroxycyclohexylbenzophenone as a photopolymerization initiator, 1.0 part by weight of Tinuvin 477 (a triazine ultraviolet absorber manufactured by BASF) as a first ultraviolet absorber (B1), and 3.0 parts by weight of DAINSORB TC-1 (a benzotriazole ultraviolet absorber manufactured by Yamato Kasei Corporation) as a second ultraviolet absorber (B2).

[0221] The resulting intermediate layer composition was applied to the untreated side of a 50 μm thick UV-absorbing polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., HB3, wavelength 360 nm, transmittance: 1.468%) that had undergone single-sided easy-to-adhere treatment. It was then heat-dried at 70°C for 1 minute and subjected to ultraviolet irradiation (at a light intensity of 200 mJ / cm²). 2 Illuminance: 190mW / cm 2 The intermediate layer is formed by irradiating it twice under certain conditions. The thickness of the intermediate layer is 1.0 μm.

[0222] Next, a perhydropolysilazane (weight-average molecular weight 10000 g / mol) was coated onto the aforementioned intermediate layer and dried at 120°C for 2 minutes, thereby forming a polysilazane layer. The thickness of the polysilazane layer was 250 nm. Then, using a plasma ion implantation device, plasma ion implantation was performed on the aforementioned polysilazane layer under the following conditions, thereby modifying the surface of the polysilazane layer. This resulted in a gas barrier film.

[0223] The plasma ion implantation apparatus and plasma ion implantation conditions used in the above modification treatment are shown below.

[0224] (Plasma ion implantation device)

[0225] • RF power supply: Model "RF56000", manufactured by Nippon Electronics Co., Ltd.

[0226] High-voltage pulse power supply: "PV-3-HSHV-0835", manufactured by Kurita Manufacturing Co., Ltd.

[0227] (Plasma ion implantation conditions)

[0228] • Plasma-generating gas: Helium (He)

[0229] • Gas flow rate: 100 sccm

[0230] • Duty ratio: 0.5%

[0231] • Repetition frequency: 1000Hz

[0232] • Applied voltage: -8kV

[0233] • RF power supply: 13.56MHz frequency, 1000W applied power

[0234] • Chamber pressure: 0.2 Pa

[0235] • Pulse width: 5μsec

[0236] • Processing time (ion implantation time): 200 seconds

[0237] [Example 2]

[0238] The amount of Tinuvin 477 (a triazine UV absorber manufactured by BASF) used as the first UV absorber (B1) was set to 1.3 parts by mass, and the amount of DAINSORB TC-1 (a benzotriazole UV absorber manufactured by Yamato Kasei Corporation) used as the second UV absorber (B2) was changed to 2.7 parts by mass. Otherwise, the gas barrier film was obtained in the same manner as in Example 1.

[0239] [Example 3]

[0240] The amount of Tinuvin 477 (a triazine UV absorber manufactured by BASF) used as the first UV absorber (B1) was set to 2.0 parts by weight, and the amount of DAINSORB TC-1 (a benzotriazole UV absorber manufactured by Yamato Kasei Corporation) used as the second UV absorber (B2) was changed to 2.0 parts by weight. Otherwise, the gas barrier film was obtained in the same manner as in Example 1.

[0241] [Comparative Example 1]

[0242] The amount of Tinuvin 477 (a triazine UV absorber manufactured by BASF) used as the first UV absorber (B1) was set to 4.0 parts by weight. No second UV absorber (B2) was used. Otherwise, the gas barrier film was obtained in the same manner as in Example 1.

[0243] [Comparative Example 2]

[0244] The first ultraviolet absorber (B1) was not used, and the amount of DAINSORB TC-1 (benzotriazole ultraviolet absorber manufactured by Daiwa Kasei Corporation) used as the second ultraviolet absorber (B2) was changed to 4.0 parts by weight. Otherwise, the gas barrier film was obtained in the same manner as in Example 1.

[0245] The physical properties and evaluation results of each embodiment and comparative example are shown in Table 1 together with the composition of the composition for forming the intermediate layer. It should be noted that "-" in the numerical columns of Table 1 indicates that the component was not incorporated.

[0246]

[0247] Based on the results in Table 1, it is clear that the gas barrier films of Examples 1-3 meet the above conditions (i) and (ii), exhibiting high substrate adhesion and UV shielding. Furthermore, the substrate adhesion is good after weathering testing. In addition, they demonstrate high gas barrier properties and high total light transmittance, with minimal turbidity and coloring.

[0248] It should be noted that, based on the critical load value of the gas barrier film of Comparative Example 1, which has an intermediate layer containing a triazine-based ultraviolet absorber as the first ultraviolet absorber (B1) and no second ultraviolet absorber (B2), and the critical load value of the gas barrier film of Comparative Example 2, which does not contain the first ultraviolet absorber (B1) and contains a benzotriazole-based ultraviolet absorber as the second ultraviolet absorber (B2), it can be clearly seen that, compared with the second ultraviolet absorber (B2), the first ultraviolet absorber (B1) is an ultraviolet absorber that exhibits higher substrate adhesion in the intermediate layer.

[0249] On the other hand, the gas barrier film of Comparative Example 1, which contains the first ultraviolet absorber (B1) and does not contain the second ultraviolet absorber (B2) in the intermediate layer, satisfies the above-mentioned condition (i) but does not satisfy the above-mentioned condition (ii), and its ultraviolet shielding performance is poor compared with the embodiment. Furthermore, the gas barrier film of Comparative Example 2, which does not contain the first ultraviolet absorber (B1) and contains the second ultraviolet absorber (B2) in the intermediate layer, satisfies the above-mentioned condition (ii) but does not satisfy the above-mentioned condition (i), and its substrate adhesion in the intermediate layer is poor compared with the embodiment. Moreover, the evaluation of substrate adhesion after weathering tests for the gas barrier films of Comparative Examples 1 and 2 both failed to meet the acceptable standard.

Claims

1. A gas barrier film comprising a substrate, an intermediate layer, and a gas barrier layer sequentially stacked, the gas barrier film having a first surface and a second surface opposite to the first surface, the first surface being the exposed surface side of the gas barrier layer, and the gas barrier film satisfying the following conditions (i) and (ii): (i) In the micro-scratch test on the first surface, the critical load value at the peeling point is 65 mN or more; (ii) The light transmittance at a wavelength of 380 nm is less than 8.0%.

2. The gas barrier membrane according to claim 1, wherein, The intermediate layer contains a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2). The critical load value when the intermediate layer contains only the first ultraviolet absorber (B1) as an ultraviolet absorber is greater than the critical load value when the intermediate layer contains only the second ultraviolet absorber (B2) as an ultraviolet absorber.

3. The gas barrier membrane according to claim 1 or 2, wherein, The intermediate layer contains a first ultraviolet absorber (B1) and a second ultraviolet absorber (B2), wherein the first ultraviolet absorber (B1) is a triazine ultraviolet absorber and the second ultraviolet absorber (B2) is a benzotriazole ultraviolet absorber.

4. The gas barrier membrane according to claim 1 or 2, wherein, The substrate is an ultraviolet-absorbing substrate.

5. The gas barrier membrane according to claim 1 or 2, wherein, The thickness of the intermediate layer is 0.5~20μm.

6. The gas barrier membrane according to claim 1 or 2, wherein, The water vapor transmission rate is less than 1.0 × 10⁻⁶ at 40℃ and 90% relative humidity. -3 g / (m 2 ·day).

7. The gas barrier membrane according to claim 1 or 2, wherein, The haze value is below 10%.

8. The gas barrier membrane according to claim 1 or 2, wherein, The total light transmittance is over 80%.

9. The gas barrier membrane according to claim 1 or 2, wherein, L * a * b * L color system * A value of 93 or higher, a * Values ​​below 0.3, b * The value is below 1.

10. A gas barrier membrane comprising a substrate, an intermediate layer, and a gas barrier layer sequentially stacked. Weather resistance tests were conducted under the following conditions (1) to (4): 100 square cuts of 1 mm each were formed in the gas barrier layer. After adhesive tape was pressed onto the cuts, the ends of the adhesive tape were kept at right angles to the gas barrier layer and peeled off. The ratio of the number of unpeeled squares to the total number of squares in the cuts was more than 50%, and the light transmittance at a wavelength of 380 nm was less than 8.0%. The conditions (1) to (4) are: (1) In an environment with a temperature of 60℃ and a relative humidity of 70%RH, with an illuminance of 100mW / cm 2 Expose the patient to ultraviolet light for 5 hours. (2) Let stand at 70℃ for 5 hours; (3) Let it stand for 5 hours at a temperature of 70℃ and a relative humidity of 90%RH; (4) Take (1) to (3) as one loop and execute a total of 8 loops.

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