Gas barrier film

Abstract

To provide a gas barrier film having high adhesion and gas barrier property and having excellent weather-resistant adhesion.SOLUTION: A gas barrier film is obtained by laminating an ultraviolet absorption substrate, an under layer, and a gas barrier layer in this order, wherein the under layer contains at least one selected from the group consisting of an ultraviolet absorber and a light stabilizer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a gas barrier film. [Background technology]

[0002] It has been proposed to use a resin film having ultraviolet blocking properties as the base material of a gas barrier film in order to reduce ultraviolet degradation of functional elements constituting an electronic device (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2015 / 152075 Summary of the Invention [Problem to be solved by the invention]

[0004] However, according to the inventors' investigations, it has been found that gas barrier films using a resin film with ultraviolet blocking properties as a substrate exhibit reduced adhesion when exposed to strong ultraviolet rays in a high-temperature environment for a long period of time, and that there is room for improvement.

[0005] In view of the above problems, an object of the present invention is to provide a gas barrier film that has high adhesion and gas barrier properties, and also has excellent weather-resistant adhesion. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by using an ultraviolet-absorbing substrate and further providing an underlayer made of a predetermined component, and have thus completed the present invention. That is, the present invention provides the following [1] to [5].

[0007] [1] A gas barrier film comprising an ultraviolet-absorbing substrate, an underlayer, and a gas barrier layer laminated in this order, wherein the underlayer contains at least one selected from the group consisting of an ultraviolet absorber and a light stabilizer. [2] The gas barrier film according to [1] above, wherein the ultraviolet absorbing substrate is a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm. [3] The gas barrier film according to the above [1] or [2], wherein the thickness of the underlayer is 0.5 to 3 μm. [4] The gas barrier film according to any one of the above [1] to [3], wherein the ultraviolet absorbing substrate has a thickness of 5 to 500 μm. [5] Water vapor permeability is 1.0 × 10 -3 g / (m 2 The gas barrier film according to any one of the above [1] to [4], wherein the gas barrier film has a shelf life of 10 days or less. [Effects of the Invention]

[0008] According to the present invention, a gas barrier film is provided which has high adhesion and gas barrier properties, and also has excellent weather-resistant adhesion. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view showing an example of a gas barrier film. DETAILED DESCRIPTION OF THE INVENTION

[0010] In this specification, preferred definitions can be selected arbitrarily, and combinations of preferred definitions can be considered more preferred. In this specification, the expression "XX to YY" means "XX or more and YY or less." In this specification, for preferred numerical ranges (e.g., ranges of content, etc.), the lower and upper limits described in stages can be independently combined. For example, the description "preferably 10 to 90, more preferably 30 to 60" can be combined with the "preferable lower limit (10)" and the "more preferable upper limit (60)" to form "10 to 60." In this specification, for example, "(meth)acrylate" refers to both "acrylate" and "methacrylate," and similar terms. In this specification, the property of inhibiting the permeation of water vapor or oxygen is referred to as "gas barrier property," and a film having gas barrier property is referred to as "gas barrier film." Although the present invention will be described using drawings in various places to facilitate understanding, the present invention is not limited to those shown in the drawings. Furthermore, the drawings are schematic diagrams, and are shown exaggerated from the actual dimensions to facilitate understanding. A gas barrier film according to an embodiment of the present invention (hereinafter, sometimes referred to as "the present embodiment") will be described below.

[0011] 1. Gas barrier film The gas barrier film according to an embodiment of the present invention comprises an ultraviolet-absorbing substrate, an underlayer, and a gas barrier layer laminated in this order, and the underlayer contains at least one selected from the group consisting of an ultraviolet absorber and a light stabilizer.

[0012] The inventors have found that providing an underlayer between a UV-absorbing substrate and a gas barrier layer to enhance adhesion between them results in UV degradation and peeling of the underlayer. After extensive research, the inventors have found that adding at least one selected from the group consisting of a light stabilizer and a UV absorber to the underlayer to prevent peeling prevents UV degradation of the underlayer, thereby ensuring adhesion between the UV-absorbing substrate and the gas barrier layer and maintaining excellent gas barrier properties even under harsh sunlight exposure conditions. Furthermore, they have found that it is more preferable that the at least one selected from the group consisting of the light stabilizer and the UV absorber is a compound in which a functional group exhibiting at least one of a light stabilizing function and a UV absorbing function is bonded to a silane coupling agent. Based on these findings, the inventors have come up with the present invention.

[0013] 1-1. Gas barrier film configuration example FIG. 1 shows an example of a specific configuration of the gas barrier film according to an embodiment of the present invention. The gas barrier film 100 shown in FIG. 1 has an ultraviolet absorbing substrate 10, an underlayer 20 formed on the ultraviolet absorbing substrate 10, and a gas barrier layer 30 formed on the underlayer 20.

[0014] The thickness of the gas barrier film can be appropriately determined depending on the use of the object to which it is attached (for example, an electronic device), etc. From the viewpoint of handleability, the thickness of the gas barrier film is preferably 5.5 to 503 μm, more preferably 10.5 to 252 μm, and more preferably 20.5 to 101.5 μm.

[0015] The water vapor transmission rate of the gas barrier film under an atmosphere of 40°C and a relative humidity of 90% is preferably 1.0 × 10 -3 g / (m 2 ·day) or less. The water vapor permeability of the gas barrier film can be set within the above numerical range by obtaining a gas barrier film that satisfies the above-mentioned requirements (1) and (2) according to the gas barrier film manufacturing method described below. The water vapor transmission rate is measured by a known method.

[0016] 1-2. UV-absorbing substrate The substrate constituting the gas barrier film according to this embodiment is an ultraviolet-absorbing substrate that absorbs ultraviolet rays and exhibits high ultraviolet blocking properties. The ultraviolet-absorbing substrate is preferably a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm. The light transmittance of the resin film at a wavelength of 360 nm is preferably 2.5% or less, and more preferably 2.0% or less, from the viewpoint of further enhancing the ultraviolet blocking property. The light transmittance at a wavelength of 360 nm is measured using an ultraviolet spectrophotometer. The resin film may be a resin film containing a resin component and an ultraviolet absorber.

[0017] Examples of the resin component of the resin film include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, acrylic resins, cycloolefin polymers, and aromatic polymers. These resin components may be used singly or in combination of two or more.

[0018] The ultraviolet absorber is not particularly limited as long as it can provide a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm. Examples of ultraviolet absorbers include salicylic acid-based ultraviolet absorbers such as pt-butylphenyl salicylate and p-octylphenyl salicylate; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and bis(2-methoxy-4-hydroxy-5-benzoylphenyl)methane; 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzoylphenyl)methyl] ... benzotriazole-based ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers such as benzotriazole-2-ylphenol; cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3'-diphenylacrylate; benzoxazinone-based ultraviolet absorbers such as 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-(p-benzoylphenyl)-3,1-benzoxazin-4-one, 2-(2-naphthyl)-3,1-benzoxazin-4-one, 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), and 2,2'-(2,6-naphthylene)bis(3,1-benzoxazin-4-one); and inorganic ultraviolet absorbers such as titanium dioxide, cerium oxide, zinc oxide, iron oxide, and barium sulfate. These ultraviolet absorbents may be used alone or in combination of two or more.

[0019] The content of the ultraviolet absorber in the resin film is preferably 0.1 to 10% by mass relative to the resin component.

[0020] The resin film may contain various additives as long as the effects of the present invention are not impaired. Examples of additives include antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, fillers, and coloring pigments. The content of these additives may be determined appropriately depending on the purpose.

[0021] The resin film can be obtained by preparing a resin composition containing a resin component, an ultraviolet absorber, and, if desired, various additives, and molding the composition into a film. The molding method is not particularly limited, and known film-forming methods such as casting and melt extrusion can be used.

[0022] The ultraviolet-absorbing substrate may have various layers such as an oligomer precipitation-preventing layer, a lubricating layer, an antistatic layer, a hard coat layer, etc. It may also be subjected to an adhesion-enhancing treatment such as a corona treatment or a flame treatment. The ultraviolet absorbing substrate may be one that has been subjected to a heat resistance treatment such as annealing treatment, or one that has not been subjected to a heat resistance treatment.

[0023] The thickness of the ultraviolet absorbing substrate is preferably 5 to 500 μm, more preferably 10 to 250 μm, and even more preferably 20 to 100 μm, from the viewpoints of ultraviolet blocking properties and light transmittance.

[0024] The ultraviolet absorbing substrate may be a commercially available ultraviolet absorbing resin film, such as the UV absorbing PET film "HB3" manufactured by Toyobo Co., Ltd., the UV absorbing PET film "HBF8W" manufactured by Teijin DuPont Films Ltd., the ultraviolet absorbing film "Arton R5300U" manufactured by JSR Corporation, and the ultraviolet absorbing film "UV Guard" manufactured by Fujifilm Corporation.

[0025] 1-3. Base layer As described above, the underlayer constituting the gas barrier film according to this embodiment contains at least one selected from the group consisting of an ultraviolet absorber (B) and a light stabilizer (C). The underlayer is preferably a cured product of a curable composition containing a curable component (A) and at least one selected from the group consisting of an ultraviolet absorber (B) and a light stabilizer (C). The curable composition used to form the underlayer may further contain a silane coupling agent (D). The light stabilizer (C) may be a silane coupling agent (C1) having a light stabilizing group.

[0026] Specific examples of the curable composition include the following embodiments (i) to (v). (i) A curable composition comprising a curable component (A) and a silane coupling agent (C1) having a light-stabilizing group. (ii) A curable composition comprising a curable component (A), a light stabilizer (C), and a silane coupling agent (D). (iii) A curable composition comprising a curable component (A) and an ultraviolet absorber (B). (iv) A curable composition comprising a curable component (A) and a light stabilizer (C). (v) A curable composition comprising a curable component (A), an ultraviolet absorber (B), and a silane coupling agent (D). Hereinafter, the curable composition used to form the underlayer may be referred to as a "curable resin composition for forming the underlayer." The thickness of the underlayer is preferably 0.5 to 3 μm, more preferably 0.5 to 2 μm, and even more preferably 0.5 to 1.5 μm, from the viewpoints of adhesion and ultraviolet blocking properties.

[0027] Hereinafter, each component constituting the curable resin composition for forming the underlayer will be described.

[0028] (1) Curable component (A) The curable component (A) contained in the curable composition for forming the underlayer is a component that is cured by a trigger such as active energy rays or heat, and examples thereof include an active energy ray-curable component, a thermosetting component, etc. In the underlayer of the present embodiment, it is preferable to use an active energy ray-curable component from the viewpoints of the hardness of the underlayer to be formed, the heat resistance of the ultraviolet-absorbing base material, etc. The active energy ray-curable component is preferably one that is cured by irradiation with active energy rays to exhibit a predetermined hardness and achieve the above-mentioned physical properties.

[0029] Specific examples of active energy ray-curable components include polyfunctional (meth)acrylate monomers, (meth)acrylate prepolymers, and active energy ray-curable polymers, among which polyfunctional (meth)acrylate monomers and / or (meth)acrylate prepolymers are preferred, and polyfunctional (meth)acrylate monomers are more preferred. The polyfunctional (meth)acrylate monomers and (meth)acrylate prepolymers may be used alone or in combination.

[0030] Examples of polyfunctional (meth)acrylate monomers include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol. Examples of the polyfunctional (meth)acrylate include dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, pentaerythritol tetra(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. These may be used alone or in combination of two or more.

[0031] On the other hand, examples of (meth)acrylate-based prepolymers include polyester acrylate-based, epoxy acrylate-based, urethane acrylate-based, and polyol acrylate-based prepolymers.

[0032] The polyester acrylate prepolymer can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends, obtained by condensation of a polycarboxylic acid and a polyhydric alcohol, with (meth)acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid, with (meth)acrylic acid.

[0033] Epoxy acrylate prepolymers can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol epoxy resin or novolac epoxy resin to esterify it.

[0034] The urethane acrylate prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate with (meth)acrylic acid.

[0035] The polyol acrylate prepolymer can be obtained, for example, by esterifying the hydroxyl groups of a polyether polyol with (meth)acrylic acid.

[0036] The above prepolymers may be used singly or in combination of two or more.

[0037] It is also preferable to use an organic-inorganic hybrid resin as the active energy ray-curable component. A preferred example of the organic-inorganic hybrid resin is a substance obtained by bonding an organic compound having a polymerizable unsaturated group to inorganic fine particles such as silica via a silane coupling agent or the like. The inorganic fine particles contained in the organic-inorganic hybrid resin do not correspond to the inorganic filler described below, but function as a binder, and can improve the hardness of the resulting underlayer. Furthermore, when an organic-inorganic hybrid resin is used, the organic component contributes to adhesion to the substrate, and the inorganic component contributes to adhesion to the gas barrier layer, making it easier to obtain an underlayer with superior adhesion between the substrate and the gas barrier layer.

[0038] The content of the curable component (A) in the curable resin composition for forming the underlayer is, relative to the total mass of the solids in the curable resin composition for forming the underlayer, preferably 90.0 mass% or more, more preferably 95.0 mass% or more, and even more preferably 97.0 mass% or more, from the viewpoint of adhesion to the ultraviolet-absorbing substrate and the gas barrier layer, and is preferably 99.9 mass% or less, more preferably 99.8 mass% or less, and even more preferably 99.7 mass% or less, from the viewpoint of making it easier to ensure weather-resistant adhesion.

[0039] (2) Ultraviolet absorber (B) The ultraviolet absorber (B) is used to absorb ultraviolet rays entering from the outside and to prevent deterioration and alteration of the resin components that make up the underlayer.

[0040] Examples of the ultraviolet absorber (B) are not particularly limited, and include, for example, triazine compounds, benzophenone compounds, benzotriazole compounds, benzoate compounds, benzoxazinone compounds, phenyl salicylate compounds, cyanoacrylate compounds, and nickel complex compounds. These may be used alone or in combination of two or more. Among the above, triazine compounds, benzophenone compounds, and benzotriazole compounds are preferred, and triazine compounds are particularly preferred.

[0041] Examples of the triazine compounds include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine and 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol.

[0042] Examples of the benzophenone compounds include 2,2-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, and 2-hydroxy-4-n-octyloxybenzophenone.

[0043] Examples of the benzotriazole-based compound include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, octyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0044] The content of the ultraviolet absorber (B) in the curable composition for forming the underlayer is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, even more preferably 0.3 part by mass or more, and is preferably 10 parts by mass or less, more preferably 6 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the curable component (A). By setting the content of the ultraviolet absorber (B) within the above range, it is easy to improve the adhesion of the underlayer to the ultraviolet-absorbing substrate, and it is also easy to improve the coatability of the curable composition for forming the underlayer.

[0045] (3) Light stabilizer (C) By including the light stabilizer (C) in the curable composition for forming the undercoat layer, the gas barrier film according to this embodiment can more easily achieve physical properties relating to adhesion, and can more easily have excellent weather-resistant adhesion.

[0046] Examples of the light stabilizer (C) are not particularly limited and include, for example, hindered amine light stabilizers, benzophenone light stabilizers, and benzotriazole light stabilizers. These light stabilizers (C) may be used alone or in combination of two or more.

[0047] Among the above-mentioned examples of the light stabilizer (C), it is preferable to use a hindered amine light stabilizer, from the viewpoint of easily realizing excellent weather-resistant adhesion. Here, the hindered amine refers to an amine having substituents on both sides of the amino group. The hindered amine light stabilizer in this embodiment is preferably a compound containing at least one skeleton represented by the following general formula (I): [ka] (In the formula, R 1 represents a hydrogen atom or an alkyl group.

[0048] The hindered amine light stabilizer of the present embodiment is a compound represented by the formula (I) above, 1 However, it is preferably an alkyl group, particularly an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0049] The hindered amine light stabilizer in this embodiment preferably has one or more skeletons of the above general formula (I), more preferably 1 to 10, particularly preferably 1 to 7, further preferably 1 to 4, and most preferably 1 to 2. The skeleton of the above general formula (I) may be present at the terminal of the hindered amine light stabilizer, or in a side chain, or may be present at the terminal and in a side chain. When the hindered amine light stabilizer has one or two skeletons of the above general formula (I), it is preferable that they be present in the side chain.

[0050] When the hindered amine light stabilizer has two or more skeletons of the general formula (I), each R 1 may be the same or different.

[0051] The hindered amine light stabilizer in this embodiment is preferably a compound in which an oxygen atom of a —COO— skeleton is bonded to the carbon atom at the 4-position in the skeleton of the general formula (I) above.

[0052] The hindered amine light stabilizer in this embodiment is particularly preferably a compound represented by the following structural formula (II) or a compound represented by the following structural formula (III). [ka] (wherein n is an integer of 1 or more). [ka] (In the formula, m is an integer of 1 or more.)

[0053] In the compound represented by the structural formula (II), n is preferably 1-20, more preferably 3-15, and even more preferably 5-10.

[0054] In the compound represented by the structural formula (III), m is preferably 1 to 20, more preferably 3 to 15, and even more preferably 5 to 10. In the formula, R 2 is preferably an alkyl group, particularly preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0055] The compound represented by the structural formula (II) and the compound represented by the structural formula (III) can be used alone, but it is preferable to use them in combination.

[0056] The content of the light stabilizer (C) in the curable composition for forming the undercoat layer is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.3 parts by mass or more, relative to 100 parts by mass of the curable component (A). This makes it easier for the gas barrier film according to this embodiment to achieve physical properties related to color change and adhesion, and to have excellent weather-resistant adhesion. Furthermore, the content of the light stabilizer (C) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the curable component (A). This improves the coatability of the curable composition for forming the undercoat layer, making it easier to form an undercoat layer with a uniform thickness, and tends to make it easier for the water contact angle to fall within the desired range.

[0057] (4) Silane coupling agent having a light stabilizing group (C1) The light stabilizer (C) contained in the curable composition for forming the underlayer may be a silane coupling agent (C1) having a light stabilizing group. The silane coupling agent (C1) having a light stabilizing group is preferably a silane coupling agent having a hindered amine light stabilizing group, and a preferred example thereof is a silane coupling agent represented by the following general formula (IV). [ka] In the above formula (IV), R3 represents an alkyl group having 1 to 3 carbon atoms. 4 represents an alkylene group or alkyleneoxy group (-O-alkylene group) having 2 to 5 carbon atoms, and X represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxyl group having 1 to 3 carbon atoms.

[0058] Specific examples of the silane coupling agent (C1) having the above-mentioned light stabilizing group include 3-(2,2,6,6-tetramethylpiperid-4-yloxypropyl)triethoxysilane and 3-(1,2,2,6,6-pentamethylpiperid-4-yloxypropyl)triethoxysilane.

[0059] By including the silane coupling agent (C1) having the above-mentioned photostabilizing group in the curable composition for forming the base layer, when an underlayer consisting of a cured coating film of the curable composition for forming the base layer is formed, it becomes possible to obtain initial adhesion to the gas barrier layer and excellent weather-resistant adhesion. In other words, the initial adhesion is due to the covalent bond between the silane coupling agent and the ultraviolet-absorbing substrate surface (i.e., the covalent bond between the silane coupling agent and a hydroxy group on the ultraviolet-absorbing substrate surface that may be present in extremely small amounts), and the excellent weather-resistant adhesion is due to the uneven distribution of the silane coupling agent near the ultraviolet-absorbing substrate interface, thereby fixing the photostabilizing group of the silane coupling agent.

[0060] Therefore, by including the silane coupling agent (C1) having the above-mentioned photostabilizing group in the curable composition for forming the base layer, a gas barrier film having superior adhesion to the gas barrier layer (initial adhesion and weather-resistant adhesion) can be obtained. The reason why a gas barrier film having better weather resistance and adhesion can be obtained by using a silane coupling agent (C1) having a light stabilizing group as the light stabilizer (C) is not limited to this, but it is presumed that one of the reasons is that the silane coupling agent (C1) having a light stabilizing group is densely present at the interface with the gas barrier layer. The peeling of the base layer described above is presumed to be mainly caused by deterioration of the interface of the base layer, and since the silane coupling agent (C1) having a light stabilizing group is densely present at the interface, it is thought that radicals generated at the interface are quickly captured and deterioration of the interface is more efficiently prevented.

[0061] The content of the silane coupling agent (C1) having the above-mentioned photostabilizing group in the curable composition for forming the undercoat layer according to this embodiment is preferably 0.1 to 3.0 parts by mass, more preferably 0.2 to 2.0 parts by mass, and even more preferably 0.3 to 1.0 part by mass, relative to 100 parts by mass of the curable component (A). By including a silane coupling agent (C1) having a light stabilizing group within the above range, it becomes easier to further improve the initial adhesion and weather-resistant adhesion between the ultraviolet absorbing substrate and the gas barrier layer.

[0062] The silane coupling agent (C1) having a light stabilizing group can be used alone or in combination of two or more kinds. In addition to the silane coupling agent (C1) having a photostabilizing group, a general silane coupling agent such as methyltrimethoxysilane can also be used in combination within a range that does not impair the effects of the present invention.

[0063] (5) Silane coupling agent (D) The silane coupling agent (D) contained in the curable composition for forming the undercoat layer does not have a light stabilizing group, unlike the silane coupling agent (C1) having the above-mentioned light stabilizing group. The silane coupling agent (D) is used together with the ultraviolet absorber (B) and the light stabilizer (C) to improve the adhesion between the ultraviolet absorber substrate and the undercoat layer, and between the gas barrier layer and the undercoat layer. Of course, the silane coupling agent (C1) having a stabilizing group and the silane coupling agent (D) may be used in combination.

[0064] The silane coupling agent (D) is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule.

[0065] Examples of the silane coupling agent (D) include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; silicon compounds having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; and mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane. Examples of the silane compound include a caprylamide group-containing silicon compound, an amino group-containing silicon compound such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, or N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, or 3-isocyanatepropyltriethoxysilane, or a condensate of at least one of these with an alkyl group-containing silicon compound such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, or ethyltrimethoxysilane. These compounds may be used alone or in combination of two or more.

[0066] The content of the silane coupling agent in the curable composition for forming the undercoat layer is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the curable component (A). The content is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less. By having the content of the silane coupling agent within the above range, the resulting undercoat layer is more likely to have improved adhesion to the ultraviolet-absorbing substrate and the gas barrier layer.

[0067] (6) Other ingredients The curable composition for forming the underlayer may contain other components as long as the effects of the present invention are not impaired. Examples of other components include photopolymerization initiators, antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, bulking agents, inorganic fillers, and coloring pigments. The content of these may be determined appropriately depending on the purpose.

[0068] 1-4.Gas barrier layer From the viewpoint of ensuring high gas barrier properties at low cost, the gas barrier film preferably has a gas barrier layer containing silicon and oxygen as main components. Here, "containing silicon and oxygen as main components" means that the total mass of silicon and oxygen is 50 mass% or more relative to the total mass of the gas barrier layer. The gas barrier layer is preferably formed from a coating of a composition containing a polysilazane compound and, optionally, a carbon-containing silicon-based polymer compound, as described below. The gas barrier layer preferably has, in the thickness direction thereof, a first region (high-nitrogen-containing region) that contains silicon, oxygen, and nitrogen, and, optionally, carbon, and has a higher nitrogen content than other regions.

[0069] As will be described later, the first region is formed by a modification process and has a relatively higher nitrogen content than the second region, which is a region other than the first region. Therefore, in the following description, the first region may also be referred to as a "modified region" or a "high-nitrogen-content region." The second region may also be referred to as a "non-modified region" or a "low-nitrogen-content region." The "high-nitrogen-content region" refers to a region that is stable over time and whose thickness does not decrease over time.

[0070] The gas barrier layer preferably has a first region containing silicon, oxygen, carbon, and nitrogen in its thickness direction, and satisfies the following requirements (1) and (2). Requirement (1): The composition of the first region is SiO x C y N z It is expressed as: x:0.20~0.50 y:0~0.30 z: 0.20~0.70 Requirement (2): The thickness d of the first region M is 10 nm or more.

[0071] The first region satisfying the above requirement (1) is thought to reflect a hard structure in which silicon and nitrogen are bonded, which is advantageous for achieving high gas barrier performance and high light transmittance. Furthermore, in the following requirement (1-1), the presence of a predetermined proportion of carbon is thought to impart appropriate flexibility to the gas barrier layer. Furthermore, as specified in the above requirement (2), it is believed that by making the thickness of the first region 10 nm or more, a region with high gas barrier properties is sufficiently ensured. In the above requirement (1), from the viewpoint of easily increasing light transmittance, it is more preferable that x, y, and z are in the following ranges (requirement (1-1)). x:0.25~0.45 y: 0.03~0.20 z: 0.20~0.65

[0072] The above thickness d MFrom the viewpoint of enhancing the gas barrier property, the thickness is preferably 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 production, it is preferably 300 nm or less, more preferably 150 nm or less, and particularly preferably 90 nm or less.

[0073] The high nitrogen content region may be located on the outermost surface of the gas barrier layer or inside the gas barrier layer, but is preferably located on the outermost surface of the gas barrier layer from the viewpoints of exhibiting good gas barrier properties and ease of production.

[0074] A plurality of high nitrogen content regions may be present in the depth direction. When a plurality of high nitrogen content regions are present, the total thickness of the regions may be 10 nm or more. From the viewpoint of preventing water vapor permeation from the edges, it is preferable that one of the plurality of high nitrogen content regions is located on the outermost surface of the gas barrier film. A gas barrier layer having a plurality of high nitrogen content regions in the depth direction can be obtained, for example, by repeating the formation of a gas barrier precursor layer for forming the gas barrier layer and the modification treatment described below.

[0075] In the depth direction of the gas barrier layer, the element ratio of nitrogen atoms can be made to gradually and continuously change from the outermost surface by forming a high nitrogen content region through a modification treatment, as will be described later. Typically, in the change in the element ratio of each element in silicon, oxygen, and nitrogen (and optionally, carbon) in the thickness direction of the gas barrier layer, there is a region where the element ratio of nitrogen is higher than in the deeper layer.

[0076] In the gas barrier film, from the viewpoint of easily ensuring high gas barrier properties and light transmittance, and good flexibility, and from the viewpoint of ease of production, the thickness d of the gas barrier layer is G and the thickness d of the first regionM However, 1.00 ≥ d M / d G ≧0.01, and 0.80≧d M / d G It is more preferable that the relationship of 0.60 ≧ d M / d G It is more preferable that the relationship is ≧0.03.

[0077] Gas barrier layer thickness d G From the viewpoint of easily ensuring gas barrier properties, light transparency, and flexibility, as well as from the viewpoint of ease of production, the thickness is preferably 30 to 1,500 nm, and more preferably 100 to 400 nm. Gas barrier layer thickness d G Even if the nitrogen content is on the order of nanometers, by providing a high nitrogen content region, a gas barrier film having sufficient gas barrier properties can be obtained.

[0078] Each of the above thicknesses d G , d M can be set within the above numerical range by producing a gas barrier film according to the gas barrier film producing method described below and adjusting the composition of the coating solution and the conditions of the modification treatment during the production.

[0079] The gas barrier layer is formed from a gas barrier precursor layer, and is preferably formed from a layer obtained by drying a coating film of a coating liquid (hereinafter also referred to as "gas barrier precursor layer coating liquid") containing a polysilazane compound and, if desired, a carbon-containing silicon-based polymer compound. The high nitrogen content region can be formed by a modification treatment described below.

[0043] By providing a high nitrogen content region obtained by subjecting the gas barrier precursor layer, which is a layer obtained by drying a coating of the above-mentioned gas barrier precursor layer coating liquid, to a modification treatment described below, a gas barrier layer with excellent gas barrier properties can be efficiently formed. In particular, when the above-mentioned modification treatment is carried out by plasma irradiation in the presence of helium gas, it becomes easier to form a high nitrogen-containing region with a sufficient thickness.

[0080]

[0023] Examples of polysilazane compounds include inorganic polysilazanes and organic polysilazanes. Examples of inorganic polysilazanes include perhydropolysilazane, and examples of organic polysilazanes include compounds in which part or all of the hydrogen atoms in perhydropolysilazane have been substituted with organic groups such as alkyl groups. Among these, inorganic polysilazanes are more preferred from the viewpoints of availability and the ability to form a gas barrier layer with excellent gas barrier properties. Furthermore, as the polysilazane compound, commercially available products available as glass coating materials and the like can also be used as they are. The polysilazane compounds can be used singly or in combination of two or more.

[0081] Examples of the carbon-containing silicon-based polymer compound include polycarbosilane-based compounds, polysilane-based compounds, and mixtures thereof.

[0082] Examples of methods for forming a layer obtained by applying and drying a coating liquid for a gas barrier precursor layer include a method in which a coating liquid for a gas barrier precursor layer containing a polysilazane compound, and optionally a carbon-containing silicon-based polymer compound, other components (for example, a curing agent, other polymers, an antioxidant, a light stabilizer, a flame retardant, etc.), a solvent, etc. is applied onto an ultraviolet-absorbing substrate by a known method, and the resulting coating film is then appropriately dried to form the layer. Since the coating liquid for the gas barrier precursor layer contains the polysilazane compound described above, a conversion reaction of the polysilazane occurs when the coating liquid is heated after coating, resulting in a coating film (gas barrier precursor layer) with gas barrier properties.

[0083] The thickness of the gas barrier precursor layer is preferably 30 to 1,500 nm, more preferably 40 to 1,000 nm, and even more preferably 100 to 400 nm. Even if the thickness of the gas barrier precursor layer is on the order of nanometers, a gas barrier film having sufficient gas barrier properties can be obtained by subsequently subjecting the layer to a modification treatment.

[0084] Examples of the modification treatment include ion implantation, vacuum ultraviolet light irradiation (irradiation with an excimer laser, etc.), etc. Among these, ion implantation is preferred because it can provide high gas barrier performance.

[0085] Examples of ions to 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 may be used alone or in combination of two or more.

[0086] The method for injecting ions is not particularly limited, but examples thereof include a method of irradiating ions (ion beam) accelerated by an electric field and a method of injecting ions in plasma. Of these, the latter method of injecting plasma ions is preferred because it allows a gas barrier film to be easily obtained.

[0087] The ion species to be implanted by plasma ion implantation include the same ions as those exemplified above as the ions to be implanted.

[0088] 1-5.Other examples of gas barrier film configurations The gas barrier film according to the embodiment of the present invention is not limited to that shown in FIG. 1, and may contain one or more other layers in one or more locations selected from the group consisting of on the ultraviolet-absorbing substrate, between the ultraviolet-absorbing substrate and the underlayer, between the underlayer and the gas barrier layer, and on the gas barrier layer, provided that the object of the present invention is not impaired. Examples of the other layers include other gas barrier layers and protective layers. The positions of the other layers are not limited to those described above.

[0089] The gas barrier film may be a long film, in which case the gas barrier film may be in the form of a roll wound around a core material.

[0090] 2. Gas barrier film manufacturing method The method for producing a gas barrier film according to an embodiment of the present invention includes the following steps. ·Process 1: Base layer formation process Step 2: Gas barrier layer formation step The above step 1 further includes the following steps. Step 1-1: Preparation of UV-absorbing substrate Step 1-2: Formation of the base layer

[0091] 2-1. Preparation of UV-absorbing substrate (Step 1-1) An ultraviolet absorbing substrate is provided.

[0092] 2-2. Formation of base layer (step 1-2) The underlayer is formed by preparing a coating liquid containing a curable composition for forming the underlayer and, if necessary, a solvent, and then coating the coating liquid on an ultraviolet-absorbing substrate by a known method, and curing the resulting coating film to form an underlayer made of a cured product of the curable composition for forming the underlayer. If necessary, a drying treatment may be performed before curing the coating film.

[0093] Examples of solvents for the coating liquid 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. These solvents can be used alone or in combination of two or more.

[0094] Examples of coating methods include bar coating, spin coating, dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing, spray coating, and gravure offset.

[0095] When drying the coating film, conventionally known drying methods such as hot air drying, heat roll drying, infrared irradiation, etc. can be used. The drying temperature is usually in the range of 60 to 130° C. The drying time is usually from a few seconds to several tens of minutes.

[0096] The coating film can be cured by irradiating the surface of the coating film (the side where the ultraviolet-absorbing substrate is not present) with active energy rays. As the active energy rays, ultraviolet rays emitted from an ultraviolet light source are preferably used. As the ultraviolet light source, light sources such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp, etc. There is no particular limitation on the amount of ultraviolet light, but it is usually 100 mJ / cm. 2 ~1,000mJ / cm 2 The irradiation time is usually from a few seconds to a few hours, and the irradiation temperature is usually from room temperature (20°C) to 100°C.

[0097] 2-3. Formation of gas barrier layer (step 2) In step 2, a gas barrier layer is formed on the underlayer according to the procedure described in the above section "1-4. Gas barrier layer." [Example]

[0098] Next, specific examples of the present invention will be described, but the present invention is not limited to these examples in any way. In the examples and comparative examples described below, the initial adhesion, initial gas barrier properties, and adhesion after weathering tests were measured and evaluated according to the following procedures.

[0099] [Initial adhesion] Following the procedures of the Examples or Comparative Examples, a base layer was formed on a UV-absorbing substrate, and then the surface of the base layer was divided into 10 x 10 sections (100 squares in total) by making incisions vertically and horizontally at 1 mm intervals. Next, a polyester adhesive tape ("No. 31B" manufactured by Nitto Denko Corporation) was pressed onto the surface of the base layer where the incisions were formed, and the tape was then peeled off while holding the edge of the adhesive tape and maintaining it perpendicular to the surface of the base layer. The percentage of peeling of the base layer from the UV-absorbing substrate was then confirmed, and the adhesion (initial adhesion) before the weathering test was evaluated. Specifically, a percentage of squares without peeling of 30% or more was evaluated as "VG," a percentage of squares without peeling of 20% to less than 30% was evaluated as "G," and a percentage of squares without peeling of less than 20% was evaluated as "NG." "VG" and "G" were evaluated as pass, and "NG" was evaluated as fail.

[0100] [Initial gas barrier properties] Following the procedures of the Examples or Comparative Examples, a base layer and a gas barrier layer were formed in this order on an ultraviolet-absorbing substrate, and then the water vapor transmission rate (WVTR) was measured to evaluate the gas barrier property before the weathering test (initial gas barrier property). -3 [g / (m 2 ·day)] or less is "G", 1.0 × 10 -3 [g / (m 2 Those exceeding 100% (100%) were evaluated as "NG." "G" was judged as pass and "NG" was judged as fail. The WVTR was measured using a water vapor transmission rate measuring device (AQUATRAN-2 (AQUATRAN is a registered trademark) manufactured by MOCON) under conditions of 90% relative humidity and 40°C.

[0101] [Adhesion after weather resistance test] Following the procedures of the Examples or Comparative Examples, a base layer and a gas barrier layer were formed in this order on an ultraviolet-absorbing substrate, and then subjected to a weathering test using an ultraviolet fluorescent lamp accelerated weathering tester QUV (Sanyo Trading Co., Ltd.) (ultraviolet lamp: UVA-340+, 60°C, 1.23 W / m 2The UV-irradiated gas barrier layer surface was divided into 10 × 10 sections (100 squares in total) by making cuts at 1 mm intervals in both the vertical and horizontal directions. A polyester adhesive tape (Nitto Denko Corporation's "No. 31B") was then attached to the cut-formed surface of the gas barrier layer, and the tape was peeled off while holding the edge of the tape perpendicular to the surface of the gas barrier layer. The percentage of peeled sections from the UV-absorbing substrate or underlayer was then checked. A percentage of unpeeled sections of 20% or more was evaluated as "VG," 10% to less than 20% as "G," and less than 10% as "NG." "VG" and "G" were evaluated as pass, and "NG" as fail.

[0102] [Example 1] A composition for forming an undercoat layer was prepared by adding 0.4 parts by mass of 3-(2,2,6,6-tetramethylpiperid-4-yloxypropyl)triethoxysilane as a silane coupling agent (C1) having a light stabilizing group to 100 parts by mass (solid content equivalent; same below) of an organic-inorganic hybrid resin (Opstar Z7530 manufactured by Arakawa Chemical Industries, Ltd., a mixture of a substance formed by bonding acryloyl groups to silica microparticles and a polyfunctional (meth)acrylate monomer) as a curable component (A) and diluting with propylene glycol monomethyl ether (PGM). The obtained undercoat layer-forming composition was applied to the untreated side of a 50 μm-thick ultraviolet-absorbing polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., HB3, transmittance at 360 nm: 1.468%) that had been subjected to a one-side easy-slip treatment, and then the film was dried by heating at 80°C for 1 minute and irradiated with ultraviolet light (light intensity: 250 mJ / cm 2 , Illuminance: 190mW / cm 2 ) to form a base layer. The thickness of the base layer was 1.0 μm. Next, perhydropolysilazane (manufactured by DNF, weight average molecular weight 10,000 g / mol) was applied onto the underlayer and dried at 120°C for 2 minutes to form a polysilazane layer with a thickness of 250 nm. Next, using a plasma ion implantation device, plasma ion implantation was performed on the polysilazane layer under the following conditions to modify the surface of the polysilazane layer (thickness of modified region: 25 nm), thereby obtaining a gas barrier film. The plasma ion implantation apparatus and plasma ion implantation conditions used in the above modification treatment are as follows: (Plasma ion implantation equipment) RF power supply: Model number "RF56000", manufactured by JEOL Ltd. High-voltage pulse power supply: "PV-3-HSHV-0835", manufactured by Kurita Manufacturing Co., Ltd. (Plasma ion implantation conditions) Plasma generating gas: Helium (He) Gas flow rate: 100sccm ·Duty ratio: 0.5% Repetition rate: 1,000Hz Applied voltage: -8kV ·RF power supply: Frequency 13.56MHz, applied power 1,000W Chamber pressure: 0.2 Pa Pulse width: 5μsec Processing time (ion implantation time): 200 seconds

[0103] [Example 2] A composition for forming a base layer was prepared in the same manner as in Example 1, except that 0.4 parts by mass of each of a hindered amine-based light stabilizer (manufactured by ADEKA Corporation, product name "LA77Y") and 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-403") was added per 100 parts by mass of the curable component (A) instead of the silane coupling agent (C1) having the above stabilizing group, and a gas barrier film was obtained using the same procedure as in Example 1.

[0104] [Example 3] A gas barrier film was obtained in the same manner as in Example 1, except that 0.4 parts by mass of a hydroxyphenyltriazine-based ultraviolet absorber (manufactured by BASF Japan Ltd., product name "Tinuvin 477") was used per 100 parts by mass of the curable component (A) instead of the silane coupling agent (C1) having the stabilizing group.

[0105] [Comparative Example 1] A gas barrier film was obtained in the same manner as in Example 1, except that the silane coupling agent (C1) having a stabilizing group was not used.

[0106] Comparative Example 2 A gas barrier film was obtained in the same manner as in Example 1, except that 0.4 parts by mass of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-403") was used per 100 parts by mass of the curable component (A) instead of the silane coupling agent (C1) having a stabilizing group.

[0107] The evaluation results for each of the examples and comparative examples are shown in Table 1.

[0108] [Table 1]

[0109] As is clear from the results in Table 1, in Examples 1 to 3, which had a UV-absorbing substrate and an undercoat layer formed from (i) a curable composition containing a curable component (A) and a silane coupling agent (C1) having a light-stabilizing group, (ii) a curable composition containing a curable component (A), a light stabilizer (C), and a silane coupling agent (D), or (iii) a curable composition containing a curable component (A) and a UV absorber (B), the initial adhesion and initial gas barrier properties were high and the adhesion after the weathering test was good. In particular, Example 1, which used a silane coupling agent (C1) having a light-stabilizing group, and Example 2, which used a light stabilizer (C) and a silane coupling agent (D), showed better adhesion after the weathering test. On the other hand, the gas barrier films of Comparative Examples 1 and 2, in which the undercoat layer did not contain any of the silane coupling agent (C1) having a light stabilizing group, the light stabilizer (C), and the ultraviolet absorber (B), had good initial adhesion and initial gas barrier properties, but their adhesion after weather resistance testing was inferior to that of the gas barrier films of Examples 1 to 3. [Explanation of symbols]

[0110] 10: UV-absorbing substrate 20: Base layer 30: Gas barrier layer 100: Gas barrier film

Claims

1. A gas barrier film comprising an ultraviolet absorbing substrate, an underlayer, and a gas barrier layer laminated in this order, the underlayer containing at least one selected from the group consisting of an ultraviolet absorber and a light stabilizer.

2. 2. The gas barrier film according to claim 1, wherein the ultraviolet absorbing substrate is a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm.

3. 3. The gas barrier film according to claim 1, wherein the thickness of the underlayer is 0.5 to 3 μm.

4. 3. The gas barrier film according to claim 1, wherein the ultraviolet absorbing substrate has a thickness of 5 to 500 μm.

5. Water vapor permeability is 1.0 x 10 －３ g / (m ２ 3. The gas barrier film according to claim 1, wherein the average temperature is 100°C or less.

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