JP7122108B2 - Ionizing radiation curable resin composition, protective film for gas barrier layer using the same, and laminated gas barrier film using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an ionizing radiation-curable resin composition, a protective film for a gas barrier layer using the same, a laminated gas barrier film using the same, and the like.

Conventionally, gas barrier films are known in which gas barrier properties are imparted by forming a thin film of an inorganic compound such as silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, or magnesium oxide on the surface of a plastic substrate or film. Gas barrier films of this type have been used in sealed packaging containers for articles such as foods, cosmetics, and pharmaceuticals, in order to prevent deterioration of articles due to gases such as water vapor and oxygen.

In recent years, such gas barrier films that prevent permeation of water vapor, oxygen, etc., have been used in photoelectric conversion elements, solar cells (PV), electronic paper, liquid crystal displays (LCDs), organic EL displays (OELDs), and other flat panel displays. It is also being used in the field of electronic devices such as (FPD). These electronic devices are particularly susceptible to the effects of moisture, etc., and the performance of the liquid crystal layer and light-emitting layer is likely to be degraded. Higher gas barrier properties (blocking properties) are required compared to gas barrier films used for packaging.

As a gas barrier film of this kind, there is widely known one in which an inorganic thin film of an inorganic compound such as silicon oxide or an organic thin film of a thermosetting resin is formed as a gas barrier layer on a base material such as polyethylene terephthalate (PET). ing. Methods for forming the gas barrier layer include physical vapor deposition (PVD) such as vacuum deposition, sputtering, and ion plating, chemical vapor deposition such as low pressure chemical vapor deposition, and plasma chemical vapor deposition. Vapor deposition (CVD: Chemical Vapor Deposition), various coating methods, and the like are known.

In addition, since the gas barrier layer of an inorganic compound film such as silicon oxide is relatively hard and brittle, it is necessary to prevent the gas barrier layer from being scratched, prevent the gas barrier layer from being peeled off by a solvent or the like, or improve the handleability. From a viewpoint, a protective layer may be further provided on the gas barrier layer. For example, when used in an organic EL display or the like, a protective layer is provided on the gas barrier layer, a transparent conductive film is further formed on this protective layer, and patterning is performed by etching or the like to form a circuit.

As a laminated gas barrier film provided with such a protective layer, Patent Document 1 discloses a base film, a vapor deposited barrier layer having a smooth surface provided on at least one surface of the base film, and the an acid-resistant protective layer having a smooth surface laminated on the vapor deposition layer with barrier properties, and having an oxygen permeability of 0.1 cc/m ² /day·atm or less and a water vapor permeability of 0.1 g/m ² . /day or less, and the barrier deposition layer is made of indium zinc oxide, and the atomic ratio of indium (In) and zinc (Zn) in the indium zinc oxide is In/(In + Zn) of 0.5 to 0. The acid resistance of the protective layer is such that the etching rate with an indium tin oxide etchant having a volume mixing ratio of hydrochloric acid:nitric acid:water of 1:0.08:1 is 0.01 μm/min or less. A gas barrier film is described which is characterized by:

Further, in Patent Document 2, a gas barrier layer composed mainly of an indium cerium-based oxide is formed on at least one side of a base material made of a plastic film, and a protective layer is further provided thereon. is a layer capable of protecting the gas barrier layer from etching.

However, the gas barrier films described in Patent Documents 1 and 2 are inferior in adhesion between the energy ray-curable resin composition and the gas barrier layer, and there is still a large room for improvement.

In order to solve such a problem, Patent Document 3 discloses a base material, a gas barrier layer provided on at least one surface of the base material, and a protective layer provided on the gas barrier layer, wherein the protective layer is , (A) an aromatic ring-containing urethane (meth) acrylate, (B) a carboxyl group-containing (meth) acrylate, and (C) a polyfunctional (meth) acrylate, and an acid value per 1 g of dry mass of 80 mg KOH / g or more There has been proposed a gas barrier film characterized by being formed using an energy ray-curable resin composition having a viscosity of 130 mgKOH/g or less.

Patent No. 4414748 Patent No. 4617583 Patent No. 5752438

However, in Patent Document 3, since a relatively highly oxidized protective layer is used, for example, the inorganic gas barrier layer is likely to be corroded or deteriorated. There was a problem that the adhesiveness tends to decrease.

The present invention has been made in view of the above problems, and an object of the present invention is to provide an ionizing radiation-curable resin composition capable of realizing a gas barrier film having excellent adhesion and durability, and a gas barrier layer using the same. It is an object of the present invention to provide a protective film and a laminated gas barrier film or the like using the protective film and having excellent adhesion and durability.

The present inventors have made intensive studies to solve the above problems. As a result, the inventors have found that the above problems can be solved by forming a protective layer with relatively low oxidation using an ionizing radiation-curable resin composition containing a predetermined adhesion promoter, and have completed the present invention. reached. That is, the present invention provides various specific aspects shown below.

[1] An adhesion promoter having an acid value of 120 (mgKOH/g) or more and 400 (mgKOH/g) or less and a molecular weight of 80 to 900, and an ionizing radiation-curable matrix-forming material (which corresponds to the adhesion promoter and an inorganic filler, and the adhesion promoter is 1 to 25 parts by mass with respect to a total of 100 parts by mass of the adhesion promoter and the ionizing radiation-curable matrix-forming material. % included,
An ionizing radiation-curable resin composition having an acid value of 20 (mgKOH/g) or more and 50 (mgKOH/g) or less per 1 g of dry mass of a cured product after curing.

[2] The adhesion promoter includes a monofunctional (meth)acrylate containing a carboxyl group, a monofunctional urethane (meth)acrylate containing a carboxyl group, a sulfonic acid ester having a (meth)acryloyl group, and (meth)acryloyl. The ionizing radiation-curable resin composition according to [1], which is at least one selected from the group consisting of phosphate esters having groups.
[3] The ionizing radiation-curable resin composition according to [1] or [2], further containing a ketone solvent.

[4] A protective film for a gas barrier layer, comprising a cured product of the ionizing radiation-curable resin composition according to any one of [1] to [3].

[5] At least a gas barrier layer and a protective layer provided on the gas barrier layer, wherein the protective layer cures the ionizing radiation curable resin composition according to any one of [1] to [3]. wherein the protective layer has an acid value of 20 (mgKOH/g) or more and 50 (mgKOH/g) or less per 1 g of dry mass.
[6] The laminated gas barrier film of [5], wherein the gas barrier layer is a water vapor barrier layer.
[7] The laminated gas barrier according to [6], wherein the gas barrier layer has a water vapor transmission rate (MOCON method, JIS K7129 compliant, 40° C. and 90% RH) of less than 1×10 ⁻¹ g/m ² ·day. sex film.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an ionizing radiation-curable resin composition capable of realizing a gas barrier film having excellent adhesion and durability, and a protective film for a gas barrier layer using the same. A gas barrier film having excellent durability can be provided.

1 is a cross-sectional view schematically showing a laminated gas barrier film of a first embodiment; FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Unless otherwise specified, positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings. Also, the dimensional ratios in the drawings are not limited to the illustrated ratios. However, the following embodiments are examples for explaining the present invention, and the present invention is not limited to these. In this specification, the expression of a numerical range such as "1 to 100" includes both the upper limit of "1" and the lower limit of "100". The same applies to the notation of other numerical ranges. Moreover, in this specification, (meth)acrylate means acrylate and/or methacrylate, and (meth)acrylic acid means acrylic acid and/or methacrylic acid. The same applies to other expressions such as (meth)acryloyl.

(First embodiment)
<Laminated gas barrier film>
FIG. 1 is a cross-sectional view schematically showing a laminated gas barrier film 100 of a first embodiment of the invention. The laminated gas barrier film 100 of the present embodiment comprises a substrate 11, a resin layer 21 provided on one main surface 11a of the substrate 11, and a resin layer 21 provided on one main surface 21a. and a protective layer 41 provided on one main surface 31a of the gas barrier layer 31 . This laminated gas barrier film 100 has a laminated structure (four-layer structure) in which at least a substrate 11, a resin layer 21, a gas barrier layer 31, and a protective layer 41 are laminated in this order.

Here, in this specification, "the resin layer 21 provided on one main surface 11a side of the base material 11" means that the resin layer 21 is formed on the surface (for example, the main surface 11a) of the base material 11 as shown in FIG. is placed directly on the surface of the substrate 11, and also includes a mode in which any layer (for example, a primer layer, an adhesive layer, an anchor layer, etc.) is interposed between the surface of the substrate 11 and the resin layer 21. In addition, other similar descriptions have the same meaning.

<Base material>
The base material 11 is a member that supports the resin layer 21 , the gas barrier layer 31 and the protective layer 41 . As the substrate 11, known substrates can be used as long as they can support these layers, and the type thereof is not particularly limited. From the viewpoint of dimensional stability, mechanical strength and the like, synthetic resin films, glass and the like are generally preferably used. Furthermore, synthetic resin films are more preferably used from the viewpoint of weight reduction and the like.

Synthetic resins used as the base material 11 include, for example, polyolefin resins such as polyolefin resins such as homopolymers or copolymers such as ethylene, polypropylene and butene; cyclic olefin polymers (COP), cyclic olefin copolymers (COC) and the like Amorphous polyolefin resins; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); polyamide resins such as nylon 6, nylon 12, and copolymerized nylon; polycarbonate resins Polystyrene resins; ABS (acrylonitrile-butadiene-styrene) resins; polyvinyl alcohol resins such as polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH); polyimide resins; Cellulose resins such as acetyl cellulose; Acrylic resins such as (meth)acrylic acid esters; Polyether sulfone resins; Polyether ether ketone resins; Polyvinyl chloride, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile Polyvinyl chloride resins such as copolymers, vinylidene chloride-acrylic copolymers; polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether Examples include fluorine-containing resins such as copolymers (PFA), but are not particularly limited to these. Among these, polyester-based resin films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are suitable as the substrate 11 . Among them, a uniaxially or biaxially oriented film, particularly a biaxially oriented polypropylene (OPP) film is particularly preferable because of its excellent mechanical strength and dimensional stability. Monoaxially or biaxially oriented polyimide films are particularly preferred for heat resistant applications. These can be used individually by 1 type, and can also be used in combination of 2 or more type. Moreover, the multilayer film which consists of several layers may be sufficient.

Although the transparency of the substrate 11 is not particularly limited, it is preferably optically transparent in electronic device applications such as touch panels. At this time, the total light transmittance of the substrate 11 is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. In addition, from the viewpoint of improving adhesion to the resin layer 21 and any of the layers described above, the surface of the base material 11 may be subjected to plasma treatment, corona discharge treatment, flame treatment, far-ultraviolet irradiation treatment, and anchor treatment, if necessary. Various known surface treatments such as treatment and chemical treatment can also be performed. For example, as an anchor treatment, an anchor coat layer is formed by applying an anchor coating agent such as polyester-based oil, isocyanate-based, urethane-based, acrylic-based, ethylene-vinyl alcohol-based, vinyl-modified, epoxy-based, modified styrene-based, or modified silicone-based anchor coating agents. By providing it, the adhesion between the base material 11 and the gas barrier layer 31 can be improved. Moreover, in order to improve durability, weather resistance, etc., the substrate 11 may contain an ultraviolet absorber or a light stabilizer.

The thickness of the base material 11 can be appropriately set according to the required performance and application, and is not particularly limited. From the viewpoint of weight reduction and thinning, handling properties, mechanical strength, etc., the thickness of the substrate 11 is generally preferably 5 to 500 μm, more preferably 10 to 300 μm.

It is preferable to select the resin film used as the base material 11 according to the application and required properties. For members, optical members, etc., it is preferable to use a resin film that itself has a high gas barrier property, such as polyethylene naphthalate, polyimide resin, polyethersulfone resin, amorphous polyolefin resin, and the like.

<Resin layer>
The resin layer 21 is for enhancing the surface smoothness and surface hardness of the substrate 11 . By providing the resin layer 21 having a smooth surface in this manner, the smoothness of the gas barrier layer 31 and the protective layer 41 provided on the upper surface side of the resin layer 21 can be improved, thereby providing a gas barrier for the entire laminated gas barrier film 100. can improve sexuality.

Various known materials can be used as the resin layer 21, and the type is not particularly limited. Generally, it is composed of a thin film of thermoplastic resin, thermosetting resin, ionizing radiation curable resin, or the like. Thermoplastic resins and thermosetting resins include saturated or unsaturated polyester resins, acrylic resins, acrylic urethane resins, polyester acrylate resins, polyurethane acrylate resins, epoxy acrylate resins, urethane resins, and epoxy resins. Resins, vinyl resins, polycarbonate resins, cellulose resins, acetal resins, polyethylene resins, polystyrene resins, polyamide resins, polyimide resins, melamine resins, phenol resins, silicone resins, etc. , but not limited to these. These can be used individually by 1 type or in combination of 2 or more types. In addition, resin thin films such as ionizing radiation-curable resins and organic-inorganic hybrid ionizing radiation-curable resins can also be preferably used. A detailed description of these will be omitted here since they will be described later in the protective layer 41 .

The thickness of the resin layer 21 can be appropriately set according to the required performance and application, and is not particularly limited. From the standpoint of weight reduction and thinning, handling properties, mechanical strength, etc., the thickness of the resin layer 21 is generally preferably 0.5 to 50 μm, more preferably 1 to 10 μm.

<Gas barrier layer>
The gas barrier layer 31 is provided on the substrate 11 side to be protected (for example, a photoelectric conversion element, a solar cell, electronic paper, a liquid crystal display (LCD), an organic EL display (OELD), a flat panel display (FPD), etc.). electronic devices, etc.) are provided to prevent performance deterioration due to contact with oxygen or water vapor. The barrier property of the gas barrier layer 31 can be appropriately set according to the type of object to be protected, required performance, application, etc., and is not particularly limited.

For example, in flexible substrate applications, the oxygen permeability of the gas barrier layer 31 is preferably less than 1×10 ⁻¹ cc/m ² ·day·atm, more preferably 1×10 ⁻² cc/m ² ·day·atm or less. is. In this specification, the oxygen transmission rate means a value measured under conditions of 40° C. and 90% RH by the MOCON method using an oxygen transmission rate measuring device in accordance with JIS K7129.

Similarly, in flexible substrate applications, the water vapor transmission rate of the gas barrier layer 31 is preferably less than 1×10 ⁻¹ g/m ² ·day, more preferably 1×10 ⁻² g/m ² ·day or less. be. In this specification, water vapor transmission rate means a value measured under conditions of 40° C. and 90% RH by the MOCON method using a water vapor transmission rate measuring device in accordance with JIS K7129. Such a gas barrier layer having a high water vapor permeability (hereinafter also referred to as a "water vapor gas barrier layer") is generally composed of an inorganic thin film, and the inorganic thin film is not only relatively hard and brittle, Many of them are inferior in adhesion to conventionally used protective films. Therefore, when a water vapor gas barrier layer made of such an inorganic thin film is used as the gas barrier layer 31, the effects of the present invention tend to be remarkably exhibited.

As the gas barrier layer 31, one known in the art can be applied, and the type is not particularly limited. Various inorganic thin films having the above-described favorable gas barrier properties are known in the art and can be used as gas barrier layer 31 . Specifically, gas barrier layers containing metals such as copper and silver, light metals such as aluminum and titanium, semimetals such as silicon, or compounds thereof (metallic compounds, inorganic compounds) (hereinafter simply referred to as "inorganic gas barrier layers") Also called.) is preferably used. Among these, a gas barrier layer made of an inorganic compound is more preferable from the viewpoint of the permeability of oxygen, water vapor, and the like, the cost, and the like.

The gas barrier layer 31 can be constructed as a thin film of a metal, a metal compound, or an inorganic compound. Here, examples of metal compounds and inorganic compounds include oxides, nitrides, carbides, oxynitrides of silicon, aluminum, magnesium, calcium, zirconium, boron, hafnium, barium, zinc, tin, titanium, selenium, indium, etc. substances, oxycarbides, nitride carbides, and those doped with other metals (tin, zinc, gallium, antimony, etc.), but are not particularly limited to these. Among these, silicon-based inorganic oxides such as silicon oxide, silicon oxynitride, and silicon oxycarbide, indium-tin oxide (ITO), indium-gallium-zinc oxide (IGZO), and indium-gallium oxide (IGO) , Gallium Zinc Oxide (GZO), Zinc Tin Oxide (ZTO), Indium Zinc Tin Oxide (IZTO), Indium Gallium Zinc Tin Oxide (IGZTO), Antimony Tin Oxide (ATO) ) is more preferably used. These can be used individually by 1 type or in combination of 2 or more types. As a method for forming the gas barrier layer 31, a method known in the art can be applied and is not particularly limited. For example, a vacuum vapor deposition method, a sputtering method, a plasma CVD method, an ion assist method, a spray method, a spin coating method and the like can be used. Moreover, the gas barrier layer 31 is preferably optically transparent, which enables the entire laminated gas barrier film 100 to be transparent, and can be suitably used for the above-described FPD applications, for example.

The thickness of the gas barrier layer 31 is not particularly limited, and can be appropriately set according to the constituent material, required performance, and application. From the standpoint of weight reduction and thinning, handling properties, mechanical strength, etc., the thickness of the gas barrier layer 31 is generally preferably 5 to 500 nm, more preferably 20 to 300 nm. The gas barrier layer 31 may be formed of only one inorganic layer made of the metal, metal compound, or inorganic compound described above, or may be formed by laminating a plurality of such inorganic layers. organic layers may be alternately laminated. In any case, it is preferable that at least the inorganic layer (inorganic gas barrier layer) of the gas barrier layer 31 and the protective layer 41 are adjacent to each other. This tends to increase the adhesion between the gas barrier layer 31 and the protective layer 41 .

<Protective layer>
The protective layer 41 is a film (protective film) for protecting the gas barrier layer 31 . By providing the protective layer 41 in this way, the gas barrier layer 31 can be prevented from being scratched, and the gas barrier layer 31 can be prevented from being partially damaged or partially peeled off, and the handleability of the laminated gas barrier film 100 as a whole can be improved.

In the present embodiment, the protective layer 41 is made of a cured product of an ionizing radiation-curable resin composition, and has an acid value of 20 (mgKOH/g) or more and 50 (mgKOH/g) or less per 1 g of dry mass. be. In addition, an acid value means the value measured by the neutralization titration method with a potassium hydroxide standard solution according to JISK0070. Since the acid value of the protective layer 41 is 20 (mgKOH/g) or more and 50 (mgKOH/g) or less, the laminated gas barrier property is not only excellent in adhesion between the gas barrier layer 31 and the protective layer 41 but also excellent in durability. A film 100 can be realized. From the viewpoint of the balance between adhesion and durability, the acid value of the protective layer 41 is preferably 20 (mgKOH/g) or more and 45 (mgKOH/g) or less per 1 g of dry mass, and 20 (mgKOH/g) or more and 40 (mgKOH/g). g) More preferably:

(Ionizing radiation curable resin composition)
The protective layer 41 having the above acid value can be obtained by curing a predetermined ionizing radiation curable resin composition. In the present embodiment, a resin material that forms a matrix (resin film) of the protective layer 41 by cross-linking and curing by irradiation with ionizing radiation (ultraviolet rays or electron beams) (hereinafter referred to as an “ionizing radiation-curable matrix-forming material”) ), an acid value of 120 (mgKOH/g) or more and 400 (mgKOH/g) or less and an adhesion promoter and an inorganic filler having a molecular weight of 80 to 900 (inorganic component and/or an externally added inorganic filler) is used to adjust the acid value of the protective layer 41 . Each component will be described in detail below.

As the ionizing radiation-curable matrix-forming material, a photo-cationically polymerizable resin, a photopolymerizable prepolymer, a photopolymerizable monomer, or the like (hereinafter sometimes referred to as an "ionizing radiation-curable matrix-forming material") .) or a mixture of two or more thereof can be used. However, in the present specification, those corresponding to adhesion promoters having an acid value of 120 (mgKOH/g) or more and 400 (mgKOH/g) or less and a molecular weight of 80 to 900 refer to this ionizing radiation-curable matrix-forming material. excluded from.

Specific examples of photo-cationically polymerizable resins include epoxy resins such as bisphenol-based epoxy resins, novolac-type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins, vinyl ether-based resins, and the like, but are particularly limited to these. not. These can be used individually by 1 type or in combination of 2 or more types.

Photopolymerizable prepolymers are generally classified into cationic polymerization type and radical polymerization type. Examples of cationic polymerization type photopolymerizable prepolymers include epoxy resins and vinyl ether resins. Examples of epoxy-based resins include bisphenol-based epoxy resins, novolak-type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Radical polymerization type photopolymerizable prepolymers include acrylic prepolymers (hard prepolymers). A photopolymerizable prepolymer can be used individually by 1 type or in combination of 2 or more types. Among these, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and forming a three-dimensional network structure by cross-linking and curing is preferably used. Specifically, polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyether (meth)acrylate, polyol (meth)acrylate, melamine (meth)acrylate, polyfluoroalkyl (meth)acrylate, Examples thereof include various (meth)acrylates such as silicone (meth)acrylate, but are not particularly limited thereto. Although these photopolymerizable prepolymers can be used alone, it is preferable to further add a photopolymerizable monomer from the viewpoint of improving cross-linking curability and further improving the hardness of the protective layer 41 .

Photopolymerizable monomers include monofunctional (meth)acrylates such as methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butoxyethyl acrylate; Bifunctional (meth)acrylates such as 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate ester neopentyl glycol diacrylate; dipentaerythritol hexaacrylate, trimethyl Trifunctional or higher (meth)acrylates such as propane triacrylate and pentaerythritol triacrylate; styrene monomers such as styrene and α-methylstyrene; unsaturated carboxylic acid amides such as (meth)acrylamide; (meth)acrylic acid -2-(N,N-diethylamino)ethyl, substituted aminoalcohol esters of unsaturated acids such as -2-(N,N-dibenzylamino)ethyl (meth)acrylate, ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, isocyanuric acid triacrylate (e.g. tris-(2-hydroxyethyl)-isocyanurate ester (meth)acrylate, etc.), 3-phenoxy-2-propanoyl acrylate , 1,6-bis(3-acryloxy-2-hydroxypropyl)-hexyl ether and other polyfunctional compounds, and trimethylolpropane trithioglycolate, pentaerythritol tetrathioglycolate having two or more molecules in the molecule. Examples include polythiol compounds having a thiol group, but are not particularly limited thereto. These can be used individually by 1 type or in combination of 2 or more types. Among these, polyfunctional (meth)acrylates having hydroxyl groups are preferable from the viewpoint of further improving the adhesion to the gas barrier layer 31 .

Among these, polyfunctional (meth)acrylates having a hydroxyl group and not having a carboxylic acid group are preferably used as the photopolymerizable monomer. Specific examples of such polyfunctional (meth)acrylates include glycerin di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene Oxide-modified trimethylolpropane di(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane di(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, butylene oxide-modified Trimethylolpropane di(meth)acrylate, butylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl)isocyanuric acid di(meth)acrylate, tris(2-hydroxyethyl)isocyanuric acid tri(meth)acrylate , pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, propylene oxide-modified pentaerythritol tetra(meth)acrylate, Propylene oxide-modified pentaerythritol tri(meth)acrylate, butylene oxide-modified pentaerythritol tetra(meth)acrylate, butylene oxide-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate ) acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate and the like, but are not particularly limited thereto. These can be used individually by 1 type or in combination of 2 or more types.

Here, when the ionizing radiation curable resin composition is cured by ultraviolet irradiation, it may be referred to as a so-called ultraviolet curable resin (composition) (hereinafter, “UV curable resin (composition)”. ) can be used as In this case, the ultraviolet-curable resin (composition) includes the above-described photocationically polymerizable resin, photopolymerizable prepolymer, or photopolymerizable monomer, as well as a photopolymerization initiator and a sensitizer (for example, an ultraviolet sensitizer). , and a photopolymerization accelerator.

Photopolymerization initiators include acetophenones, benzophenones, Michler's ketone, benzoin, benzyl methyl ketal, benzoyl benzoate, hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-(methylthio)phenyl)-2-(4-morpholinyl )-In addition to 1-propane, α-acyl oxime esters, thioxanthone, etc., onium such as aromatic sulfonium ion, aromatic oxosulfonium ion, aromatic iodonium ion, tetrafluoroborate, hexafluorophosphate, hexafluoroantimony onium salts, sulfonate esters, organometallic complexes, and the like, which are composed of anions such as hexafluoroarsenate and the like, but are not particularly limited thereto. Examples of UV sensitizers include n-butylamine, triethylamine, tri-n-butylphosphine and the like, but are not particularly limited to these. In addition, the photopolymerization accelerator can reduce the polymerization hindrance caused by air during curing and increase the curing speed. Examples include isoamyl p-dimethylaminobenzoate and ethyl p-dimethylaminobenzoate. Examples include, but are not limited to, these. A hardening auxiliary agent can be used individually by 1 type or in combination of 2 or more types.

The content of these auxiliaries can be appropriately set according to the desired performance, and is not particularly limited, but is generally 0.1 to 10 mass in total with respect to the total solid content of the ionizing radiation curable resin composition. %, more preferably 0.5 to 5% by mass.

If necessary, a reactive resin obtained by introducing a photocurable unsaturated group into a thermoplastic resin or a thermosetting resin can also be used. Examples of thermoplastic resins used here include polyester-based resins, acrylic-based resins, polycarbonate-based resins, cellulose-based resins, acetal-based resins, vinyl-based resins, polyethylene-based resins, polystyrene-based resins, polypropylene-based resins, and polyamide-based resins. , polyimide-based resins, fluorine-based resins, and the like, but are not particularly limited to these. Examples of thermosetting resins include polyester acrylate-based resins, polyurethane acrylate-based resins, epoxy acrylate-based resins, epoxy-based resins, melamine-based resins, phenol-based resins, and silicone-based resins. Not limited. The photocurable unsaturated group to be introduced into the thermoplastic resin or thermosetting resin is preferably an ionizing radiation-curable unsaturated group. Specific examples thereof include ethylenically unsaturated bonds such as (meth)acryloyl groups, styryl groups, vinyl groups and allyl groups, and epoxy groups. A (meth)acryloyl group is more preferred.

The glass transition temperature (Tg) of the reactive resin described above is not particularly limited, but is preferably 45° C. or higher, more preferably 80° C., from the viewpoint of easily suppressing the flow of the ionizing radiation curable resin during the curing process. °C or higher, more preferably 90°C or higher. The Tg referred to here is the value before the resin A is cured. Also, the weight average molecular weight (Mw) of the reactive resin is not particularly limited, but from the same viewpoint, it is preferably 70,000 or more, more preferably 80,000 or more. The value of the weight average molecular weight (Mw) is obtained by measuring the molecular weight distribution of the compound by, for example, a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID), and obtaining a chromatogram ( Chart) can be calculated using standard polystyrene as a calibration curve.

In addition, as the ionizing radiation-curable resin composition, a material that forms an ionizing radiation-curable organic-inorganic hybrid resin by cross-linking and curing by irradiation with ionizing radiation (ultraviolet rays or electron beams) (hereinafter referred to as “organic-inorganic matrix-forming material ) can also be used. Here, the ionizing radiation-curable organic-inorganic hybrid resin is different from the traditional composites represented by glass fiber reinforced plastics (FRP), in which the organic matter and the inorganic matter are closely mixed, and the dispersed state is at the molecular level. or a similar one, in which the inorganic component and the organic component react with each other upon exposure to ionizing radiation to form a film. When the protective layer 41 contains the ionizing radiation-curable organic-inorganic hybrid resin, the adhesion to the gas barrier layer 31 tends to be further enhanced. When using an organic-inorganic matrix-forming material containing an inorganic component, the ionizing radiation-curable resin composition of the present embodiment is treated as containing the inorganic component of the organic-inorganic matrix-forming material as an inorganic filler, as described above. .

Examples of the inorganic component of the organic-inorganic matrix-forming material include metal oxides such as silica and titania, with silica being preferred. Examples of silica include reactive silica into which a photosensitive group having photopolymerization reactivity is introduced on the surface. For example, four groups represented by the following general formulas (1) and (2), a hydrolyzable silyl group, and a polymerizable unsaturated group are added to the base powdery silica or colloidal silica in the molecule. A compound having a compound chemically bonded via a silyloxy group by hydrolysis reaction of a hydrolyzable silyl group can be used.

（式（１）中、Ｘは－ＮＨ－、酸素原子又は硫黄原子を表し、Ｙは酸素原子又は硫黄原子を表し、但し、Ｘが酸素原子のとき、Ｙは硫黄原子である。）

(In formula (1), X represents -NH-, an oxygen atom or a sulfur atom, Y represents an oxygen atom or a sulfur atom, provided that when X is an oxygen atom, Y is a sulfur atom.)

Examples of hydrolyzable silyl groups include carboxylylate silyl groups such as alkoxyryl groups and acetoxyryl groups, halogenated silyl groups such as crosilyl groups, aminosilyl groups, oximesilyl groups, and hydridosilyl groups. is not particularly limited to Examples of polymerizable unsaturated groups include acryloyloxy, methacryloyloxy, vinyl, propenyl, butadienyl, styryl, ethynyl, cinnamoyl, maleate, and acrylamide groups, but are not particularly limited thereto. .

The average particle diameter _D50 of the reactive silica can be appropriately set according to the desired performance, and is not particularly limited, but is preferably 1 nm or more and 10 μm or less, more preferably less than 100 nm, and still more preferably 10 nm or less. By using reactive silica having an average particle diameter D ₅₀ within a predetermined range, it tends to be easy to maintain high adhesion to the protective layer 41 and high transparency of the protective layer 41 . The average particle diameter D ₅₀ of reactive silica means the median diameter measured with a laser diffraction particle size distribution analyzer (eg, SALD-7000, Shimadzu Corporation).

The content of the inorganic component in the organic-inorganic hybrid resin can be appropriately set according to the desired performance, and is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 70% by mass or less. , more preferably 60% by mass or less. When the content of the inorganic component is within the above preferred range, the adhesion between the gas barrier layer 31 and the protective layer 41 tends to be improved while maintaining the transparency of the protective layer 41 .

As the organic component in the organic-inorganic hybrid resin, the above inorganic component (preferably reactive silica) and a compound having a polymerizable unsaturated group (for example, two or more polymerizable unsaturated groups in the molecule or a monounsaturated organic compound having one polymerizable unsaturated group in the molecule, etc.).

Examples of polyunsaturated organic compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, 1,4-butanediol di(meth)acrylate. , 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dicyclopentanyl di(meth)acrylate, pentaerythritol tri(meth)acrylate, penta Erythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate , tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate and the like (meth)acrylates, but are not particularly limited thereto. These can be used individually by 1 type or in combination of 2 or more types. Among these, polyfunctional (meth)acrylates having no carboxylic acid group are preferably used as the polyunsaturated organic compound.

Examples of monounsaturated organic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, and lauryl (meth) acrylate. ) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylates, glycerol (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, butoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-methoxypropyl (meth)acrylate, methoxydipropylene glycol (meth)acrylate , methoxytripropylene glycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate and the like (meth)acrylates, but are not particularly limited thereto. These can be used individually by 1 type or in combination of 2 or more types. Among these, monofunctional (meth)acrylates having no carboxylic acid group are preferably used as monounsaturated organic compounds.

The content of the inorganic component in the organic-inorganic hybrid resin can be appropriately set according to the desired performance, and is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass, and preferably 65% by mass or less. , more preferably 40% by mass or less. When the content of the organic component is within the above preferable range, the adhesion between the gas barrier layer 31 and the protective layer 41 tends to be improved while maintaining the transparency of the protective layer 41 .

(adhesion promoter)
The adhesion promoter improves adhesion to the gas barrier layer 31 . In this embodiment, an adhesion promoter having an acid value of 120 (mgKOH/g) or more and 400 (mgKOH/g) or less and a molecular weight of 80 to 900 is used. Here, the acid value of the adhesion promoter is preferably 130 (mgKOH/g) or more and 380 (mgKOH/g) or less, more preferably 140 (mgKOH/g) or more and 360 (mgKOH/g) or less. Further, the molecular weight of the adhesion promoter is preferably 80-750, more preferably 80-600.

Examples of adhesion promoters include monofunctional (meth)acrylates containing carboxyl groups, monofunctional urethane (meth)acrylates containing carboxyl groups, sulfonic acid esters containing (meth)acryloyl groups, and phosphors containing (meth)acryloyl groups. An acid ester is preferably used, and a monofunctional (meth)acrylate containing a carboxyl group and a phosphate ester having a (meth)acryloyl group are more preferable. Any of these can be suitably used as long as the acid value and molecular weight are within the ranges described above. As long as they have the above-described acid value and molecular weight, they do not correspond to the above-described ionizing radiation-curable matrix-forming materials. Various commercial products can be used as the adhesion promoter having such an acid value and molecular weight. Specifically, CD9050 manufactured by Sartmer, M-5300 and M-5400 manufactured by Toagosei Co., Ltd., β-CEA manufactured by Daicel Ornex, KAYAMER PM-2 and PM-21 manufactured by Nippon Kayaku, Examples include JPA-514 manufactured by Johoku Kagaku Co., Ltd.

The content ratio of the adhesion promoter in the ionizing radiation-curable resin composition can be appropriately set according to the desired performance, and is not particularly limited. , preferably 1 to 25% by mass, more preferably 1.5 to 20% by mass, and still more preferably 2 to 15% by mass. When the content of the adhesion promoter is within the above preferable range, the protective layer 41 having excellent adhesion to the gas barrier layer 31 and adhesion (durability) over time tends to be easily obtained. Similarly, the content of the ionizing radiation-curable matrix-forming material in the ionizing radiation-curable resin composition can be appropriately set according to the desired performance, and is not particularly limited. It is preferably 75 to 99% by mass, more preferably 80 to 98.5% by mass, and still more preferably 85 to 98% by mass with respect to the total 100 parts by mass.

(Inorganic filler)
The ionizing radiation-curable resin composition (and protective layer 41, which is a cured product thereof) contains an inorganic filler together with the components described above. By containing the inorganic filler, the adhesion to the gas barrier layer 31 tends to be further enhanced. As described above, the inorganic filler includes the inorganic component of the organic-inorganic matrix-forming material, and the inorganic filler externally added separately (hereinafter, sometimes referred to as "externally added inorganic filler"). are included. The inorganic component of the organic-inorganic matrix-forming material has already been explained. On the other hand, examples of external inorganic fillers include inorganic particles such as silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, and zirconium oxide. Not limited. These can be used individually by 1 type or in combination of 2 or more types. Even when an organic-inorganic matrix-forming material containing an inorganic component is used as the ionizing radiation-curable matrix-forming material, the ionizing radiation-curable resin composition of the present embodiment contains the inorganic component of the organic-inorganic matrix-forming material. Separately, it may further contain an externally added inorganic filler.

The average particle diameter D ₅₀ of the externally added inorganic filler can be appropriately set according to the desired performance, and is not particularly limited, but is preferably 1 nm or more and 10 μm or less. Within this range, high adhesion to the protective layer 41 and high transparency of the protective layer 41 tend to be easily maintained. From the viewpoint of easily obtaining high adhesion to the protective layer 41, the thickness is more preferably less than 100 nm, and still more preferably 10 nm or less. On the other hand, when the externally added inorganic filler also functions as an unevenness imparting agent described later, the average particle diameter _D50 is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.5 μm or more. , 8 μm or less, more preferably 1 μm or more and 5 μm or less. The average particle diameter D ₅₀ of the externally added inorganic filler means the median diameter measured by a laser diffraction type particle size distribution analyzer (eg, Shimadzu Corporation: SALD-7000, etc.). An external inorganic filler having an average particle size of less than 100 nm and/or an inorganic component of the organic/inorganic matrix-forming material described above and an external inorganic filler having an average particle size of 0.1 μm or more can be used in combination. .

The content ratio of the inorganic filler in the ionizing radiation curable resin composition (and the protective layer 41 that is a cured product thereof) can be appropriately set according to the desired performance, and is not particularly limited. The total content is preferably 10% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 75% by mass or less.

(Irregularity imparting agent)
The ionizing radiation curable resin composition (and the protective layer 41 which is a cured product thereof) contains, in addition to the components described above, resin particles for imparting an uneven shape to the surface of the protective layer 41 as necessary. It may further contain an unevenness imparting agent consisting of. Examples of resin particles include acrylic resin particles, silicone resin particles, nylon resin particles, styrene resin particles, polyethylene resin particles, benzoguanamine resin particles, and urethane resin particles. It is not particularly limited. These can be used individually by 1 type or in combination of 2 or more types.

The average particle diameter _D50 of the unevenness imparting agent is not particularly limited, but is preferably 0.1 μm or more and 10 μm or less, more preferably 0.5 μm or more and 8 μm or less, and still more preferably 1 μm or more and 5 μm or less. is. The average particle diameter D ₅₀ of the roughening agent means the median diameter measured with a laser diffraction particle size distribution analyzer (eg, Shimadzu Corporation: SALD-7000, etc.). An externally added inorganic filler having an average particle size of less than 100 nm and/or the inorganic component of the organic/inorganic matrix-forming material described above may be used in combination with an unevenness imparting agent having an average particle size of 0.1 μm or more.

(other ingredients)
The ionizing radiation-curable resin composition (and the protective layer 41 that is a cured product thereof) may contain various additives known in the art, if necessary. Various additives include surface modifiers, lubricants, colorants, pigments, dyes, fluorescent brighteners, flame retardants, antibacterial agents, antifungal agents, light stabilizers, heat stabilizers, antioxidants, plasticizers, and leveling agents. agents, flow control agents, antifoaming agents, dispersants, storage stabilizers, cross-linking agents, silane coupling agents, matting agents and the like, but are not particularly limited to these. These can be used individually by 1 type or in combination of 2 or more types.

As a specific embodiment of a preferred ionizing radiation-curable resin composition, (X) an ionizing radiation-curable resin containing at least the above-described adhesion promoter, an ionizing radiation-curable matrix-forming material, and an inorganic filler such as silica (Y) an ionizing radiation-curable resin composition containing at least the adhesion promoter described above and an organic-inorganic matrix-forming material (including an inorganic filler as an inorganic component); (Z) the adhesion promoter described above; , an ionizing radiation-curable resin composition containing at least an organic-inorganic matrix-forming material (including an inorganic filler as an inorganic component) and an externally added inorganic filler different from the inorganic component in the organic-inorganic matrix-forming material, etc. is mentioned.

The protective layer 41 can be obtained by curing the above-described ionizing radiation-curable resin composition, and the formation method thereof is not particularly limited and any method known in the art can be applied. For example, a coating liquid is prepared by dissolving or dispersing the ionizing radiation curable resin composition described above in a solvent, and the coating liquid is applied onto the gas barrier layer 31 and cured to form the protective layer 41. can be done. As a coating method at this time, a conventionally known coating method can be applied, and there is no particular limitation. Examples thereof include doctor coating, dip coating, roll coating, bar coating, die coating, blade coating, air knife coating, kiss coating, spray coating, spin coating and the like.

Water; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; ether solvents such as methyl cellosolve and ethyl cellosolve; Alcohol-based solvents such as alcohol and isopropyl alcohol, and mixed solvents thereof, which are known in the art can be used. Among these, ketone-based solvents and mixed solvents containing ketone-based solvents are preferably used. The protective layer 41 can be formed by subjecting the thus applied coating film to ionizing radiation treatment, heat treatment, and/or pressure treatment as necessary. The protective layer 41 can also be provided on the other main surface 11b side of the substrate 11. In this case, both surfaces of the laminated gas barrier film 100 have the protective layer 41. will be excellent.

The light source used for ionizing radiation irradiation is not particularly limited. For example, ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, electron beam accelerators and the like can be used. In addition, the irradiation dose at this time can also be appropriately set according to the type of light source used, ^output performance, etc., and is not particularly limited. is the target.

Also, the heat source used in the heat treatment is not particularly limited. Either contact type or non-contact type can be suitably used. For example, far-infrared heaters, short-wave infrared heaters, medium-wave infrared heaters, carbon heaters, ovens, heat rollers, and the like can be used. The treatment temperature in the heat treatment is not particularly limited, but is generally 50 to 200°C, preferably 50 to 180°C, more preferably 60 to 150°C.

The thickness of the protective layer 41 is not particularly limited, and can be appropriately set according to the constituent material, required performance, and application. From the viewpoint of weight reduction and thinning, handling properties, mechanical strength, etc., the thickness of the protective layer 41 is generally preferably 0.01 to 20 μm, more preferably 0.5 to 15 μm, and even more preferably. is 1-10 μm. In addition, although the protective layer 41 may be formed of only one layer, it may be formed by laminating a plurality of layers, or the gas gallia layer 31 and the protective layer 41 may be formed by laminating a plurality of layers alternately.

<Action>
In the laminated gas barrier film 100 of the present embodiment, a protective layer 41 having excellent adhesion using an adhesion promoter is provided on the gas barrier layer 31, and the protective layer 41 is relatively low in oxidation compared to the conventional technology. 41, corrosion and deterioration of the gas barrier layer 31 are less likely to occur, and deterioration of adhesion to the gas barrier layer 31 is suppressed even when exposed to a high-temperature and high-humidity environment. there is Therefore, the laminated gas barrier film 100 of the present embodiment can maintain its performance for a long period of time even in a severe storage or use environment of high temperature and high humidity. Therefore, the laminated gas barrier film 100 of the present embodiment can be used not only for sealed packaging of articles such as foods, cosmetics, and pharmaceuticals, but also for photoelectric conversion elements, solar cells (PV), electronic paper, liquid crystal displays (LCD), and organic EL displays. It can be suitably used as a high-performance gas barrier film in the field of electronic devices such as flat panel displays (FPD) such as (OELD).

Hereinafter, the present embodiment will be described in more detail using examples and comparative examples. However, the present invention is not limited by these. Various production conditions and evaluation result values in the following examples have the meaning of preferable upper limit values or preferable lower limit values in the embodiments of the present invention, and the preferable range is the above-mentioned upper limit value or lower limit value and the values in the following examples or the values between the examples.

[Example 1]
First, on one main surface of a base material (transparent polyester film, manufactured by Toyobo Co., Ltd., Cosmoshine A4300) having a thickness of 125 μm and both sides of which are subjected to an easy-adhesion treatment, a coating solution a having the following formulation is applied, dried, and then exposed to ultraviolet light. was irradiated to form a resin layer having a thickness of 3 μm.

<Coating liquid a>
- Photopolymerizable prepolymer 140 parts by mass (ionizing radiation-curable matrix-forming material)
(Desolite Z7503: manufactured by JSR Corporation, solid content 50% by mass, silica content 38% by mass as an inorganic filler)
・ Thermoplastic resin 70 parts by mass (Acrydic A166: manufactured by DIC, solid content 45% by mass, glass transition temperature 49 ° C.)
- Photopolymerization initiator 0.8 parts by mass (Irgacure 651: manufactured by Ciba Japan)
・ Dilution solvent (methyl ethyl ketone) 230 parts by mass

Next, a film having a thickness of 100 nm and a water vapor transmission rate of 1 × 10 ^-1 g/m according to JIS K7129 was formed on the resin layer of the obtained laminated substrate by a sputtering method under vacuum (5 × 10 ^-5 torr). A gas barrier layer composed of a ZTO (zinc tin oxide) film was formed for less than ² ·day.

Next, the following coating liquid b1 (ionizing radiation-curable resin composition) was applied onto the gas barrier layer by a bar coating method and dried. Thereafter, heat treatment at 80° C. is performed using a circulating hot air dryer, and then UV irradiation treatment is performed using a high-pressure mercury lamp (accumulated light amount: 1000 mJ/cm ² ) to form a 1.5 μm-thick and acid-free layer on the gas barrier layer. A laminated gas barrier film of Example 1 was obtained by forming a protective layer having a value of 25 mgKOH/g.

<Coating liquid b1>
- Photopolymerizable prepolymer 50 parts by mass (organic-inorganic matrix-forming material)
(KZ6445A: manufactured by Arakawa Chemical Industries, Ltd., Opstar (registered trademark), solid content 50% by mass, nanosilica content 30% by mass, which is an inorganic component)
Adhesion promoter 0.8 parts by mass (M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl phthalate acrylate, acid value 205 mgKOH/g, molecular weight 260 g, solid content 100% by mass)
・ Dilution solvent (methyl ethyl ketone) 78 parts by mass

[Example 2]
A protective layer having a thickness of 1.5 µm and an acid value of 27 mgKOH/g was formed on the gas barrier layer in the same manner as in Example 1 except that the following coating solution b2 was used instead of the coating solution b1. No. 2 laminated gas barrier film was obtained.

<Coating liquid b2>
- Photopolymerizable prepolymer 50 parts by mass (organic-inorganic matrix-forming material)
(KZ6445A: manufactured by Arakawa Chemical Industries, Ltd., Opstar (registered trademark), solid content 50% by mass, nanosilica content 30% by mass, which is an inorganic component)
Adhesion promoter 1.3 parts by mass (M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl phthalate acrylate, acid value 205 mgKOH/g, molecular weight 260 g, solid content 100% by mass)
・ Dilution solvent (methyl ethyl ketone) 78 parts by mass

[Example 3]
A protective layer having a thickness of 1.5 μm and an acid value of 39 mgKOH/g was formed on the gas barrier layer in the same manner as in Example 1 except that the following coating liquid b3 was used instead of the coating liquid b1. A laminated gas barrier film No. 3 was obtained.

<Coating liquid b3>
- Photopolymerizable prepolymer 50 parts by mass (organic-inorganic matrix-forming material)
(KZ6445A: manufactured by Arakawa Chemical Industries, Ltd., Opstar (registered trademark), solid content 50% by mass, nanosilica content 30% by mass, which is an inorganic component)
Adhesion promoter 1.9 parts by mass (M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl phthalate acrylate, acid value 205 mgKOH/g, molecular weight 260 g, solid content 100% by mass)
・ Dilution solvent (methyl ethyl ketone) 78 parts by mass

[Comparative Example 1]
A protective layer having a thickness of 1.5 μm and an acid value of 17 mgKOH/g was formed on the gas barrier layer in the same manner as in Example 1 except that the following coating liquid b4 was used instead of the coating liquid b1. A laminated gas barrier film No. 1 was obtained.

<Coating liquid b4>
- Photopolymerizable prepolymer 50 parts by mass (organic-inorganic matrix-forming material)
(KZ6445A: manufactured by Arakawa Chemical Industries, Ltd., Opstar (registered trademark), solid content 50% by mass, nanosilica content 30% by mass, which is an inorganic component)
- Photopolymerization initiator 2.2 parts by mass (Irgacure 651: manufactured by Ciba Japan)
・ Dilution solvent (methyl ethyl ketone) 78 parts by mass

[Comparative Example 2]
A protective layer having a thickness of 1.5 μm and an acid value of 21 mgKOH/g was formed on the gas barrier layer in the same manner as in Example 1 except that the following coating liquid b5 was used instead of the coating liquid b1. No. 2 laminated gas barrier film was obtained.

<Coating liquid b5>
- Photopolymerizable prepolymer 50 parts by mass (ionizing radiation-curable matrix-forming material)
(Shikou UV-1700B: manufactured by Nippon Synthetic Chemical Co., Ltd., solid content 100% by mass)
- Photopolymerization initiator 1.5 parts by mass (Irgacure 651: manufactured by Ciba Japan)
- Adhesion accelerator 4.0 parts by mass (M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl phthalate acrylate, acid value 205 mgKOH/g, molecular weight 260 g, solid content 100% by mass)
・ Dilution solvent (methyl ethyl ketone) 200 parts by mass

[Example 4]
A protective layer having a thickness of 1.5 µm and an acid value of 21 mgKOH/g was formed on the gas barrier layer in the same manner as in Example 1 except that the following coating solution b6 was used instead of the coating solution b1. No. 4 laminated gas barrier film was obtained.

<Coating liquid b6>
- Photopolymerizable prepolymer 50 parts by mass (ionizing radiation-curable matrix-forming material)
(Shikou UV-1700B: manufactured by Nippon Synthetic Chemical Co., Ltd., solid content 100% by mass)
- Photopolymerization initiator 1.5 parts by mass (Irgacure 651: manufactured by Ciba Japan)
Adhesion promoter 4.0 parts by mass (M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl phthalate acrylate, acid value 205 mgKOH/g, molecular weight 260 g, solid content 100% by mass)
・ External inorganic filler 125 parts by mass (nano silica, MEK-ST-40: manufactured by Nissan Chemical Industries, Ltd., solid content 40%)
・ Dilution solvent (methyl ethyl ketone) 300 parts by mass

[Evaluation of adhesion]
The obtained laminated gas barrier films of Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated for adhesion and adhesion after a wet heat resistance test. Here, based on the cross-cut tape method in JIS K5400: 1990, cuts were made in the protective layer of the laminated gas barrier film, and a peeling test of the substrate was performed. counted. Note that the adhesion over time was evaluated after being left for 500 hours under the conditions of 85° C. and 85% RH. Table 1 shows the results.

The ionizing radiation-curable resin composition and the laminated gas barrier film of the present invention not only have excellent adhesion, but also are resistant to corrosion and deterioration of the gas barrier layer, and can be used even when exposed to high-temperature and high-humidity environments. Since the deterioration of the adhesion to the gas barrier layer is suppressed, it is used not only in the sealed packaging field of articles such as foods, cosmetics, and pharmaceuticals, but also in the field of photoelectric conversion elements, solar cells (PV), electronic paper, and liquid crystal displays (LCDs). , organic EL displays (OELD) and other flat panel displays (FPDs), and other electronic devices.

DESCRIPTION OF SYMBOLS 100... Laminated gas barrier film 11... Base material 11a... Main surface 11b... Main surface 21... Resin layer 21a... Main surface 31... Gas barrier layer 31a... Main surface 41 protective layer

Claims (7)

an adhesion promoter having an acid value of 120 (mgKOH/g) or more and 400 (mgKOH/g) or less and a molecular weight of 80 to 900;
an ionizing radiation-curable matrix-forming material (excluding those corresponding to the adhesion promoter);
an inorganic filler;
containing at least
The adhesion promoter has a monofunctional (meth)acrylate containing a carboxyl group, a monofunctional urethane (meth)acrylate containing a carboxyl group, a sulfonic acid ester having a (meth)acryloyl group, and a (meth)acryloyl group. At least one selected from the group consisting of phosphate esters,
The inorganic filler contains silica,
The adhesion promoter is contained in an amount of 1.5 to 20% by mass with respect to a total of 100 parts by mass of the adhesion promoter and the ionizing radiation-curable matrix-forming material,
The ionizing radiation-curable matrix-forming material is contained in an amount of 80 to 98.5% by mass with respect to a total of 100 parts by mass of the adhesion promoter and the ionizing radiation-curable matrix-forming material,
The acid value per 1 g of dry mass of the cured product after curing is 20 (mgKOH / g) or more and 50 (mgKOH / g) or less,
An ionizing radiation-curable resin composition for a gas barrier layer protective film. The total content of silica is 35% by mass or more and 80% by mass or less with respect to the total amount of solid content.
The ionizing radiation-curable resin composition for gas barrier layer protective film according to claim 1 . The acid value per 1 g of dry mass of the cured product after curing is 20 (mgKOH/g) or more and 45 (mgKOH/g) or less,
The ionizing radiation-curable resin composition for a gas barrier layer protective film according to claim 1 or 2. Consisting of a cured product of the ionizing radiation curable resin composition for a gas barrier layer protective film according to any one of claims 1 to 3,
Protective film for gas barrier layer. comprising at least a gas barrier layer and a protective layer provided on the gas barrier layer;
The protective layer is a cured product of the ionizing radiation curable resin composition for gas barrier layer protective film according to claim 1 or 2 ,
The protective layer has an acid value of 20 (mgKOH/g) or more and 50 (mgKOH/g) or less per 1 g of dry mass.
Laminated gas barrier film. wherein the gas barrier layer is a water vapor barrier layer;
The laminated gas barrier film according to claim 5. The gas barrier layer has a water vapor transmission rate (MOCON method, JIS K7129 compliant, 40° C. and 90% RH) of less than 1×10 ⁻¹ g/m ² ·day.
The laminated gas barrier film according to claim 6.

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