TW201936649A - Ionization radiation curable resin composition, protective film of gas barrier layer using the same, and laminated gas barrier thin film using the same - Google Patents

Abstract

The present invention provides an ionization radiation curable resin composition capable of realizing a gas barrier thin film excellent in adhesion and durability, a protective film of a gas barrier layer using the same, and a laminated gas barrier thin film using the same and being excellent in adhesion and durability. The present invention provides an ionization radiation curable resin composition that at least contains an adhesion promoter having an acid value of 120 (mg KOH/g) or more and 400 (mg KOH/g) or less and a molecular weight of 80 to 900, an ionization radiation curable substrate-forming material (excluding the one equivalent to the previous adhesion promoter) and an inorganic filler. The content of the adhesion promoter is 1 to 25 % by mass based on 100 parts by mass of the previous adhesion promoter and the previous ionization radiation curable substrate-forming material. After curing, the cured product has an acid value of 20 (mg KOH/g) or more and 50 (mg KOH/g) or less per 1 g dry weight of the cured product.

Description

Ionizing radiation curable resin composition, protective film using the gas barrier layer, and laminated gas barrier film using the same

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

In the past, a gas barrier film which imparts gas barrier properties by forming a thin film of an inorganic compound such as cerium oxide, cerium nitride, cerium oxynitride, aluminum oxide or magnesium oxide on the surface of a plastic substrate or a film has been known. Such a gas barrier film can be used for prematurely preventing deterioration of articles caused by gases such as water vapor or oxygen, and can be used, for example, in sealed packaging containers for articles such as foods, cosmetics, and pharmaceuticals.

In recent years, a gas barrier film that prevents the passage of water vapor or oxygen has been used in addition to photoelectric conversion elements or solar cells (PV), and is also used in electronic paper or liquid crystal display (LCD) or organic EL display (OELD). In the field of electronic devices such as flat panel displays (FPDs). These electronic devices are particularly susceptible to moisture and the like, and are liable to cause deterioration of the performance of the liquid crystal layer or the light-emitting layer. Therefore, the gas barrier film used for protection of these electronic devices is compatible with gas barrier properties used for sealed packages such as foods and pharmaceuticals. Higher gas barrier properties (interruption) are required for films.

As such a gas barrier film, an inorganic film such as an inorganic compound such as cerium oxide as a gas barrier layer or an organic film such as a thermosetting resin is formed on a substrate such as polyethylene terephthalate (PET). By. As a method of forming the gas barrier layer, a physical vapor deposition method (PVD: Physical Vapor Deposition) such as a vacuum deposition method, a sputtering method, or an ion plating method, a reduced pressure chemical vapor growth method, and a plasma chemical vapor phase are known. Chemical vapor deposition method (CVD: Chemical Vapor Deposition), various coating methods, and the like.

Further, since the gas barrier layer of the inorganic compound film such as cerium oxide is relatively hard and brittle, it is improved from the prevention of the occurrence of the flaw of the gas barrier layer, or the peeling of the gas barrier layer by a solvent or the like, or the improvement of the handleability. Sometimes a protective layer is further provided on the gas barrier layer. For example, when it is used in an organic EL display or the like, a protective layer is provided on the gas barrier layer, and a transparent conductive film is formed on the protective layer, and patterned by etching or the like to form a loop.

As a laminated gas barrier film provided with such a protective layer, Patent Document 1 discloses that a base film is provided, and at least one surface of the base film is provided with a barrier vapor deposition layer having a smooth surface, and is laminated on the barrier. An acid-resistant protective layer having a smooth surface of the vapor deposited layer, wherein the oxygen permeability is 0.1 cc/m ² /day·atm or less, and the water vapor transmission rate is 0.1 g/m ² /day or less, and the barrier vapor deposition layer is Indium zinc oxide, the indium (In) and zinc (Zn) atomic ratio In / (In + Zn) in the indium zinc oxide is in the range of 0.5 to 0.8, and the acid resistance of the protective layer is Hydrochloric acid: a gas barrier film characterized by an oxidation rate of an indium tin oxide etching solution having a volume mixing ratio of 1:0.08:1 of 0.01 μm/min or less.

Further, Patent Document 2 discloses that a gas barrier layer mainly composed of an indium-lanthanide-based oxide is formed on at least one surface of a substrate made of a plastic film, and a protective layer is further provided on the surface, and the protective layer is provided. A gas barrier film characterized by a layer that protects the gas barrier layer from etching.

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

In order to solve this problem, Patent Document 3 proposes a substrate, a gas barrier layer on at least one surface of the substrate, and a protective layer on the gas barrier layer, wherein the protective layer contains (A) an aromatic ring. Amino methacrylate (meth) acrylate, (B) a carboxyl group-containing (meth) acrylate, and (C) a polyfunctional (meth) acrylate having an acid value of 80 mg KOH per dry weight of 1 g unit. A gas barrier film characterized by being formed of an energy ray-curable resin composition of 130 mg or more and g or less.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] Patent No. 4414748
[Patent Document 2] Patent No. 4617583
[Patent Document 3] Patent No. 5752438

[Problems solved by the invention]

However, in Patent Document 3, since a relatively high-oxidation protective layer is used, it is likely to cause corrosion or deterioration of, for example, an inorganic gas barrier layer, and if it is exposed to light in a high-temperature and high-humidity environment, adhesion to a gas barrier layer is easy. Reduce the problem.

In view of the above, 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, a protective film using the gas barrier layer, and the like. A laminated gas barrier film having excellent adhesion and durability.

[Means for solving the problem]

The inventors of the present invention have made a detailed review to solve the above problems. As a result, it has been found that when the protective layer having a relatively low oxidation is formed by using an ionizing radiation curable resin composition containing a predetermined adhesion promoter, the above problems can be solved and the present invention has been completed. That is, the present invention provides various specific aspects shown below.

[1] An ionizing radiation curable resin composition containing at least an acid 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. In the case of the inorganic filler, the content of the adhesion promoter is 1 in total of 100 parts by mass of the adhesion promoter and the ionizing radiation curable matrix-forming material. ~25% by mass, the dry mass of the cured product after hardening is 1 g unit of acid value of 20 (mgKOH / g) or more and 50 (mgKOH / g) or less.

The ionizing radiation curable resin composition according to the above aspect, wherein the adhesion promoter is selected from a monofunctional (meth) acrylate containing a carboxyl group and a monofunctional urethane containing a carboxyl group (A) At least one of a group of an acrylate, a sulfonate having a (meth)acryl fluorenyl group, and a phosphate having a (meth) acryl fluorenyl group.
[3] The ionizing radiation curable resin composition according to [1] or [2], further comprising a ketone solvent.

[4] A cured film of a gas barrier layer, which is obtained by a cured product of the ionizing radiation curable resin composition according to any one of [1] to [3].

[5] A laminated gas barrier film comprising at least a gas barrier layer and a protective layer provided on the gas barrier layer, wherein the protective layer is as described in any one of [1] to [3] In the cured product of the ionizing radiation curable resin composition, the protective layer has an acid value of 20 g (mgKOH/g) or more and 50 (mgKOH/g) or less in a dry mass of 1 g.
[6] The laminated gas barrier film according to [5], wherein the gas barrier layer is a water vapor barrier layer.
[7] The laminated gas barrier film according to [6], wherein the gas barrier layer has a water vapor transmission rate of less than 1 × 10 ^-1 g/m ² day (MOCON method, according to JIS K7129, 40 °C and 90% RH).

[Effects of the Invention]

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 using the gas barrier layer, and providing excellent adhesion and Durable gas barrier film.

[Formation of the Invention]

The embodiments of the present invention will be described in detail below with reference to the drawings. Further, the positional relationship such as up, down, left, and right, if not particularly limited, depends on the positional relationship shown in the drawing. Moreover, the dimensional ratio of the drawing is not limited to the illustrated ratio. However, the following embodiments are illustrative of the invention, and the invention is not limited thereto. Further, in the present specification, for example, the numerical value range of "1 to 100" includes both the upper limit value "100" and the lower limit value "1". Also, the labels of other numerical ranges are the same. Further, in the present specification, the (meth) acrylate means acrylate and/or methacrylate, and the (meth) acryl means acrylic acid and/or methacrylic acid. Others indicate that the expressions such as (meth)acrylonitrile are also the same.

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

In the present specification, the "resin layer 21 provided on one main surface 11a side of the substrate 11" means not only the surface of the substrate 11 (for example, the main surface 11a) but the resin layer 21 is directly placed as shown in FIG. In the aspect, it indicates a state in which any surface (for example, a primer layer, an adhesive layer, an anchor layer, or the like) is interposed between the surface of the substrate 11 and the resin layer 21. In addition, the same meaning is also given to the other similar descriptions.

<Substrate>
The substrate 11 is a member that supports the resin layer 21, the gas barrier layer 31, and the protective layer 41. As the substrate 11, only those layers can be supported, and those skilled in the art can be used. The type is not particularly limited. From the viewpoints of dimensional stability, mechanical strength, and the like, a synthetic resin film, glass, or the like is generally used. Further, from the viewpoint of lightness and the like, a synthetic resin film is preferably used.

Examples of the synthetic resin used for the substrate 11 include a polyolefin resin such as a polyolefin resin such as a homopolymer or a copolymer such as ethylene, polypropylene or butylene; a cyclic olefin polymer (COP) and a cyclic olefin. Amorphous polyolefin resin such as copolymer (COC); polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate Polyester resin such as (PEN); polyamine resin such as nylon 6, nylon 12, copolymerized nylon; polycarbonate resin; polystyrene resin; ABS (acrylonitrile-butadiene-styrene) system Resin; polyvinyl alcohol resin such as polyvinyl alcohol (PVA) or ethylene-vinyl alcohol copolymer (EVOH); polyimide resin; polyether quinone resin; cellulose system such as triacetyl cellulose Acrylic resin; acrylic resin such as (meth) acrylate; poly fluorene resin; polyether ether ketone resin; polyvinyl chloride, vinyl chloride-vinyl chloride copolymer, vinyl chloride-propylene Polyvinyl chloride resin such as nitrile copolymer, vinylidene chloride-acrylic acid copolymer; polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene- Fluoro-propyl extending copolymer (FEP), tetrafluoroethylene - perfluoroalkyl vinyl ether copolymer (PFA) resin, fluorine and the like, but is not limited thereto and the like. Among these, as the substrate 11, a polyester resin film such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate is preferable. Moreover, the one-axis or two-axis stretch film, particularly the biaxially stretched polypropylene (OPP) film, is particularly excellent because of its excellent mechanical strength and dimensional stability. Further, in the heat-resistant use, it is particularly preferable to extend the polyimide film in one-axis or two-axis. These may be used alone or in combination of two or more. Further, it may be a multilayer film made of a plurality of layers.

The transparency of the substrate 11 is not particularly limited, and for example, it is preferably optically transparent for use in an electronic device such as a touch panel. At this time, the total light transmittance of the substrate 11 is preferably 80% or more, preferably 85% or more, and more preferably 90% or more. Further, from the viewpoint of improving the adhesion to the resin layer 21 or any of the above layers, the surface of the substrate 11 may be subjected to plasma treatment, corona discharge treatment, flame treatment, extreme ultraviolet irradiation treatment, or anchor treatment, if necessary. Various known surface treatments such as drug treatment. For example, as an anchor treatment, a coating polyester resin, an isocyanate type, an urethane type, an acrylic type, an ethylene vinyl alcohol type, a vinyl denatured type, an epoxy type, a modified styrene type, a denatured polyoxyl can be provided. The anchor coating layer of the anchor coating agent can further improve the adhesion between the substrate 11 and the gas barrier layer 31. Moreover, in order to improve durability, weather resistance, etc., the base material 11 may contain an ultraviolet absorber or a light stabilizer.

The thickness of the substrate 11 can be appropriately set in accordance with the required properties and use, and is not particularly limited. The thickness of the substrate 11 is preferably from 5 to 500 μm, preferably from 10 to 300 μm, from the viewpoints of weight reduction and film formation, and further considering handling properties or mechanical strength.

The resin film used as the substrate 11 is preferably selected for use in combination with desired properties. For example, for packaging such as foods or chemicals, polyethylene terephthalate, polypropylene, nylon, etc. are cost-effective. It is preferable to use a resin film having a high gas barrier property such as polyethylene naphthalate, polyimide resin, polymylon resin, or amorphous polyolefin resin for electronic components or optical members. good.

<Resin layer>
The resin layer 21 is for improving the surface smoothness and surface hardness of the substrate 11. By providing the resin layer 21 having such a smooth surface, 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, whereby the gas barrier of the entire laminated gas barrier film 100 can be improved. Sex.

As the resin layer 21, various known ones can be used, and the kind is not particularly limited. Generally, it is composed of a film such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation curable resin. Examples of the thermoplastic resin and the thermosetting resin include a saturated or unsaturated polyester resin, an acrylic resin, an urethane acrylate resin, a polyester acrylate resin, and a polyurethane acrylate. An ester resin, an epoxy acrylate resin, a urethane resin, an epoxy resin, a vinyl resin, a polycarbonate resin, a cellulose resin, an acetal resin, a polyethylene resin, The polystyrene resin, the polyamine resin, the polyimide resin, the melamine resin, the phenol resin, the polyoxyn resin, and the like are not particularly limited thereto. These may be used alone or in combination of two or more. Further, a resin film such as an ionizing radiation curable resin or an organic-inorganic hybrid ionizing radiation curable resin is also preferable. These details are described in the protective layer 41 to be described later, and thus are omitted here.

The thickness of the resin layer 21 can be appropriately set in accordance with the required properties and use, and is not particularly limited. The thickness of the resin layer 21 is preferably from 0.5 to 50 μm, preferably from 1 to 10 μm, from the viewpoints of weight reduction and film formation, and further considering handling properties or mechanical strength.

<Gas barrier layer>
The gas barrier layer 31 is intended to prevent an electronic device such as a photoelectric conversion element, a solar cell, an electronic paper, a liquid crystal display (LCD), or an organic EL display (OELD), such as a flat panel display (FPD), from being placed on the substrate 11 side. Etc.) The performance is deteriorated after contact with oxygen or water vapor. The barrier property of the gas barrier layer 31 can be appropriately set in accordance with the type of the object to be protected, the required performance, the use, and the like, and is not particularly limited.

For example, in the case of the flexible substrate, the oxygen barrier rate of the gas barrier layer 31 is preferably less than 1 × 10 ^-1 cc / m ² · day · atm, preferably 1 × 10 ^-2 cc / m ² · Day・atm or less. Further, in the present specification, the oxygen permeability is a value obtained by measuring the value obtained by the MOCON method at 40 ° C and 90% RH using an oxygen permeability measuring device in accordance with JIS K7129.

Further, similarly, for the flexible substrate application, the water vapor transmission rate of the gas barrier layer 31 is preferably less than 1 × 10 ^-1 g/m ² day, preferably 1 × 10 ^-2 g / m. ^{2 days} or less. Further, in the present specification, the water vapor transmission rate is a value measured by a MOCON method under the conditions of 40 ° C and 90% RH using a water vapor transmission rate measuring device in accordance with JIS K7129. Such a gas barrier layer having a high water vapor transmission rate (hereinafter also referred to as "water vapor gas barrier layer") is generally composed of an inorganic thin film, and the inorganic thin film is not only hard and brittle, but is often used as a protective film used in the past. Poor adhesion. Therefore, when the water vapor barrier layer formed of such an inorganic thin film is used as the gas barrier layer 31, the effects of the present invention tend to be remarkably easy to express.

As the gas barrier layer 31, those well known in the art can be used, and the kind is not particularly limited. The above various inorganic thin films having better gas barrier properties are known in the art, and these can be used as the gas barrier layer 31. Specifically, a gas barrier layer (hereinafter, simply referred to as "inorganic gas barrier layer") containing a metal such as copper or silver, a light metal such as aluminum or titanium, or a semimetal such as ruthenium or a compound (metal compound or inorganic compound) is used. good. Among these, a gas barrier layer made of an inorganic compound is preferable from the viewpoints of transmittance and cost such as oxygen or water vapor.

The gas barrier layer 31 may be composed of a thin film of a metal, a metal compound or an inorganic compound. In addition, examples of the metal compound or the inorganic compound include oxides, nitrides, carbides, and nitrogen oxides such as lanthanum, aluminum, magnesium, calcium, zirconium, boron, lanthanum, cerium, zinc, tin, titanium, selenium, and indium. The compound, the oxidized carbide, the carbonitride, and the like, etc., are blended with other metals (tin, zinc, gallium, antimony, etc.), but are not limited thereto. Among these, lanthanum-based inorganic oxides such as yttrium oxide, lanthanum oxynitride, and lanthanum carbide oxide, indium/tin oxide (ITO), indium, gallium, zinc oxide (IGZO), and indium gallium oxide (IGO) are used. ), gallium, zinc oxide (GZO), zinc, tin oxide (ZTO), indium, zinc, tin oxide (IZTO), indium, gallium, zinc, tin oxide (IGZTO), tantalum, tin oxide ( ATO) is preferred. These may be used alone or in combination of two or more. Further, as a method of forming the gas barrier layer 31, a method known in the art can be used, and it 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, or the like can be given. Moreover, it is preferable that the gas barrier layer 31 is optically transparent, whereby the entire laminated gas barrier film 100 can be made transparent, and for example, it can be suitably used for the above-mentioned FPD use.

The thickness of the gas barrier layer 31 can be appropriately set in accordance with the materials, required properties, and uses, and is not particularly limited. The thickness of the gas barrier layer 31 is preferably from 5 to 500 nm, preferably from 20 to 300 nm, from the viewpoints of light weight and film formation, and further considering handling properties or mechanical strength. Further, the gas barrier layer 31 may be composed of only one layer of an inorganic layer made of the above-mentioned metal, metal compound or inorganic compound, and the inorganic layer may be laminated in a plurality of layers, or may be formed by an inorganic layer and a resin. The organic layers are laminated in an interactive manner. In all cases, it is preferable that at least the inorganic layer (inorganic gas barrier layer) of the gas barrier layer 31 is adjacent to the protective layer 41. Thereby, there is a tendency that the adhesion between the gas barrier layer 31 and the protective layer 41 is improved.

<protection layer>
The protective layer 41 is a film (protective film) used for the protective gas barrier layer 31. By providing such a protective layer 41, it is possible to simultaneously suppress the occurrence of scratches in the gas barrier layer 31, a part of the gas barrier layer 31 from being damaged or partially peeled off, and it is possible to improve the overall rationality of the laminated gas barrier film 100.

In the present embodiment, the protective layer 41 is composed of a cured product of an ionizing radiation curable resin composition, and the acid value is 20 (mgKOH/g) or more and 50 (mgKOH/g) or less in a unit of dry mass of 1 g. Further, the acid value is a value measured by a neutralization titration method using a potassium hydroxide standard solution in accordance with JIS K 0070. When the acid value of the protective layer 41 is 20 (mgKOH/g) or more and 50 (mgKOH/g) or less, not only the adhesion between the gas barrier layer 31 and the protective layer 41 but also the durability can be improved. The laminated gas barrier film 100. From the viewpoint of the balance between adhesion and durability, when the acid value of the protective layer 41 is 1 g unit of dry mass, it is preferably 20 (mgKOH/g) or more and 45 (mgKOH/g) or less, and is 20 (mgKOH/min). g) The above 40 (mgKOH/g) or less is preferred.

(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 (hereinafter sometimes referred to as "ionizing radiation hardening" which forms a matrix (resin film) of the protective layer 41 by crosslinking hardening by irradiation with ionizing radiation (ultraviolet rays or electron beams) is used. At the same time, it contains at least an acid 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 inorganic filler (containing an organic-inorganic substrate described later). The ionized radiation curable resin composition of both the inorganic component in the material and/or the inorganic filler to be added may 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 photocationic polymerizable resin, a photopolymerizable prepolymer, or a photopolymerizable monomer capable of photocationic polymerization can be used (hereinafter referred to as "ionizing radiation curable matrix forming material" One type or a mixture of two or more types. In the present specification, the adhesion promoter corresponding to an acid value of 120 (mgKOH/g) or more and 400 (mgKOH/g) or less and a molecular weight of 80 to 900 is removed from the ionizing radiation curable matrix forming material.

Specific examples of the photocationic polymerizable resin include an epoxy resin such as a bisphenol epoxy resin, a novolak epoxy resin, an alicyclic epoxy resin, or an aliphatic epoxy resin, or a vinyl ether resin. Etc., but not limited to this. These may be used alone or in combination of two or more.

The photopolymerizable prepolymer can be roughly classified into a cationic polymerization type and a radical polymerization type. The photopolymerizable prepolymer of the cationic polymerization type may, for example, be an epoxy resin or a vinyl ether resin. Examples of the epoxy resin include a bisphenol epoxy resin, a novolak epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin. The radical polymerization type photopolymerizable prepolymer includes an acrylic prepolymer (hard prepolymer). The photopolymerizable prepolymer may be used singly or in combination of two or more. In the above, the photopolymerizable prepolymer is preferably an acrylic prepolymer having two or more acrylonitrile groups in one molecule and having a three-dimensional lattice structure by crosslinking and hardening. Specific examples thereof include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, and polyol (meth) acrylate. Various (meth) acrylates, such as an ester, a melamine (meth) acrylate, a polyfluoroalkyl (meth) acrylate, and a poly methoxy (meth) acrylate, are not specifically limited. Although these photopolymerizable prepolymers can be used singly, it is preferable to add a photopolymerizable monomer from the viewpoint of improving the crosslinking hardenability and further increasing the hardness of the protective layer 41.

Examples of the photopolymerizable monomer include methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate. Monofunctional (meth) acrylates such as esters, butoxyethyl acrylates, etc.; 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, poly Bifunctional (meth) acrylates such as ethylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate; dipentaerythritol hexaacrylate, trimethylpropane triacrylate, pentaerythritol triacrylate, etc. 3 (meth)acrylates having a functional group or higher; styrene monomers such as styrene and α-methylstyrene; and carboxylic acid amides such as (meth)acrylamide, and (meth)acrylic acid-2 -(N,N-Diethylamino)ethyl, substituted amino acid esters of unsaturated acids such as 2-(N,N-diphenylmethylamino)ethyl (meth)acrylate, B Diol (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, isocyanuric acid triacrylate (eg gin-(2-hydroxyethyl) )-isocyanurate (meth) acrylate, etc., 3-phenoxy-2-propenyl acrylate, 1,6-bis(3-propenyloxy-2-hydroxypropyl)- A polyfunctional compound such as hexyl ether, and trimethylolpropane trithioglycolate or pentaerythritol tetrathioglycolate are equal to a polythiol compound having two or more thiol groups in the molecule, but there is no It is particularly limited to these. These may be used alone or in combination of two or more. Among them, a polyfunctional (meth) acrylate having a hydroxyl group is preferred from the viewpoint of further improving the adhesion to the gas barrier layer 31.

Among them, as the photopolymerizable monomer, a polyfunctional (meth) acrylate having a hydroxyl group and having no carboxylic acid group is preferably used. Specific examples of such a polyfunctional (meth) acrylate include glycerol di(meth)acrylate, glycerol tri(meth)acrylate, trimethylolpropane di(meth)acrylate, and three. Hydroxymethylpropane tri(meth)acrylate, ethylene oxide-denatured trimethylolpropane di(meth)acrylate, ethylene oxide-denatured trimethylolpropane tri(meth)acrylate, epoxy Propane-denatured trimethylolpropane di(meth)acrylate, propylene oxide-denatured trimethylolpropane tri(meth)acrylate, butylene oxide-denatured trimethylolpropane di(meth)acrylate, Butylene oxide denatured trimethylolpropane tri(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, ginseng(2-hydroxyethyl)isocyanuric acid Tris(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, ethylene oxide modified pentaerythritol tris(methyl) Acrylate, propylene oxide, modified pentaerythritol tetra(meth) acrylate, propylene oxide, modified pentaerythritol, tri(methyl) propyl Ethylide, butylene oxide-modified pentaerythritol tetra(meth)acrylate, butylene oxide-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-denatured pentaerythritol Tris(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol five ( Methyl) acrylate or the like is not particularly limited thereto. These may be used alone or in combination of two or more.

When the composition of the ionizing radiation curable resin is cured by ultraviolet irradiation, it can be used as a so-called ultraviolet curable resin (composition) (hereinafter sometimes referred to as "UV curable resin (composition)"). In this case, the ultraviolet curable resin (composition) contains a photopolymerization initiator, a photopolymerizable prepolymer or a photopolymerizable monomer, and further contains a photopolymerization initiator and a sensitizer (for example, ultraviolet sensitization). An agent such as a photopolymerization accelerator is preferred.

Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler's ketone, benzoin, benzylmethyl ketal, benzhydryl benzoate, and hydroxycyclohexyl phenyl ketone. , 2-methyl-1-(4-(methylthio)phenyl)-2-(4-morpholinyl)-1-propane, α-mercapto oxime ester, thioxanthone, etc. Examples of an anthracene such as an aromatic sulfonium ion, an aromatic oxosulfonium ion, or an aromatic iodonium ion, and an anion such as tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate or hexafluoroarsenate The onium salt, the sulfonate, the organometallic complex, and the like are not particularly limited thereto. Further, examples of the ultraviolet sensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine, but are not particularly limited thereto. Further, the photopolymerization accelerator is one which can reduce the polymerization barrier and accelerate the hardening speed by the air at the time of hardening, and examples thereof include p-dimethylamino benzoic acid isoamyl ester and p-dimethylamino benzoin. The acid ethyl ester or the like is not particularly limited thereto. The curing aid may be used singly or in combination of two or more.

The content of the auxiliaries can be appropriately set in accordance with the required properties, and is not particularly limited. However, in general, the total amount of solid components of the ionizing radiation curable resin composition is 0.1 to 10% by mass in total. Preferably, it is preferably 0.5 to 5% by mass.

Moreover, a reactive resin which introduces a photocurable unsaturated group into a thermoplastic resin or a thermosetting resin can be used as needed. Examples of the thermoplastic resin used therein include a polyester resin, an acrylic resin, a polycarbonate resin, a cellulose resin, an acetal resin, a vinyl resin, a polyethylene resin, and a polyphenylene. The vinyl resin, the polypropylene resin, the polyamine resin, the polyimide resin, the fluorine resin, or the like is not particularly limited. In addition, examples of the thermosetting resin include a polyester acrylate resin, a polyurethane acrylate resin, an epoxy acrylate resin, an epoxy resin, a melamine resin, and a phenol resin. The polysiloxane resin or the like is not particularly limited thereto. The photocurable unsaturated group to be introduced into the thermoplastic resin or the thermosetting resin is preferably an ionizing radiation curable unsaturated group. Specific examples of the epoxy group include an ethylenically unsaturated bond such as a (meth)acryl fluorenyl group, a styryl group, a vinyl group, and an allyl group, and an epoxy group. Preferred is a (meth) acrylonitrile group.

The glass transition temperature (Tg) of the above-mentioned reactive resin is not particularly limited, but is preferably 45° C. or higher, and more preferably 80° C. or higher, from the viewpoint of easily suppressing the flow of the ionizing radiation curable resin during curing. More preferably 90 ° C or more. Further, the term "Tg" means the former of the resin A. Further, the weight average molecular weight (Mw) of the reactive resin is not particularly limited, but is preferably 70,000 or more, and more preferably 80,000 or more from the same viewpoint. Further, the value of the weight average molecular weight (Mw), for example, the molecular weight distribution of the compound can be determined by a gel permeation chromatography (GPC) equipped with a differential refractive index detector (RID), from the obtained chromatogram (chart), The standard polystyrene was calculated as a standard curve.

In addition, as the ionizing radiation-curable resin composition, a material which forms a ionizing radiation-curable organic-inorganic hybrid resin by crosslinking by irradiation with ionizing radiation (ultraviolet rays or electron beams) (hereinafter sometimes referred to as "organic" Inorganic matrix forming material"). Among them, the ionizing radiation curable organic-inorganic hybrid resin is different from the conventional composite represented by glass fiber reinforced plastic (FRP), and is closely mixed with organic matter and inorganic matter, and the dispersed state is molecular level. Alternatively, the inorganic component and the organic component may be reacted by irradiation with ionizing radiation to form a film. Since the protective layer 41 contains an ionizing radiation curable organic-inorganic hybrid resin, the adhesion to the gas barrier layer 31 tends to be higher. When the organic-inorganic matrix-forming material containing an inorganic component is used, the ionizing radiation curable resin composition of the present embodiment can be used as an inorganic component containing an organic-inorganic matrix forming material as an inorganic filler as described above. .

The inorganic component of the organic-inorganic matrix forming material may, for example, be a metal oxide such as cerium oxide or titanium dioxide, and cerium oxide is preferred. Examples of the cerium oxide include reactive cerium oxide which is introduced into a photosensitive group having photopolymerization reactivity on its surface. For example, powdery cerium oxide or colloidal cerium oxide which is a precursor can be used for a group having a group represented by the following general formulae (1) and (2), a hydrolyzable thiol group, and a polymerizable unsaturated group in the molecule. The four kinds of compounds are chemically bonded via a mercaptooxy group by a hydrolysis reaction of a hydrolyzable mercapto group.

(In the formula (1), X represents -NH-, an oxygen atom or a sulfur atom, and Y represents an oxygen atom or a sulfur atom, but when X is an oxygen atom, Y is a sulfur atom)

Examples of the hydrolyzable thiol group include a methoxyalkyl group such as an alkoxy fluorenyl group or an ethoxylated oxon group, a halogenated fluorenyl group such as Chlosilyl, an amine fluorenyl group, a fluorenyl group, or a hydrazinyl group. It is not particularly limited to this. Examples of the polymerizable unsaturated group include an acrylonitrile group, a methacryloxy group, a vinyl group, a propylene group, a butadienyl group, a styryl group, an ethynyl group, a cinnamyl group, and a malic acid group. The acrylamide group or the like is not particularly limited thereto.

The average particle diameter D _{50 of the} reactive cerium oxide is appropriately set in accordance with the desired properties, and is not particularly limited, and 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 the reactive cerium oxide having an average particle diameter D ₅₀ within a predetermined range, it is easy to maintain high adhesion to the protective layer 41 or high transparency of the protective layer 41. In addition, the average particle diameter D ₅₀ of the reactive cerium oxide means the median diameter measured by a laser diffraction type particle size distribution measuring apparatus (for example, Shimadzu Corporation: SALD-7000, etc.).

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

Examples of the organic component in the organic-inorganic hybrid resin include the above inorganic component (preferably, reactive ceria) and a compound having a polymerizable polymerizable unsaturated group (for example, having two or more polymerizable groups in the molecule) a saturated polyvalent unsaturated organic compound or a monovalent unsaturated organic compound having one polymerizable unsaturated group in the molecule, or the like).

Examples of the polyvalent unsaturated organic compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, and glycerol tri(methyl). Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane Tris (meth) acrylate, dicyclopentyl di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol 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 (Meth) acrylate such as di(meth)acrylate or polypropylene glycol di(meth)acrylate, but is not particularly limited thereto. These may be used alone or in combination of two or more. Among these, as the polyvalent unsaturated organic compound, a polyfunctional (meth) acrylate having no carboxylic acid group is preferably used.

Examples of the monovalent unsaturated organic compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-B. Hexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (Meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Ester, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-B Oxyethoxyethyl)ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxy diethylene glycol (A Acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2-methoxypropyl (meth) acrylate, methoxy Dipropylene glycol (meth) acrylate, (Meth) acrylate such as methoxytripropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate Class, but is not particularly limited to this. These may be used alone or in combination of two or more. Among these, as the monovalent unsaturated organic compound, a monofunctional (meth) acrylate having no carboxylic acid group is preferably used.

The content ratio of the inorganic component in the organic-inorganic hybrid resin can be appropriately set in accordance with the desired properties, and is not particularly limited, and is preferably 10% by mass or more, more preferably 20% by mass, and preferably 65% by mass or less. It is preferably 40% by mass or less. When the content ratio of the organic component is within the above preferred range, the transparency of the protective layer 41 can be maintained, and the adhesion between the gas barrier layer 31 and the protective layer 41 tends to be easily improved.

(adhesion promoter)
The adhesion promoter is one that can improve the adhesion to the gas barrier layer 31. In the present 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. The acid value of the adhesion promoter is preferably 130 (mgKOH/g) or more and 380 (mgKOH/g) or less, preferably 140 (mgKOH/g) or more and 360 (mgKOH/g) or less. Further, the molecular weight of the adhesion promoter is preferably from 80 to 750, more preferably from 80 to 600.

As the adhesion promoter, a monofunctional (meth) acrylate having a carboxyl group, a monofunctional urethane (meth) acrylate having a carboxyl group, a sulfonate having a (meth) acryl fluorenyl group, and having ( A methyl phosphate propylene group phosphate is preferred, and a monofunctional (meth) acrylate having a carboxyl group and a phosphate having a (meth) acryl fluorenyl group are preferred. When the acid value and molecular weight of these are within the above range, they can be suitably used. Further, when these have the above acid value and molecular weight, they do not correspond to the ionizing radiation curable matrix forming material. As the adhesion promoter having such an acid value and molecular weight, various commercially available products can be used. Specifically, CD9050 manufactured by Sartmer Co., Ltd., M-5300, M-5400 manufactured by Toagosei Co., Ltd., β-CEA manufactured by Daicel Co., Ltd., or KAYAMER PM-2 manufactured by Nippon Kayaku Co., Ltd., and PM-21, JPA-514 made by Chengbei Chemical Company.

The content ratio of the adhesion promoter in the ionizing radiation curable resin composition can be appropriately set in accordance with the desired properties, and is not particularly limited, but is 100 parts by mass in total of the adhesion promoter and the ionizing radiation curable matrix forming material. In other words, it is preferably 1 to 25% by mass, more preferably 1.5 to 20% by mass, still more preferably 2 to 15% by mass. When the content ratio of the adhesion promoter is within the above preferred range, the protective layer 41 which is excellent in adhesion to the gas barrier layer 31 and excellent in durability (durability) can be easily obtained. In the same manner, the content ratio of the ionizing radiation-curable matrix-forming material in the ionizing radiation-curable resin composition can be appropriately set in accordance with the desired properties, and is not particularly limited, but for the adhesion promoter and the ionizing radiation curable matrix. The total mass of the forming materials is preferably from 75 to 99% by mass, more preferably from 80 to 98.5% by mass, even more preferably from 85 to 98% by mass.

(inorganic filler)
The ionizing radiation curable resin composition (and the protective layer 41 to be the cured product) contains the above components and also contains an inorganic filler. By containing an inorganic filler, the adhesion to the gas barrier layer 31 tends to be improved. In the above, as the inorganic filler, the inorganic component of the organic-inorganic matrix forming material and the other inorganic filler (hereinafter sometimes referred to as "additional inorganic filler") may be contained. The inorganic component of the organic-inorganic matrix-forming material is as described above. On the other hand, examples of the inorganic filler to be added include inorganic particles such as cerium oxide, aluminum oxide, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium oxide, and zirconium oxide. There is no particular limitation. These may be used alone or in combination of two or more. In the case of using an organic-inorganic matrix forming material containing an inorganic component as the ionizing radiation curable matrix forming material, the ionizing radiation curable resin composition of the present embodiment is different from the inorganic component of the organic-inorganic matrix forming material. Further, an inorganic filler additionally added may be contained.

Further, the inorganic filler to be added has an average particle diameter D ₅₀ which can be appropriately set in accordance with the desired properties, and is not particularly limited, and is preferably 1 nm or more and 10 μm or less. Within this range, there is a tendency to easily maintain high adhesion to the protective layer 41 or high transparency of the protective layer 41. From the viewpoint of easily obtaining high adhesion to the protective layer 41, it is preferably less than 100 nm, more preferably 10 nm or less. On the other hand, when the unevenness imparting agent of the inorganic filler to be added, which is to be described later, exhibits its function, the average particle diameter D _{50 is} not particularly limited, but is preferably 0.1 μm or more, preferably 0.5 μm or more and 8 μm. Hereinafter, it is more preferably 1 μm or more and 5 μm or less. The average particle diameter D ₅₀ of the inorganic filler to be added is the meaning of the median diameter measured by a laser diffraction type particle size distribution measuring apparatus (for example, Shimadzu Corporation: SALD-7000, etc.). Further, an inorganic filler to be added having an average particle diameter of less than 100 nm and/or an inorganic component of the organic-inorganic matrix-forming material and an inorganic filler having an average particle diameter of 0.1 μm or more may be used in combination.

The content ratio of the inorganic filler in the composition of the ionizing radiation-curable resin (and the protective layer 41 to be a cured product thereof) can be appropriately set in accordance with the desired properties, and is not particularly limited, but is the total amount of the solid components. In general, it is preferably 10% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 75% by mass or less.

(concave and convex agent)
The ionizing radiation curable resin composition (and the protective layer 41 to be a cured product) may have an uneven shape on the surface of the protective layer 41 as necessary, and may further contain a concavo-convex imparting agent made of resin particles. . Examples of the resin-based particles include acrylic resin particles, polyoxynenoid resin particles, nylon resin particles, styrene resin particles, polyethylene resin particles, benzoguanamine resin particles, and urethane. The type of the ester resin particles or the like is not particularly limited. These may be used alone or in combination of two or more.

The average particle diameter D _{50 of the} unevenness imparting agent is not particularly limited, and 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. Further, the average particle diameter D _{50 of the} unevenness-imparting agent means the median diameter measured by a laser diffraction type particle size distribution measuring apparatus (for example, Shimadzu Corporation: SALD-7000 or the like). Further, the inorganic filler to be added having an average particle diameter of less than 100 nm and/or the inorganic component of the organic-inorganic matrix-forming material and the unevenness-imparting agent having an average particle diameter of 0.1 μm or more can be used in combination.

(other ingredients)
Further, the ionizing radiation curable resin composition (and the protective layer 41 to be a cured product thereof) may contain various additives known to the industry as necessary. Examples of various additives include surface conditioners, slip agents, colorants, pigments, dyes, fluorescent whitening agents, flame retardants, antibacterial agents, antifungal agents, photosensitizers, thermal stabilizers, antioxidants, and plasticizers. The agent, the leveling agent, the flow regulator, the antifoaming agent, the dispersing agent, the storage stabilizer, the crosslinking agent, the decane coupling agent, the matting agent, and the like are not particularly limited. These may be used alone or in combination of two or more.

Specific examples of the composition of the ionizing radiation curable resin are preferably (X) an ionizing radiation curable resin containing at least the above-mentioned adhesion promoter, an ionizing radiation curable matrix forming material, and an inorganic filler such as cerium oxide. And (Y) an ionizing radiation curable resin composition containing at least the above-mentioned adhesion promoter and an organic-inorganic matrix forming material (including an inorganic filler as an inorganic component), and (Z) containing at least the above-mentioned adhesion promoter and organic inorganic substrate The forming material (the inorganic filler is contained as an inorganic component) and the ionizing radiation curable resin composition in which the inorganic component in the organic-inorganic matrix forming material is another inorganic filler added separately.

The protective layer 41 can be obtained by curing the ionizing radiation curable resin composition. The method for forming the film can be used in the art, and is not particularly limited. For example, the ionizing radiation-curable resin composition is dissolved or dispersed in a solvent to prepare a coating liquid, and the coating liquid is applied onto the gas barrier layer 31, whereby the protective layer 41 can be formed by curing. As a coating method at this time, a conventionally known coating method can be used, and it is not specifically limited. For example, a doctor blade method, a dip coating method, a roll coating method, a bar coating method, a die coating method, a knife coating method, an air knife coating method, a kiss coating method, a spray coating method, a spin coating method, and the like can be exemplified.

Further, as the solvent, water; a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; an ester solvent such as methyl acetate, ethyl acetate or butyl acetate; methyl cellulose fiber; An ether solvent such as a solvent or an ethyl cellosolve; an alcohol solvent such as methyl alcohol, ethyl alcohol or isopropyl alcohol; and such a mixed solvent are well known in the art. It is also preferred to use a mixed solvent containing a ketone solvent or a ketone solvent. The coating film thus applied can be subjected to ionizing radiation treatment, heat treatment, and/or pressure treatment as necessary, and the protective layer 41 can be produced. Further, the protective layer 41 may be provided on the other main surface 11b side of the substrate 11. In this case, since both surfaces of the laminated gas barrier film 100 have the protective layer 41, they have excellent handleability. .

The light source used for the ionizing radiation irradiation is not particularly limited. For example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, an electron beam accelerator, or the like can be used. In addition, the amount of irradiation at this time can be appropriately set in accordance with the type of the light source to be used, the output performance, and the like, and is not particularly limited. The amount of ultraviolet light irradiation is generally preferably about 100 to 6,000 mJ/cm ² .

Further, the heat source used for the heat treatment is also not particularly limited. It can be used in either contact or non-contact type. For example, a far-infrared heater, a short-wavelength infrared heater, a medium-wavelength infrared heater, a carbon heater, an oven, a heat roller, or the like can be used. The treatment temperature in the heat treatment is not particularly limited, and is usually 50 to 200 ° C, preferably 50 to 180 ° C, preferably 60 to 150 ° C.

The thickness of the protective layer 41 can be appropriately set in accordance with the materials, required properties, and uses, and is not particularly limited. The thickness of the protective layer 41 is preferably from 0.01 to 20 μm, more preferably from 0.5 to 15 μm, still more preferably from 1 to 10 μm, from the viewpoints of weight reduction and film formation, and further considering handling properties or mechanical strength. The protective layer 41 may be formed only in one layer, but may be formed in a plurality of lamination modes, or may be designed such that the gas barrier layer 31 and the protective layer 41 are alternately laminated.

<action>
In the laminated gas barrier film 100 of the present embodiment, the protective layer 41 having excellent adhesion using an adhesion promoter can be provided on the gas barrier layer 31, and the protective layer 41 which can achieve relatively low oxidation can be realized by the prior art. Therefore, it is difficult to cause corrosion or deterioration of the gas barrier layer 31, and even if it is exposed to a high-temperature and high-humidity environment, the adhesion to the gas barrier layer 31 can be suppressed. Therefore, the laminated gas barrier film 100 of the present embodiment can maintain its performance over a long period of time even in a high-temperature, high-humidity, too cold storage environment or use environment. Therefore, the laminated gas barrier film 100 of the present embodiment can be applied not only to a sealed package of articles such as foods, cosmetics, and pharmaceuticals, but also to photoelectric conversion elements, solar cells (PV), electronic paper, and liquid crystal displays ( A high-performance gas barrier film in the field of electronic devices such as flat panel displays (FPDs) such as LCDs and organic EL displays (OELDs).

[Examples]

Hereinafter, the present embodiment will be more specifically described using examples and comparative examples. However, the present invention is not limited to this and the like. Moreover, the numerical values of the various manufacturing conditions or evaluation results in the following examples represent the preferred upper limit or the preferred lower limit in the embodiment of the present invention, and the preferred range may also be the value of the above upper or lower limit. The range specified by the combination of values of the following examples or values between the examples.

[Example 1]
First, a coating liquid a of the following formulation is applied to a main surface of a substrate having a thickness of 125 μm (transparent polyester film, Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) on both sides of a thickness of 125 μm, and dried to emit ultraviolet rays to form a thickness. 3 μm of resin layer.

<coating liquid a>
・Photopolymerizable prepolymer 140 parts by mass
(ionizing radiation hardening matrix forming material)
(Desolight Z7503: 50% by mass of solid content manufactured by JSR, and 38% by mass of cerium oxide of inorganic filler)
・70 parts by mass of thermoplastic resin
(ACRYDICA166: solid content of 430% by DIC company, glass transition temperature of 49 °C)
・Photopolymerization initiator 0.8 parts by mass
(IRGACURE651: manufactured by Chiba Japan Ltd.)
・Diluted solvent (methyl ethyl ketone) 230 parts by mass

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

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

<coating liquid b1>
・Photopolymerizable prepolymer 50 parts by mass
(organic inorganic matrix forming material)
(KZ6445A: manufactured by Arakawa Chemical Industries Co., Ltd., Opster (registered trademark), solid content 50% by mass, inorganic component nano cerium oxide content 30% by mass)
・Adhesive accelerator 0.8 parts by mass
(M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl phthalate, acid value: 205 mgKOH/g, molecular weight: 260 g, solid content: 100% by mass)
・Diluted solvent (methyl ethyl ketone) 78 parts by mass

[Embodiment 2]
In the same manner as in Example 1, except that the coating liquid b1 was used as the coating liquid b1, 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 to obtain a laminated gas barrier property of Example 2. film.

<coating liquid b2>
・Photopolymerizable prepolymer 50 parts by mass
(organic inorganic matrix forming material)
(KZ6445A: Opster (registered trademark) manufactured by Arakawa Chemical Industries Co., Ltd., 50% by mass of solid content, and 30% by mass of nano-sized cerium oxide of inorganic component)
・Adhesive accelerator 1.3 parts by mass
(M5400: phthalic acid monohydroxyethyl acrylate manufactured by Toagosei Co., Ltd., acid value: 205 mgKOH/g, molecular weight: 260 g, solid content: 100% by mass)
・Diluted solvent (methyl ethyl ketone) 78 parts by mass

[Example 3]
The coating liquid b1 was used in the same manner as in Example 1 except that the coating liquid b1 was used, and a laminated gas barrier of Example 3 was obtained by forming a protective layer having a thickness of 1.5 μm and an acid value of 39 mgKOH/g on the gas barrier layer. Film.

<coating liquid b3>
・Photopolymerizable prepolymer 50 parts by mass
(organic inorganic matrix forming material)
(KZ6445A: Opster (registered trademark) manufactured by Arakawa Chemical Industries Co., Ltd., 50% by mass of solid content, and 30% by mass of nano-sized cerium oxide of inorganic component)
・Adhesive accelerator 1.9 parts by mass
(M5400: phthalic acid monohydroxyethyl acrylate manufactured by Toagosei Co., Ltd., acid value: 205 mgKOH/g, molecular weight: 260 g, solid content: 100% by mass)
・Diluted solvent (methyl ethyl ketone) 78 parts by mass

[Comparative Example 1]
The coating liquid b1 was used in the same manner as in Example 1 except that the coating liquid b1 was used. The gas barrier layer was lifted to a protective layer having a thickness of 1.5 μm and an acid value of 17 mgKOH/g to obtain a laminated gas barrier of Comparative Example 1. Film.

<coating liquid b4>
・Photopolymerizable prepolymer 50 parts by mass
(organic inorganic matrix forming material)
(KZ6445A: Opster (registered trademark) manufactured by Arakawa Chemical Industries Co., Ltd., 50% by mass of solid content, and 30% by mass of nano-sized cerium oxide of inorganic component)
・Photopolymerization initiator 2.2 parts by mass
(IRGACURE651: manufactured by Chiba Japan Ltd.)
・Diluted solvent (methyl ethyl ketone) 78 parts by mass

[Comparative Example 2]
The coating liquid b1 was used in the same manner as in Example 1 except that the coating liquid b1 was used, and a protective gas layer of Comparative Example 2 was obtained by forming a protective layer having a thickness of 1.5 μm and an acid value of 21 mgKOH/g on the gas barrier layer. Film.

<coating liquid b5>
・Photopolymerizable prepolymer 50 parts by mass
(ionizing radiation hardening matrix forming material)
(Purple UV-1700B: 100% by mass of solid content manufactured by Nippon Synthetic Chemical Co., Ltd.)
・Photopolymerization initiator 1.5 parts by mass
(IRGACURE651: manufactured by Chiba Japan Ltd.)
・Adhesive accelerator 4.0 parts by mass
(M5400: phthalic acid monohydroxyethyl acrylate manufactured by Toagosei Co., Ltd., acid value: 205 mgKOH/g, molecular weight: 260 g, solid content: 100% by mass)
・Diluted solvent (methyl ethyl ketone) 200 parts by mass

[Example 4]
The coating liquid b1 was used in the same manner as in Example 1 except that the coating liquid b1 was used, and a protective gas layer of Example 4 was obtained by forming a protective layer having a thickness of 1.5 μm and an acid value of 21 mgKOH/g on the gas barrier layer. Film.

<coating liquid b6>
・Photopolymerizable prepolymer 50 parts by mass
(ionizing radiation hardening matrix forming material)
(Purple UV-1700B: 100% by mass of solid content manufactured by Nippon Synthetic Chemical Co., Ltd.)
・Photopolymerization initiator 1.5 parts by mass
(IRGACURE651: manufactured by Chiba Japan Ltd.)
・Adhesive accelerator 4.0 parts by mass
(M5400: phthalic acid monohydroxyethyl acrylate manufactured by Toagosei Co., Ltd., acid value: 205 mgKOH/g, molecular weight: 260 g, solid content: 100% by mass)
・Additional inorganic filler 125 parts by mass
(Nano-cerium oxide, MEK-ST-40: 40% solid content manufactured by Nissan Chemical Co., Ltd.)
・Diluted solvent (methyl ethyl ketone) 300 parts by mass

[Evaluation of adhesion]
The laminated gas barrier films of Examples 1 to 4 and Comparative Examples 1 and 2 obtained were evaluated for adhesion after adhesion and damp heat resistance test. Among them, the protective layer of the laminated gas barrier film was cut according to the lattice tape method in JIS K5400:1990, and the peeling test of the lattice was performed to calculate the number of peeled lattices for 100 lattices. For the time-dependent adhesion, the evaluation was carried out after leaving it at 85 ° C and 85% RH for 500 hours. The results are shown in Table 1.

[Industrial availability]

The ionizing radiation curable resin composition and the laminated gas barrier film of the present invention have excellent adhesion and are less likely to cause corrosion or deterioration of the gas barrier layer, and can be suppressed even when exposed to high temperature and high humidity. Since the adhesion to the gas barrier layer is lowered, it can be used not only in the field of sealed packaging of articles such as foods, cosmetics, and pharmaceuticals, but also in photoelectric conversion elements, solar cells (PV), electronic paper, and liquid crystal. The field of electronic devices such as a flat panel display (FPD) such as a display (LCD) or an organic EL display (OELD) can be widely and effectively utilized.

100‧‧‧Laminated gas barrier film

11‧‧‧Substrate

11a‧‧‧Main face

11b‧‧‧Main face

21‧‧‧ resin layer

21a‧‧‧Main face

31‧‧‧ gas barrier

31a‧‧‧Main face

41‧‧‧Protective layer

Fig. 1 is a schematic cross-sectional view showing a laminated gas barrier film of the first embodiment.

Claims (8)

An ionizing radiation curable resin composition comprising at least an acid 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. In the case of the inorganic filler, the content of the adhesion promoter is 1% by mass in total of 100 parts by mass of the adhesion promoter and the ionizing radiation curable matrix-forming material. 25 mass%, the dry mass of the cured product after hardening, the acid value of 1 g unit is 20 (mgKOH / g) or more and 50 (mgKOH / g) or less. The ionizing radiation curable resin composition according to claim 1, wherein the adhesion promoter is selected from the group consisting of a monofunctional (meth) acrylate having a carboxyl group, a monofunctional urethane (meth) acrylate having a carboxyl group, At least one of a group of a sulfonic acid ester having a (meth)acryl fluorenyl group and a phosphate ester having a (meth) acrylonitrile group. The ionizing radiation curable resin composition of claim 1, which further contains a ketone solvent. The ionizing radiation curable resin composition of claim 2, further comprising a ketone solvent. A protective film of a gas barrier layer, which is characterized by being a cured product of the ionizing radiation curable resin composition according to any one of claims 1 to 4. A laminated gas barrier film comprising at least a gas barrier layer and a protective layer provided on the gas barrier layer, wherein the protective layer is composed of an ionizing radiation curable resin according to any one of claims 1 to 4. In the cured product, the protective layer has an acid value of from 20 (mgKOH/g) to 50 (mgKOH/g) in a dry mass of 1 g unit. The laminated gas barrier film of claim 6, wherein the gas barrier layer is a water vapor barrier layer. The laminated gas barrier film of claim 7, wherein the gas barrier layer has a water vapor transmission rate of less than 1 × 10 ^-1 g / m ² · day (MOCON method, according to JIS K7129, 40 ° C and 90% RH ).