JP2019104791A - Ionization radiation curable resin composition, protective film of gas barrier layer using the same, and laminate gas barrier film using them - Google Patents

Abstract

An ionizing radiation curable resin composition capable of realizing a gas barrier film having excellent adhesion and durability, a protective film for a gas barrier layer using the same, and a laminate having excellent adhesion and durability using the same. Provide gas barrier film and the like. The present invention relates to an adhesion promoter having an acid value of 120 (mg KOH / g) to 400 (mg KOH / g) and a molecular weight of 80 to 900, an ionizing radiation curable matrix forming material (provided that the above-mentioned And at least an inorganic filler, and the adhesion promoter is based on a total of 100 parts by mass of the adhesion promoter and the ionizing radiation curable matrix-forming material. An ionizing radiation curable resin composition containing 1 to 25% by mass and having an acid value per 1 g of dry mass of the cured product after curing of 20 (mgKOH / g) to 50 (mgKOH / g) is provided. To do. [Selection] Figure 1

Description

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

  Conventionally, a gas barrier film is 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, for example, in sealed packaging containers for articles such as food, cosmetics, and pharmaceuticals in order to prevent deterioration of articles due to gas such as water vapor and oxygen.

  In recent years, a gas barrier film that prevents such water vapor, oxygen, etc. transmission is used in flat panel displays such as electronic paper, liquid crystal display (LCD) and organic EL display (OELD) as well as photoelectric conversion elements and solar cells (PV). It is also being used in the field of electronic devices such as (FPD). Since these electronic devices are particularly susceptible to the influence of moisture and the like, and the performance deterioration of the liquid crystal layer and the light emitting layer is easily caused, the gas barrier films used for protecting these electronic devices Higher gas barrier properties (barrier properties) are required compared to gas barrier films used for packaging.

  As such a gas barrier film, it is widely known that an inorganic thin film of an inorganic compound such as silicon oxide or an organic thin film such as a thermosetting resin is formed as a gas barrier layer on a substrate such as polyethylene terephthalate (PET). ing. The gas barrier layer may be formed by physical vapor deposition (PVD) such as vacuum evaporation, sputtering or ion plating, chemical vapor deposition such as reduced pressure chemical vapor deposition, or plasma chemical vapor deposition. Chemical 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 prevents the generation of a scratch of the gas barrier layer or prevents the peeling of the gas barrier layer by a solvent or the like, or improves the handleability. From the viewpoint, a protective layer may be further provided on the gas barrier layer. For example, when it is used for an organic EL display etc., a protective layer is provided on a gas barrier layer, a transparent conductive film is further formed on this protective layer, and patterning is carried out by etching etc., and a circuit is constituted.

As a laminated gas barrier film provided with such a protective layer, Patent Document 1 discloses a base film, a barrier deposition layer having a smooth surface provided on at least one surface of the base film, and the barrier film. An acid resistant protective layer having a smooth surface laminated on a barrier deposited layer, 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, the barrier deposition layer is made of indium zinc oxide, and the atomic ratio of indium (In) to zinc (Zn) in the indium zinc oxide is 0.5 to 0 as In / (In + Zn). The acid resistance of the protective layer is such that the etching rate by the indium tin oxide etching solution having a volume ratio of hydrochloric acid: nitric acid: water of 1: 0.08: 1 is 0.01 μm / min or less. The It describes a gas barrier film, characterized in that those.

  Further, according to Patent Document 2, a gas barrier layer mainly composed of an indium-cerium oxide is formed on at least one surface of a substrate made of a plastic film, and a protective layer is further provided thereon, and the protective layer A gas barrier film is described, which is a layer capable of protecting the gas barrier layer from etching.

  However, the gas barrier films described in these Patent Documents 1 and 2 are poor in the 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 this problem, Patent Document 3 includes a substrate, a gas barrier layer provided on at least one surface of the substrate, and a protective layer provided on the gas barrier layer, and the protective layer And (A) aromatic ring-containing urethane (meth) acrylate, (B) carboxyl group-containing (meth) acrylate, and (C) polyfunctional (meth) acrylate, and having an acid value of 80 mg KOH / g or more per 1 g of dry mass There has been proposed a gas barrier film which is formed using an energy ray-curable resin composition which is 130 mg KOH / g or less.

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

  However, in the patent document 3, since the protective layer of relatively high oxidation is used, for example, the corrosion and deterioration of the inorganic gas barrier layer are easily caused, and further, when exposed to a high temperature and high humidity environment, the gas barrier layer is There is a problem that adhesion is likely to be reduced.

  The present invention has been made in view of the above problems, and an object thereof is an ionizing radiation curable resin composition capable of realizing a gas barrier film excellent in 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 which is excellent in adhesion and durability using the same.

  The present inventors diligently studied to solve the above problems. As a result, it is found that the above-mentioned problems can be solved by forming a protective layer of relatively low oxidation using an ionizing radiation curable resin composition containing a predetermined adhesion promoter, and the present invention is completed. It came to That is, the present invention provides various specific embodiments shown below.

[1] An adhesion promoter having an acid value of 120 (mg KOH / g) or more and 400 (mg KOH / g) and a molecular weight of 80 to 900, an ionizing radiation curable matrix-forming material (but corresponding to the adhesion promoter) And an inorganic filler, and the adhesion promoter is 1 to 25 parts by weight with respect to a total of 100 parts by weight of the adhesion promoter and the ionizing radiation-curable matrix-forming material. % Included,
The ionizing radiation curable resin composition whose acid value per dry weight 1g of hardened | cured material after hardening is 20 (mgKOH / g) or more and 50 (mgKOH / g) or less.

[2] The adhesion promoter includes a carboxyl group-containing monofunctional (meth) acrylate, a carboxyl group-containing monofunctional urethane (meth) acrylate, a sulfonic acid ester having a (meth) acryloyl group, and (meth) acryloyl group. Ionizing radiation curable resin composition as described in [1] which is at least 1 sort (s) selected from the group which consists of phosphate ester which has group.
[3] The ionizing radiation curable resin composition as described in [1] or [2], further containing a ketone solvent.

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

[5] A gas barrier layer, and at least a protective layer provided on the gas barrier layer, wherein the protective layer is cured of the ionizing radiation curable resin composition according to any one of [1] to [3]. The protective gas barrier film, wherein the protective layer has an acid value of 20 (mg KOH / g) or more and 50 (mg KOH / g) or less per 1 g of dry mass.
[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 according to [6], wherein the gas barrier layer has a water vapor transmission rate (MOCON method, according to JIS K 7129, 40 ° C. and 90% RH) less than 1 × 10 ⁻¹ g / m ² · day Film.

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

It is sectional drawing which shows typically the lamination | stacking gas-barrier film of 1st Embodiment.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The positional relationship such as upper, lower, left, and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratio in the drawings is not limited to the illustrated ratio. However, the following embodiments are examples for explaining the present invention, and the present invention is not limited to these. In the present specification, for example, the notation of the numerical range “1 to 100” includes both of the upper limit “1” and the lower limit “100”. In addition, the notation of other numerical ranges is the same. Also, in the present 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 according to a first embodiment of the present invention. The laminated gas barrier film 100 of the present embodiment is provided on the substrate 11, the resin layer 21 provided on the side of one main surface 11 a of the substrate 11, and the side of the one main surface 21 a of the resin layer 21. At least the gas barrier layer 31 and the protective layer 41 provided on one principal surface 31 a side of the gas barrier layer 31 are provided. The laminated gas barrier film 100 has a laminated structure (four-layer structure) in which a substrate 11, a resin layer 21, a gas barrier layer 31, and a protective layer 41 are laminated at least in this order.

  Here, in the present specification, “the resin layer 21 provided on the side of one main surface 11 a of the substrate 11” refers to the resin layer 21 on the surface of the substrate 11 (for example, the main surface 11 a) as shown in FIG. In addition to the embodiment in which the substrate is directly mounted, the embodiment includes an embodiment in which an optional 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. The same applies to other similar descriptions.

<Base material>
The base 11 is a member that supports the resin layer 21, the gas barrier layer 31, and the protective layer 41. As this base material 11, as long as it can support these layers, a well-known thing can be used and the kind in particular is not limited. From the viewpoint of dimensional stability, mechanical strength, etc., generally, a synthetic resin film or glass is preferably used. Furthermore, from the viewpoint of weight reduction etc., a synthetic resin film is more preferably used.

  Examples of synthetic resins used as the substrate 11 include 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), etc. Amorphous polyolefin resin; Polyester resin such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN); Polyamide resin such as nylon 6, nylon 12, copolymer nylon, etc .; Polycarbonate resin Polystyrene-based resin; ABS (acrylonitrile-butadiene-styrene) -based resin; polyvinyl alcohol-based resin such as polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), etc .; polyimide Resins; polyetherimide resins; cellulose resins such as triacetyl cellulose; acrylic resins such as (meth) acrylates; polyethersulfone resins; polyetheretherketone resins; polyvinyl chloride, vinylidene chloride-chloride Polyvinyl chloride resins such as vinyl copolymer, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-acrylic copolymer; polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) And fluorine-containing resins such as tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) and the like, but not limited thereto. Among these, polyester-based resin films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate are preferable as the substrate 11. Among them, uniaxially or biaxially oriented film, particularly biaxially oriented polypropylene (OPP) film is particularly preferable because it is excellent in mechanical strength and dimensional stability. In addition, uniaxially or biaxially oriented polyimide films are particularly preferable for heat resistant applications. One of these may be used alone, or two or more of these may be used in combination. Moreover, the multilayer film which consists of a several layer may be sufficient.

  The transparency of the substrate 11 is not particularly limited, but is preferably optically transparent, for example, in an electronic device application such as a touch panel. 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 the above-described optional layer, the surface of the substrate 11 may be subjected to plasma treatment, corona discharge treatment, flame treatment, far ultraviolet irradiation treatment, anchor, as 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 applied by applying polyester type oil, isocyanate type, urethane type, acrylic type, ethylene vinyl alcohol type, vinyl modified type, epoxy type, modified styrene type, modified silicone type anchor coat agent. By providing them, the adhesion between the substrate 11 and the gas barrier layer 31 can be improved. Further, in order to improve the durability, the 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 according to the required performance and the application, and is not particularly limited. Generally, the thickness of the substrate 11 is preferably 5 to 500 μm, more preferably 10 to 300 μm, in view of weight reduction and thin film formation, as well as handleability and mechanical strength.

  The resin film used as the substrate 11 is preferably selected according to the application and required characteristics, and for example, polyethylene terephthalate, polypropylene, nylon or the like is preferable from the viewpoint of cost for packaging food or chemicals, etc. It is preferable to use a resin film having high gas barrier properties, such as polyethylene naphthalate, polyimide resin, polyether sulfone resin, and amorphous polyolefin resin, as the member, the optical member, etc.

<Resin layer>
The resin layer 21 is for enhancing the surface smoothness and the surface hardness of the substrate 11. By thus providing the resin layer 21 having 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 enhanced, whereby the gas barrier of the entire laminated gas barrier film 100 is achieved. It is possible to improve the quality.

  Various known materials can be used as the resin layer 21, and the type is not particularly limited. Generally, it is composed of thin films of thermoplastic resin, thermosetting resin, ionizing radiation curable resin and the like. As thermoplastic resin and thermosetting resin, saturated or unsaturated polyester resin, acrylic resin, acrylic urethane resin, polyester acrylate resin, polyurethane acrylate resin, epoxy acrylate resin, urethane resin, epoxy resin Resin, vinyl resin, polycarbonate resin, cellulose resin, acetal resin, polyethylene resin, polystyrene resin, polyamide resin, polyimide resin, melamine resin, phenol resin, silicone resin, etc. There is no particular limitation on these. These can be used singly or in combination of two or more. In addition, resin thin films such as ionizing radiation curable resins and organic-inorganic hybrid ionizing radiation curable resins can also be preferably used. The detailed description of these is given in the protective layer 41 to be described later, so it is omitted here.

  The thickness of the resin layer 21 can be appropriately set according to the required performance and the use, and is not particularly limited. Generally, the thickness of the resin layer 21 is preferably 0.5 to 50 μm, and more preferably 1 to 10 μm, in view of weight reduction and thin film formation, as well as handleability, mechanical strength, and the like.

<Gas barrier layer>
The gas barrier layer 31 is a protection target (for example, a photoelectric conversion element, a solar cell, an electronic paper, a flat panel display (FPD) such as a liquid crystal display (LCD) or an organic EL display (OELD)) disposed on the substrate 11 side. An electronic device or the like is 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 the object to be protected, the required performance, the application and the like, 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 It is. In the present specification, the oxygen permeability means a value measured under the conditions of 40 ° C. and 90% RH by the MOCON method using an oxygen permeability measuring device in accordance with JIS K7129.

Similarly, in 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, more preferably 1 × 10 ⁻² g / m ² · day or less is there. In the present specification, the water vapor transmission rate refers to a value measured under the conditions of 40 ° C. and 90% RH by the MOCON method using a water vapor transmission rate measuring device in accordance with JIS K7129. As described above, 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 in many cases, and the inorganic thin film is not only relatively hard and brittle, Many are poor in adhesion to the protective film conventionally used. Therefore, when the 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 prominent.

  As the gas barrier layer 31, those known in the art can be applied, and the type is not particularly limited. Various inorganic thin films having the preferable gas barrier properties described above 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, a semimetal such as silicon, or a compound thereof (metal compound or inorganic compound) Is also preferably used. Among these, a gas barrier layer made of an inorganic compound is more preferable from the viewpoint of the transmittance of oxygen, water vapor and the like, cost and the like.

  The gas barrier layer 31 can be configured as a thin film of metal, metal compound or inorganic compound. Here, as metal compounds and inorganic compounds, for example, oxides such as silicon, aluminum, magnesium, calcium, zirconium, boron, hafnium, barium, zinc, tin, titanium, selenium, indium, nitrides, carbides, oxynitrides , Oxidized carbides, nitrided carbides, and those doped with other metals (tin, zinc, gallium, antimony, etc.), etc., but not limited thereto. Among these, silicon-based inorganic oxides such as silicon oxide, silicon oxynitride and silicon oxide carbide, indium tin oxide (ITO), indium gallium zinc oxide (IGZO), indium gallium oxide (IGO) , Gallium Zinc Oxide (GZO), Zinc Tin Oxide (ZTO), Indium Zinc Zinc Oxide (IZTO), Indium Gallium Zinc Zinc Oxide (IGZTO), Antimony Tin Oxide (ATO) Is more preferably used. These can be used singly or in combination of two or more. In addition, as a formation method of the gas barrier layer 31, a well-known method in this industry can be applied, It does not specifically limit. For example, a vacuum evaporation method, a sputtering method, a plasma CVD method, an ion assist method, a spray method, a spin coating method and the like can be mentioned. Further, the gas barrier layer 31 is preferably optically transparent, which makes it possible to make the entire laminated gas barrier film 100 transparent, and can be suitably used, for example, in the above-described FPD application.

  The thickness of the gas barrier layer 31 can be appropriately set according to the material to be configured, the required performance, and the use, and is not particularly limited. The thickness of the gas barrier layer 31 is generally preferably 5 to 500 nm, more preferably 20 to 300 nm, in view of weight reduction and thin film formation, as well as handleability and mechanical strength. The gas barrier layer 31 may be formed of only one inorganic layer comprising the above-described metal, metal compound, and inorganic compound, but a plurality of such inorganic layers may be laminated, and from the inorganic layer and the resin The organic layers may be alternately stacked. 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 be adjacent to each other. Thereby, the adhesion between the gas barrier layer 31 and the protective layer 41 tends to be enhanced.

<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 manner, generation of scratches in the gas barrier layer 31, partial damage or partial peeling of the gas barrier layer 31 is suppressed, and the handleability of the entire laminated gas barrier film 100 is enhanced.

  In the present embodiment, the protective layer 41 is composed of a cured product of the ionizing radiation curable resin composition, and the acid value thereof is 20 (mg KOH / g) or more and 50 (mg KOH / g) or less per 1 g of dry mass. is there. In addition, an acid value means the value measured by the neutralization titration method by potassium hydroxide standard liquid according to JISK 0070. Not only the adhesion between the gas barrier layer 31 and the protective layer 41 is excellent, but also the durability is excellent, when the acid value of the protective layer 41 is 20 (mg KOH / g) to 50 (mg KOH / g). Film 100 can be realized. The acid value of the protective layer 41 is preferably 20 (mg KOH / g) or more and 45 (mg KOH / g) or less, and 20 (mg KOH / g) or more and 40 (mg KOH / g) from the viewpoint of the balance between adhesion and durability. g) or less is more preferable.

(Ionizing radiation curable resin composition)
The protective layer 41 having the above-mentioned acid value can be obtained by curing a predetermined ionizing radiation curable resin composition. In the present embodiment, a resin material (hereinafter referred to as “ionizing radiation curable matrix forming material”) which forms a matrix (resin film) of the protective layer 41 by crosslinking and curing by irradiation of ionizing radiation (ultraviolet light or electron beam) Adhesion promoter and inorganic filler having an acid value of 120 (mg KOH / g) to 400 (mg KOH / g) and a molecular weight of 80 to 900 (inorganic inorganic matrix-forming material described later) The acid value of the protective layer 41 is adjusted by using the ionizing radiation curable resin composition containing at least the components and / or the inorganic filler to be externally added. Each component will be described in detail below.

  As the ionizing radiation curable matrix forming material, a photocationically polymerizable photocationic polymerizable resin, a photopolymerizable prepolymer, a photopolymerizable monomer, etc. (hereinafter sometimes referred to as "ionizing radiation curable matrix forming material" ) Or mixtures of two or more can be used. However, in the present specification, a material corresponding to an adhesion accelerator having an acid value of 120 (mg KOH / g) or more and 400 (mg KOH / g) and a molecular weight of 80 to 900 is this ionizing radiation curable matrix-forming material It is excluded from

  Specific examples of the cationic photopolymerizable resin include epoxy resins such as bisphenol epoxy resin, novolac epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, and vinyl ether resins, but are particularly limited thereto. I will not. These can be used singly or in combination of two or more.

  Photopolymerizable prepolymers are generally classified roughly into cationic polymerization type and radical polymerization type. Examples of the cationically polymerizable photopolymerizable prepolymers include epoxy resins and vinyl ether resins. Examples of the epoxy resin include bisphenol epoxy resin, novolac epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and the like. As a radically polymerizable photopolymerizable prepolymer, an acrylic prepolymer (hard prepolymer) may be mentioned. The photopolymerizable prepolymers can be used alone or in combination of two or more. Among these, as a photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and becoming a three-dimensional network structure by crosslinking 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, Although various (meth) acrylates, such as silicone (meth) acrylate, etc. are mentioned, it is not specifically limited to these. Although these photopolymerizable prepolymers can be used alone, it is preferable to further add a photopolymerizable monomer from the viewpoint of improving the crosslinking curability and further improving the hardness of the protective layer 41.

  Monofunctional (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butoxyethyl acrylate etc. as the photopolymerizable monomer; Bifunctional (meth) acrylates such as 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalic ester neopentyl glycol diacrylate; dipentaerythritol hexaacrylate, trimethyl Trifunctional or higher functional (meth) acrylates such as propane triacrylate and pentaerythritol triacrylate; styrene, α-methyl methacrylate Styrene-based monomers such as styrene, unsaturated carboxylic acid amides such as (meth) acrylamide, (meth) acrylic acid-2- (N, N-diethylamino) ethyl, (meth) acrylic acid-2- (N, N- Substituted amino alcohol esters of unsaturated acids such as dibenzylamino) ethyl, ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, isocyanuric acid triacrylate (eg tris- ( Multifunctional compounds such as 2-hydroxyethyl) -isocyanuric acid ester (meth) acrylate etc., 3-phenoxy-2-propanoyl acrylate, 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether , And trimethylol pro Examples thereof include polythiol compounds having two or more thiol groups in the molecule such as pantrithioglycolate and pentaerythritol tetrathioglycolate, but are not particularly limited thereto. These can be used singly or in combination of two or more. Among these, from the viewpoint of further improving the adhesion to the gas barrier layer 31, etc., polyfunctional (meth) acrylates having a hydroxyl group are preferable.

  Among these, as the photopolymerizable monomer, polyfunctional (meth) acrylates having a hydroxyl group and no carboxylic acid group are preferably used. Specific examples of such polyfunctional (meth) acrylates are, for example, 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-hydroxy) (Tyl) 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 penta Erythritol tri (meth) acrylate, caprolactone modified pentaerythritol Tra (meth) acrylate, caprolactone modified with pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) Although an acrylate etc. are mentioned, it is not specifically limited to these. These can be used singly or in combination of two or more.

  Here, the ionizing radiation curable resin composition may be referred to as a so-called ultraviolet curable resin (composition) (hereinafter referred to as “UV curable resin (composition)”) when it is cured by ultraviolet irradiation. Can be used as In this case, the ultraviolet curable resin (composition) is a photopolymerization initiator, a sensitizer (for example, an ultraviolet sensitizer), in addition to the above-mentioned photo cationic polymerizable resin, photo polymerizable prepolymer or photo polymerizable monomer. It is preferable to further contain an auxiliary agent such as a photopolymerization accelerator.

  As the photopolymerization initiator, acetophenones, benzophenones, Michler's ketone, benzoin, benzyl methyl ketal, benzoylbenzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) In addition to -1-propane, α-acyloxime ester, thioxanthones, etc., onium such as aromatic sulfonium ion, aromatic oxosulfonium ion, aromatic iodonium ion, etc., tetrafluoroborate, hexafluorophosphate, hexafluoroantimolyb Although there may be mentioned onium salts, sulfonic acid esters, organic metal complexes and the like, which are composed of anions such as nitrate and hexafluoroarsenate, these are not particularly limited. In addition, examples of the UV sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine and the like, but are not particularly limited thereto. Further, the photopolymerization accelerator is capable of reducing the polymerization trouble due to air at the time of curing and accelerating the curing rate, and for example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester and the like Although it mentions, it is not especially limited to these. The curing assistants can be used alone or in combination of two or more.

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

  Moreover, the reactive resin which introduce | transduced the photocurable unsaturated group into the thermoplastic resin or the thermosetting resin can also be used as needed. As a thermoplastic resin used here, for example, polyester resin, acrylic resin, polycarbonate resin, cellulose resin, acetal resin, vinyl resin, polyethylene resin, polystyrene resin, polypropylene resin, polyamide resin And polyimide resins and fluorine resins, but not limited thereto. Further, as the thermosetting resin, for example, polyester acrylate resin, polyurethane acrylate resin, epoxy acrylate resin, epoxy resin, epoxy resin, melamine resin, phenol resin, silicone resin and the like can be mentioned. It is not limited. The photocurable unsaturated group introduced into the thermoplastic resin or thermosetting resin is preferably an ionizing radiation curable unsaturated group. Specific examples thereof include ethylenic unsaturated bonds such as (meth) acryloyl group, styryl group, vinyl group and allyl group, and epoxy group. More preferably, it is a (meth) acryloyl group.

  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, from the viewpoint of easily suppressing the flow of the ionizing radiation curable resin in the curing process. C. or higher, more preferably 90.degree. C. or higher. In addition, Tg here is a thing before hardening of resin A. Further, the weight average molecular weight (Mw) of the reactive resin is not particularly limited, but from the same viewpoint, 70,000 or more is preferable, and more preferably 80,000 or more. In addition, the value of the weight average molecular weight (Mw) is obtained by, for example, measuring the molecular weight distribution of the compound by gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID). From the chart, standard polystyrene can be calculated as a calibration curve.

  In addition, as the above-mentioned ionizing radiation curable resin composition, a material which is crosslinked and cured by irradiation of ionizing radiation (ultraviolet light or electron beam) to form an ionizing radiation curable organic-inorganic hybrid resin (hereinafter referred to as “organic inorganic matrix forming material May also be used). Here, the ionizing radiation curable organic-inorganic hybrid resin is different from an old complex represented by glass fiber reinforced plastic (FRP), in which the mixing method of the organic substance and the inorganic substance is tight, and the dispersion state is the molecular level It is possible to form a film by reacting an inorganic component and an organic component by irradiation with ionizing radiation. 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. In addition, when using the organic-inorganic matrix formation material containing an inorganic component, the ionizing radiation curable resin composition of this embodiment handles the inorganic component of an organic-inorganic matrix formation material as an inorganic filler as it mentioned above .

  As an inorganic component of said organic-inorganic matrix formation material, although metal oxides, such as a silica and a titania, are mentioned, Preferably it is a silica. Examples of the silica include reactive silica in which a photosensitive group having photopolymerization reactivity is introduced on the surface. For example, with respect to powdery silica or colloidal silica as a matrix, four groups represented by the following general formulas (1) and (2), a hydrolyzable silyl group, and a polymerizable unsaturated group are contained in the molecule: It is possible to use one having a compound having a compound chemically linked via a silyloxy group by a hydrolysis reaction of a hydrolyzable silyl group.

(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 the hydrolyzable silyl group include a carboxysilylated silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl group and a hydridosilyl group. It is not particularly limited. Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, acrylamide group and the like, but are not particularly limited thereto. .

The average particle diameter D ₅₀ of the reactive silica can be set appropriately according to the desired performance, is not particularly limited, but is preferably 1nm or more, 10 [mu] m or less, more preferably less than 100 nm, still more preferably 10nm or less. By using the reactive silica having an average particle diameter D ₅₀ in a predetermined range, high adhesion to the protective layer 41 and high transparency of the protective layer 41 tend to be easily maintained. The average particle diameter D ₅₀ of the reactive silica is a laser diffraction particle size distribution analyzer (e.g., Shimadzu Corporation: SALD-7000 etc.) means a median diameter measured by.

  The content ratio 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 preferably 10% by mass or more, more preferably 20% by mass or more, preferably 70% by mass or less And more preferably 60% by mass or less. When the content ratio of the inorganic component is within the above-described preferable range, the adhesiveness between the gas barrier layer 31 and the protective layer 41 tends to be easily improved while maintaining the transparency of the protective layer 41.

  As the organic component in the organic-inorganic hybrid resin, a compound having a polymerizable unsaturated group capable of polymerizing with the above-mentioned inorganic component (preferably reactive silica) (for example, two or more polymerizable unsaturated groups in the molecule) And polyunsaturated organic compounds having one or more unitary unsaturated organic compounds having one polymerizable unsaturated group in the molecule.

  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 monohydroxy penta (meth) acrylate, ditrimethylolpropane tetra ( And (meth) acrylates such as acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc. It is not limited. These can be used singly or in combination of two or more. Among these, as the polyunsaturated organic compound, polyfunctional (meth) acrylates having no carboxylic acid group are preferably used.

  As a unitary unsaturated organic compound, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (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, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxy ether X) Ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2- (Methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, etc. Acrylates are included, but not limited thereto. These can be used singly or in combination of two or more. Among these, monofunctional (meth) acrylates having no carboxylic acid group are preferably used as the unitary unsaturated organic compound.

  The content ratio 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 preferably 10% by mass or more, more preferably 20% by mass, preferably 65% by mass or less And more preferably 40% by mass or less. When the content ratio of the organic component is within the above-described preferable range, the adhesiveness between the gas barrier layer 31 and the protective layer 41 tends to be easily improved while maintaining the transparency of the protective layer 41.

(Adhesive promoter)
The adhesion promoter is to improve the adhesion to the gas barrier layer 31. In this embodiment, 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 is used. Here, the acid value of the adhesion promoter is preferably 130 (mg KOH / g) or more and 380 (mg KOH / g) or less, and more preferably 140 (mg KOH / g) or more and 360 (mg KOH / g) or less. The molecular weight of the adhesion promoter is preferably 80 to 750, more preferably 80 to 600.

  As an adhesion promoter, a monofunctional (meth) acrylate having a carboxyl group, a monofunctional urethane (meth) acrylate having a carboxyl group, a sulfonic acid ester having a (meth) acryloyl group, a phosphorus having a (meth) acryloyl group An acid ester is preferably used, and a carboxyl group-containing monofunctional (meth) acrylate and a phosphoric acid ester having a (meth) acryloyl group are more preferable. Any of these may be used as long as the acid value and the molecular weight are in the above-mentioned ranges. In addition, as long as these have the acid value and molecular weight which were mentioned above, they shall not correspond to the ionizing radiation curable matrix formation material mentioned above. Various commercial products can be used as an adhesion promoter having such an acid value and molecular weight. Specifically, CD 9050 made by Sartmer, M-5300 and M-5400 made by Toagosei, β-CEA made by Daicel Ornex, KAYAMER PM-2 made by Nippon Kayaku Co., PM-21, and the like JPA-514 manufactured by Johoku Chemical Co., Ltd., etc. may be mentioned.

  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, but the total content of 100 parts by mass of the adhesion promoter and the ionizing radiation curable matrix forming material 1 to 25% by mass is preferable, more preferably 1.5 to 20% by mass, and still more preferably 2 to 15% by mass. When the content ratio of the adhesion promoter is in the above-described preferable range, the protective layer 41 having excellent adhesion to the gas barrier layer 31 and adhesion (durability) with time tends to be easily obtained. Similarly, the content ratio 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. However, the adhesion promoter and the ionizing radiation curable matrix forming material Preferably it is 75-99 mass% with respect to a total of 100 mass parts, More preferably, it is 80-98.5 mass%, More preferably, it is 85-98 mass%.

(Inorganic filler)
The ionizing radiation curable resin composition (and the protective layer 41 to be a cured product thereof) contains an inorganic filler together with the above-described components. By containing the inorganic filler, the adhesion to the gas barrier layer 31 tends to be further enhanced. Here, as the inorganic filler, as described above, the inorganic component of the organic / inorganic matrix-forming material and the inorganic filler to be externally added separately (hereinafter, may be referred to as "externally added inorganic filler"). Both are included. The inorganic components of the organic-inorganic matrix-forming material are as described above. On the other hand, examples of the externally added inorganic filler include inorganic particles such as silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide, etc. It is not limited. These can be used singly or in combination of two or more. 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 this embodiment is the inorganic component of the organic-inorganic matrix-forming material Alternatively, it may further contain an externally added inorganic filler.

Outer添無machine filler average particle diameter D ₅₀ of the can appropriately set according to the desired performance, is not particularly limited, but is preferably 1nm or more and 10μm or less. Within this range, high adhesion to the protective layer 41 and high transparency of the protective layer 41 tend to be maintained. From the viewpoint that high adhesion to the protective layer 41 is easily obtained, 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 is also functioned as an unevenness imparting agent described later, the average particle diameter D ₅₀ is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.5 μm or more And 8 μm or less, more preferably 1 μm or more and 5 μm or less. The average particle diameter D ₅₀ of the outer添無machine filler, a laser diffraction particle size distribution analyzer (e.g., Shimadzu Corporation: SALD-7000 etc.) means a median diameter measured by. The 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 the externally added inorganic filler having an average particle size of 0.1 μm or more. .

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

(Conventional agent)
The ionizing radiation-curable resin composition (and the protective layer 41 to be a cured product thereof) is a resin-based particle for imparting an uneven shape to the surface of the protective layer 41 as required, in addition to the above-described components. It may further contain an unevenness imparting agent consisting of Examples of the resin-based particles include acrylic resin particles, silicone resin particles, nylon resin particles, styrene resin particles, polyethylene resin particles, benzoguanamine resin particles, urethane resin particles and the like. It is not particularly limited. These can be used singly or in combination of two or more.

The average particle diameter D ₅₀ 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 It is. The average particle diameter D ₅₀ of the irregularities imparting agent, a laser diffraction particle size distribution analyzer (e.g., Shimadzu Corporation: SALD-7000 etc.) means a median diameter measured by. The 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 to be a cured product thereof) may contain various additives known in the art, as needed. As various additives, surface conditioners, lubricants, colorants, pigments, dyes, optical brighteners, flame retardants, antibacterial agents, antifungal agents, light stabilizers, heat stabilizers, antioxidants, plasticizers, leveling agents Although an agent, a flow control agent, an antifoamer, a dispersing agent, a storage stabilizer, a crosslinking agent, a silane coupling agent, a matting agent etc. are mentioned, it is not specifically limited to these. These can be used singly or in combination of two or more.

  Specific embodiments of the preferred ionizing radiation curable resin composition include (X) an ionizing radiation curable resin containing at least the adhesion promoter described above, an ionizing radiation curable matrix forming material, and an inorganic filler such as silica. Composition, (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 and And 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 Can be mentioned.

  The protective layer 41 can be obtained by curing the above-mentioned ionizing radiation curable resin composition, and the method for forming the same can be any method known in the art, and is not particularly limited. For example, a protective layer 41 is formed by preparing a coating liquid in which the ionizing radiation-curable resin composition described above is dissolved or dispersed in a solvent, and the coating liquid is applied onto the gas barrier layer 31 and cured. Can. As a coating method at this time, a conventionally known coating method can be applied, and it is not particularly limited. For example, a doctor coat method, dip coat method, roll coat method, bar coat method, die coat method, blade coat method, air knife coat method, kiss coat method, spray coat method, spin coat method and the like are exemplified.

  As solvents, 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; methyl alcohol, ethyl Alcohols, alcohol solvents such as isopropyl alcohol, and mixed solvents thereof, such as those known in the art can be used. Among these, ketone solvents and mixed solvents containing ketone solvents are preferably used. The protective layer 41 can be formed by performing ionizing radiation treatment, heat treatment, and / or pressure treatment, etc., as necessary, on the coating film applied in this manner. In addition, the protective layer 41 can also be provided on the other main surface 11b side of the base material 11. In this case, both surfaces of the laminated gas barrier film 100 have the protective layer 41, so that it is easy to handle. It will be excellent.

The light source used in 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. Further, the irradiation amount at this time can be appropriately set according to the type of light source to be used, output performance, etc., and is not particularly limited. The irradiation amount of ultraviolet light is generally about 100 to 6,000 mJ / cm ^{2 of} integrated light amount Is a standard.

  Further, the heat source used in the heat treatment is not particularly limited. Either contact or non-contact can be used suitably. For example, a far infrared heater, a short wavelength infrared heater, a middle wavelength infrared heater, a carbon heater, an oven, a heat roller or the like can be used. Although the processing temperature in heat processing is not specifically limited, Generally it is 50-200 degreeC, Preferably it is 50-180 degreeC, More preferably, it is 60-150 degreeC.

  The thickness of the protective layer 41 can be appropriately set according to the material to be configured, the required performance, and the use, and is not particularly limited. In view of weight reduction and thin film formation, and in consideration of handleability and mechanical strength, generally, the thickness of the protective layer 41 is preferably 0.01 to 20 μm, more preferably 0.5 to 15 μm, and further preferably Is 1 to 10 μm. The protective layer 41 may be formed of only one layer, or may be formed by laminating a plurality of layers, or may be formed by alternately laminating a plurality of gas barrier layers 31 and protective layers 41.

<Function>
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 a protective layer having a relatively low oxidation compared to the prior art. As 41 is realized, it is difficult to cause corrosion, deterioration, etc. of the gas barrier layer 31, and a decrease in 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 this embodiment can maintain its performance over a long period of time even in a severe storage environment of high temperature and high humidity or a use environment. Therefore, the laminated gas barrier film 100 of the present embodiment is not only sealed and packaged for articles such as food, cosmetics, and pharmaceuticals, but also photoelectric conversion elements, solar cells (PV), electronic paper, liquid crystal displays (LCD), 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 more specifically described using examples and comparative examples. However, the present invention is not limited at all by these. The values of various manufacturing conditions and evaluation results in the following examples have meanings as preferable upper limit values or preferable lower limit values in the embodiment of the present invention, and the preferable range is the value of the upper limit or the lower limit described above. And a range defined by a combination of the values of the following examples or the values of the examples.

Example 1
First, the coating liquid a of the following formulation is applied to one main surface of a substrate (transparent polyester film, Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., Cosmos Shine A4300) with 125 μm thickness on which both surfaces are easily adhered To form a resin layer with a thickness of 3 μm.

<Coating solution a>
. 140 parts by mass of photopolymerizable prepolymer (ionizing radiation curable matrix forming material)
(Desolite Z7503 manufactured by JSR, solid content 50% by mass, silica content as inorganic filler 38% by mass)
・ 70 parts by mass of thermoplastic resin (Aclidic A 166: manufactured by DIC, solid content 45% by mass, glass transition temperature 49 ° C.)
-0.8 parts by mass of a photopolymerization initiator (IRGACURE 651: manufactured by Ciba Japan Ltd.)
-Diluted solvent (methyl ethyl ketone) 230 parts by mass

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

Subsequently, on the above-mentioned gas barrier layer, the following coating liquid b1 (ionizing radiation curable resin composition) was applied by a bar coat method and dried. Thereafter, heat treatment at 80 ° C. is performed using a circulating hot air dryer, and then UV irradiation treatment (integrated light quantity: 1000 mJ / cm ² ) is performed using a high pressure mercury lamp to obtain a 1.5 μm thick and acid on the gas barrier layer. The laminated gas barrier film of Example 1 was obtained by forming a protective layer of 25 mg KOH / g.

<Coating solution b1>
. 50 parts by mass of photopolymerizable prepolymer (organic-inorganic matrix forming material)
(KZ 6445A: Arakawa Chemical Industries, Ltd., Opstar (registered trademark), solid content 50% by mass, inorganic silica content 30% by mass)
-Adhesion promoter 0.8 parts by mass (M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl acrylate phthalate, acid value 205 mg KOH / g, molecular weight 260 g, solid content 100 mass%)
-Diluted solvent (methyl ethyl ketone) 78 parts by mass

Example 2
The procedure is carried out in the same manner as in Example 1 except that the following coating solution b2 is used instead of the coating solution b1, and a protective layer having a thickness of 1.5 μm and an acid value of 27 mg KOH / g is formed on the gas barrier layer. A laminated gas barrier film of 2 was obtained.

<Coating solution b2>
. 50 parts by mass of photopolymerizable prepolymer (organic-inorganic matrix forming material)
(KZ 6445A: Arakawa Chemical Industries, Ltd., Opstar (registered trademark), solid content 50% by mass, inorganic silica content 30% by mass)
Adhesion promoter 1.3 parts by mass (M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl acrylate phthalate, acid value 205 mg KOH / g, molecular weight 260 g, solid content 100 mass%)
-Diluted solvent (methyl ethyl ketone) 78 parts by mass

[Example 3]
The procedure is carried out in the same manner as in Example 1 except that the following coating solution b3 is used in place of the coating solution b1, and a protective layer having a thickness of 1.5 μm and an acid value of 39 mg KOH / g is formed on the gas barrier layer. A laminated gas barrier film of 3 was obtained.

<Coating solution b3>
. 50 parts by mass of photopolymerizable prepolymer (organic-inorganic matrix forming material)
(KZ 6445A: Arakawa Chemical Industries, Ltd., Opstar (registered trademark), solid content 50% by mass, inorganic silica content 30% by mass)
Adhesion promoter 1.9 parts by mass (M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl acrylate phthalate, acid value 205 mg KOH / g, molecular weight 260 g, solid content 100 mass%)
-Diluted solvent (methyl ethyl ketone) 78 parts by mass

Comparative Example 1
The same procedure as in Example 1 is carried out except that the coating liquid b4 described below is used instead of the coating liquid b1, and a protective layer having a thickness of 1.5 μm and an acid value of 17 mg KOH / g is formed on the gas barrier layer. A laminated gas barrier film of 1 was obtained.

<Coating solution b4>
. 50 parts by mass of photopolymerizable prepolymer (organic-inorganic matrix forming material)
(KZ 6445A: Arakawa Chemical Industries, Ltd., Opstar (registered trademark), solid content 50% by mass, inorganic silica content 30% by mass)
-Photopolymerization initiator 2.2 parts by mass (IRGACURE 651: manufactured by Ciba Japan Ltd.)
-Diluted solvent (methyl ethyl ketone) 78 parts by mass

Comparative Example 2
The same procedure as in Example 1 is carried out except that the coating liquid b5 described below is used instead of the coating liquid b1, and a protective layer having a thickness of 1.5 μm and an acid value of 21 mg KOH / g is formed on the gas barrier layer. A laminated gas barrier film of 2 was obtained.

<Coating solution b5>
. 50 parts by mass of photopolymerizable prepolymer (ionizing radiation curable matrix forming material)
(Silver UV-1700B: manufactured by Japan Synthetic Chemical Industry, solid content 100% by mass)
Photopolymerization initiator 1.5 parts by mass (IRGACURE 651: manufactured by Ciba Japan Ltd.)
Adhesion promoter 4.0 parts by mass (M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl acrylate phthalate, acid value 205 mg KOH / g, molecular weight 260 g, solid content 100 mass%)
-Dilution solvent (methyl ethyl ketone) 200 parts by mass

Example 4
The procedure is carried out in the same manner as in Example 1 except that the coating solution b6 described below is used instead of the coating solution b1 and a protective layer having a thickness of 1.5 μm and an acid value of 21 mg KOH / g is formed on the gas barrier layer. A laminated gas barrier film of 4 was obtained.

<Coating solution b6>
. 50 parts by mass of photopolymerizable prepolymer (ionizing radiation curable matrix forming material)
(Silver UV-1700B: manufactured by Japan Synthetic Chemical Industry, solid content 100% by mass)
Photopolymerization initiator 1.5 parts by mass (IRGACURE 651: manufactured by Ciba Japan Ltd.)
Adhesion promoter 4.0 parts by mass (M5400: manufactured by Toagosei Co., Ltd., monohydroxyethyl acrylate phthalate, acid value 205 mg KOH / g, molecular weight 260 g, solid content 100 mass%)
· Externally added inorganic filler 125 parts by mass (nano silica, MEK-ST-40: manufactured by Nissan Chemical Industries, 40% solid content)
-Dilution solvent (methyl ethyl ketone) 300 parts by mass

[Evaluation of adhesion]
About the lamination | stacking gas-barrier film of the obtained Examples 1-4 and Comparative Examples 1 and 2, adhesiveness and evaluation of the adhesiveness after a moisture-heat-resistance test were performed. Here, based on the cross-cut tape method in JIS K 5400: 1990, the protective layer of the laminated gas barrier film is incised and the peeling test of the base is carried out. Was counted. The adhesion over time was evaluated after leaving for 500 hours under the conditions of 85 ° C. and 85% RH. The results are shown in Table 1.

  The ionizing radiation curable resin composition and the laminated gas barrier film and the like of the present invention not only have excellent adhesion, but are less likely to cause corrosion or deterioration of the gas barrier layer, and are exposed to high temperature and high humidity environments. Since the decrease in adhesion to the gas barrier layer is suppressed, for example, it is not only in the field of sealed packaging of articles such as food, cosmetics, and pharmaceuticals, but also photoelectric conversion elements, solar cells (PV), electronic paper, liquid crystal displays (LCD) And in the field of electronic devices such as flat panel displays (FPDs) such as organic EL displays (OELDs).

100 ... laminated gas barrier film 11 ... base material 11 a ... principal surface 11 b ... principal surface 21 ... resin layer 21 a ... principal surface 31 ... gas barrier layer 31 a ... principal surface 41 ・ ・ ・ Protective layer

Claims (7)

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 ionizing radiation curable matrix-forming material (but excluding the one corresponding to the adhesion promoter);
Inorganic filler,
Contains at least
The adhesion promoter is contained in an amount of 1 to 25% 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 dry weight of the cured product after curing is 20 (mg KOH / g) or more and 50 (mg KOH / g) or less.
Ionizing radiation curable resin composition. The adhesion promoter has a carboxyl group-containing monofunctional (meth) acrylate, a carboxyl group-containing monofunctional urethane (meth) acrylate, a sulfonic acid ester having a (meth) acryloyl group, and a (meth) acryloyl group. At least one selected from the group consisting of phosphoric acid esters,
The ionizing radiation curable resin composition according to claim 1. Further contains a ketone solvent,
The ionizing radiation curable resin composition according to claim 1 or 2. It consists of hardened | cured material of the ionizing radiation curable resin composition as described in any one of Claims 1-3.
Protective film of gas barrier layer. 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 according to any one of claims 1 to 3,
The protective layer has an acid value of 20 (mg KOH / g) or more and 50 (mg KOH / g) or less per 1 g of dry weight.
Laminated gas barrier film. 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, according to JIS K7129, 40 ° C. and 90% RH) less than 1 × 10 ⁻¹ g / m ² · day.
The laminated gas barrier film according to claim 6.