TW201609426A - Gas barrier laminate, electronic device-use member, and electronic device - Google Patents

Abstract

A gas barrier laminate characterized by having a substrate, a gas barrier layer, and a resin layer that contains a bluing agent; an electronic device-use member that comprises this gas barrier laminate; and an electronic device provided with this electronic device-use member. The present invention provides: a gas barrier laminate with outstanding gas barrier properties and colorless transparency; an electronic device-use member comprising this gas barrier laminate; and an electronic device provided with this electronic device-use member.

Description

Gas barrier laminate, electronic device component, and electronic device

The present invention relates to a gas barrier laminate having excellent gas barrier properties and colorless transparency, an electronic device element comprising the gas barrier laminate, and an electronic device having the electronic device component.

In recent years, in order to reduce the thickness, weight, and flexibility of displays such as liquid crystal displays and electroluminescence (EL) displays, a so-called inorganic compound layer (gas barrier layer) is laminated on a transparent plastic film. A gas barrier film is used as a substrate having an electrode instead of a glass substrate.

For example, Patent Document 1 discloses that a high-oxidation yttrium oxide layer having x of SiO _x of 1.8 or more is provided on one surface or both surfaces of a substrate made of a plastic film, and is high by a dry coating method. The oxidized cerium oxide layer is provided with a low-oxidation cerium oxide layer having _x of SiO _x of 1.0 to 1.6 or more, and one or more of oxygen, nitrogen, argon or helium are applied to the low-oxidation cerium oxide layer. After the plasma treatment of the gas, the polymer is laminated on the plasma treatment surface of the oxidized ruthenium oxide layer to form a transparent gas barrier laminated film.

Further, Patent Document 2 discloses a transparent gas-resistance substrate in which a hafnium oxynitride layer and a tantalum nitride layer are sequentially laminated on one surface or both surfaces of a transparent resin substrate.

[First technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-351832

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-062305

As described above, many gas barrier films having an inorganic compound layer as a gas barrier layer have been proposed so far. However, such a gas barrier layer generally has a high refractive index, and the refractive index difference with other adjacent layers becomes large, and a short-wavelength light is reflected at the interface of the layers to make the color tone of the gas barrier film yellow. Class problem.

The present invention has been made in view of the above-described conventional art, and an object of the present invention is to provide a gas-shielded laminate having excellent gas barrier properties and colorless transparency, and an electronic device component comprising the gas barrier laminate. An electronic device having such an element for an electronic device.

In order to solve the above problems, the inventors of the present invention have found that a resin layer containing a bluing agent is provided in a gas-repellent laminate to obtain a gas-repellent laminate having excellent colorless transparency, and the present invention has been completed.

According to the present invention, the gas barrier laminate of the following (1) to (6), the electronic device element of (7), and the electronic device of (8) are provided.

(1) A gas-resistive laminate comprising a substrate, a gas barrier layer, and a resin layer containing a bluing agent.

(2) The gas-resistive laminate according to (1), wherein the gas barrier layer is composed of an inorganic vapor-deposited film or ion-implanted to a layer containing a polymer compound Dealing with it.

(3) The gas-resistance laminate according to (1), wherein the bluing agent has a maximum absorption wavelength in a range of 520 to 600 nm.

(4) The gas barrier laminate according to (1), wherein the vapor barrier layer has a water vapor transmission rate of 0.05 g/(m ² .day) at a temperature of 40 ° C and a relative humidity of 90%. the following.

(5) The gas resistive laminate according to (1), wherein the b* value of the CIE L*a*b* color system of the gas barrier laminate specified in JIS Z 8729-1994 is -1.2~1.2.

(6) The gas resistive laminate according to (1), wherein the gas barrier layer has a light transmittance of 85% or more at a wavelength of 550 nm.

(7) The gas barrier layered product according to the above aspect, wherein the content of the bluing agent is 0.01 to 30% by mass based on the entire resin layer containing the bluing agent.

(8) The gas resistive laminate according to (1), wherein the resin layer containing the bluing agent has a thickness of 0.1 to 100 μm.

(9) The gas-resistance laminate according to (1), wherein the gas barrier laminate is a layer composed of a bluing agent-containing layer/a gas barrier layer/substrate.

(10) The gas-resistance laminate according to (1), wherein the gas barrier laminate is a layer composed of a gas barrier layer/blue agent-containing layer/substrate.

(11) The gas resistive laminate according to (1), wherein the gas barrier laminate is a layer of a gas barrier layer/substrate/bluening agent-containing layer.

(12) An element for an electronic device comprising the gas-resistive laminate according to (1).

(13) An electronic device comprising the component for an electronic device according to (12).

According to the present invention, there is provided a gas barrier laminate having excellent gas barrier properties and colorless transparency, an electronic device component comprising the gas barrier laminate, and an electronic device having the electronic device component.

Hereinafter, the sub-items are: 1) a gas-repellent laminate, 2) an electronic device element, and an electronic device, and the present invention will be described in detail.

1) Gas barrier laminate

The gas-repellent laminate of the present invention has a base material, a gas barrier layer, and a resin layer containing a bluing agent (hereinafter referred to as a "blue-light-containing agent-containing layer").

(1) Substrate

The base material constituting the gas-resistance laminate of the present invention is not particularly limited as long as it can adhere to the gas barrier layer or the bluing agent-containing layer. As the substrate, a film or a sheet is usually used.

The thickness of the substrate is not particularly limited, and may be determined according to the purpose of the gas barrier laminate. The thickness of the substrate is usually from 0.5 to 500 μm, preferably from 1 to 100 μm.

The raw material of the substrate is not particularly limited as long as it is in accordance with the purpose of the gas barrier laminate of the present invention.

As a raw material of the substrate, polyimine, polyamine, polyamidoximine, polyphenylene ether, polyether ketone, polydiether ketone, polyolefin, polyester, polycarbonate, poly Bismuth, polyether oxime, polyphenylene sulfide, propylene resin, cycloolefin polymer, A resin substrate such as an aromatic polymer; a paper substrate such as cellophane, coated paper, or mold paper; and laminated paper of the above resin laminated on these paper substrates.

Among these, a resin substrate is preferred because it is excellent in transparency and versatility, and is preferably a polyester, a polyamide, a polyfluorene, a polyether oxime, a polyphenylene sulfide or a cycloolefin polymer. Preferably, it is a polyester or a cyclic olefin polymer.

Examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate.

Examples of the polyamines include wholly aromatic polyamines, nylon 6, nylon 66, and nylon copolymers.

Examples of the cycloolefin polymer include a norbornene-based polymer, a monocyclic cycloolefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and a hydride of these. Specific examples thereof include APEL (ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals Co., Ltd.), ARTON (northene-based copolymer manufactured by JSR Corporation), and ZEONOR (northene-based copolymerization manufactured by Nippon Seon & Co., Ltd.) Things).

(2) Gas barrier layer

The gas barrier layer constituting the gas barrier layered body of the present invention is a layer having a property (gas barrier property) for suppressing the permeation of a gas such as oxygen or water vapor.

The gas barrier layer is, for example, an inorganic vapor deposited film; and the layer containing the polymer compound (hereinafter referred to as "polymer layer") is subjected to ion implantation treatment, plasma treatment, and ultraviolet irradiation treatment. [In this case, the gas barrier layer does not mean a region that is modified only by ion implantation treatment or the like, but means "a polymer layer containing a modified region"].

As the inorganic vapor deposited film, inorganic compounds, gold can be cited A vapor deposited film of the same type.

Examples of the raw material of the inorganic compound include inorganic oxides such as cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide; and inorganic nitrides such as cerium nitride, aluminum nitride, and titanium nitride; Inorganic carbide; inorganic sulfide; inorganic oxynitride such as lanthanum oxynitride; inorganic oxidized carbide; inorganic carbide carbide; inorganic oxynitride carbide.

Examples of the raw material of the vapor deposited film of metal include aluminum, magnesium, zinc, tin, and the like.

These materials may be used alone or in combination of two or more.

Among these materials, an inorganic vapor-deposited film containing an inorganic oxide, an inorganic nitride or a metal as a raw material is preferable from the viewpoint of gas barrier properties; and, from the viewpoint of transparency, an inorganic oxide or an inorganic nitride is used. An inorganic vapor deposited film as a raw material is preferred.

Examples of the method of forming the inorganic vapor-deposited film include PVD (physical vapor deposition) methods such as vacuum vapor deposition, sputtering, and ion plating; thermal CVD (chemical vapor deposition), and plasma CVD. A CVD method such as a method or a photo CVD method.

The thickness of the inorganic vapor-deposited film varies depending on the inorganic compound to be used, and is preferably from 10 to 2,000 nm, preferably from 20 to 1,000 nm, more preferably from 30 to 500 nm, from the viewpoints of gas barrier properties and handleability. Good range of 40~200nm.

In the gas barrier layer obtained by ion-implanting the polymer layer, examples of the polymer compound to be used include a fluorene-containing polymer compound such as a polyorganosiloxane or a polyazane-based compound, and a polysiloxane compound.醯imine, polyamine, polyamidimide, polyphenylene ether, polyether ketone, polydiether ketone, polyolefin, polyester, poly Carbonate, polyfluorene, polyether oxime, polyphenylene sulfide, polyarylate, propylene resin, cycloolefin polymer, aromatic polymer, and the like.

These polymer compounds may be used alone or in combination of two or more.

Among these, a gas barrier layer having a superior gas barrier property can be formed, and a polymer compound is preferable as the polymer compound. Examples of the ruthenium-containing polymer compound include a polyazane-based compound, a polycarbosilane-based compound, a polydecane-based compound, and a polyorganosiloxane compound. Among these, a polyazinane-based compound is preferred because a gas barrier layer having excellent gas barrier properties can be formed. The ion-implantation treatment of the layer containing the polyazane-based compound forms a layer (tantalum oxynitride layer) having oxygen, nitrogen, and ruthenium as main constituent atoms.

As the polyazane compound, a publicly known substance such as an organic polyazane, an inorganic polyazide or a modified polyazane can be used. The polyazane-based compound can also be used as a commercially available product such as a glass coating material as it is.

The polyazane-based compound may be used alone or in combination of two or more.

The polymer layer may contain other components in addition to the above-described polymer compound insofar as it does not inhibit the object of the present invention. Examples of other components include a curing agent, an anti-aging agent, a photostabilizer, and a flame retardant.

The content of the polymer compound in the polymer layer is preferably 50% by mass or more, and more preferably 70% by mass or more, since a gas barrier layer having more excellent gas barrier properties can be obtained.

The thickness of the polymer layer is not particularly limited, and is usually 20 nm to 10 μm, preferably 30 to 500 nm, more preferably 40 to 200 nm.

In the present invention, even if the layer containing the polymer compound is of a nanometer order, a gas barrier layer having sufficient gas barrier properties can be obtained.

The method of forming the polymer layer is not particularly limited. For example, a solution for forming a polymer layer containing at least one polymer compound, a desired component, and a solvent is prepared, and then the solution for forming a polymer layer is applied by a method known to the public, and the obtained polymer layer is obtained by a method known to the public. The coating film is dried to form a polymer layer.

Examples of the solvent used for the solution for forming a polymer layer include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, and methyl isobutyl amide. A ketone solvent such as a ketone; an aliphatic hydrocarbon solvent such as n-pentane, n-hexane or n-heptane; an alicyclic hydrocarbon solvent such as cyclopentane or cyclohexane.

These solvents may be used alone or in combination of two or more.

Examples of the method for applying the solution for forming a polymer layer include a bar coating method, a spin coating method, a dipping method, a roll coating method, a gravure coating method, a blade coating method, a pneumatic blade coating method, and a roll coating method on a roll. Mold coating, screen printing method, spray coating, flat concave method, and the like.

As a method of drying the formed coating film, a drying method known in the past such as hot air drying, hot roll drying, or infrared irradiation may be employed. The heating temperature is usually in the range of 60 to 130 °C. Heating time, usually from a few seconds to tens of minutes.

Examples of the ions to be implanted in the polymer layer include ions of rare gases such as argon, helium, neon, krypton, and xenon; ions such as fluorocarbons, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; methane; Derivation of alkane gases such as ethane An ion of an olefinic gas such as ethylene or propylene; an ion of a diene gas such as pentadiene or butadiene; an ion of an acetylene gas such as acetylene; and an aromatic hydrocarbon such as benzene or toluene. Gas-based ions; ions of a naphthenic gas such as cyclopropane; ions of a cycloolefin-based gas such as cyclopentene; ions of a metal; ions of an organic ruthenium compound.

These may be used alone or in combination of two or more.

Among these, since it is possible to implant ions more easily and obtain a gas barrier layer having more excellent gas barrier properties, it is preferable to use ions of a rare gas such as argon, helium, neon, krypton or xenon.

The amount of ions to be implanted can be appropriately determined in accordance with the purpose of use of the laminate (necessary gas barrier properties, transparency, etc.).

Examples of the method of implanting ions include a method of irradiating ions (ion beams) accelerated by an electric field, a method of implanting ions in the plasma, and the like. In particular, in the present invention, since the intended barrier layer can be easily obtained, the latter method of implanting plasma ions is preferred.

Plasma ion implantation is to generate plasma in an atmosphere containing a plasma generating gas such as a rare gas, and ions (cations) in the plasma can be generated by applying a negative high voltage pulse to the polymer layer. It is carried out by implanting the surface portion of the polymer layer.

By ion implantation, the thickness of the ion-implanted region can be controlled by the implantation conditions such as the type of ions, the applied voltage, the processing time, etc., and can be in accordance with the thickness of the polymer layer, the purpose of use of the laminate, and the like. The decision is usually 10~400nm. The ion-implanted region preferably has a thickness of 10 to 400 nm in the depth direction from the surface portion of the polymer layer.

(3) Blue agent containing layer

The bluing agent-containing layer constituting the gas-resistance laminate of the present invention is a layer containing a bluing agent and a resin component.

Generally, since the gas barrier layer has a high refractive index and the refractive index difference with other adjacent layers becomes large, light of a short wavelength is easily reflected at the interface of these layers. Therefore, the conventional gas barrier laminate tends to have a yellowish hue.

On the other hand, the gas-repellent laminate of the present invention has a bluing agent-containing layer accompanying the gas barrier layer to suppress yellowing, and has excellent colorless transparency.

The bluing agent is a coloring agent which exhibits a blue to purple color by absorbing orange to yellow light, and is a substance having a function of adjusting the hue of the resin.

The bluing agent is preferably a material having a maximum absorption wavelength in the range of 520 to 600 nm, and preferably has a maximum absorption wavelength in the range of 540 to 580 nm.

The type of the bluing agent is not particularly limited, and an organic coloring agent or an inorganic coloring agent known to the public can be used.

As an organic coloring agent, a chromophore may be exemplified by a monoazo dye having one azo group (-N=N-) in the molecule, and three aromatic amines having methane as a center (including The aromatic heterocyclic ring is a triarylmethane dye having a molecular structure in which a point is symmetrically connected, an anthracycline dye having an anthraquinone skeleton in a molecule, an anthraquinone dye such as a derivative of ruthenium, and the like.

As the inorganic coloring agent, iron blue, enzyl n blue, Berlin blue, Turnbull blue, milori blue, and back are mentioned. Indigo (ferric cyanide-based coloring agent) such as Chinese blue, Paris blue, ultramarine blue, ultramarine violet, etc.; cobalt blue (CoO.Al ₂ O) ₃ ) Wait.

Among these, as the bluing agent, lanthanide dye, ultramarine blue, and cobalt blue are preferred.

The bluing agent may be used alone or in combination of two or more.

The content of the bluing agent in the bluing agent-containing layer is preferably from 0.01 to 30% by mass, preferably from 0.05 to 20, based on the total amount of the bluing agent-containing layer from the viewpoint of obtaining more excellent effects of the present invention. The mass% is more preferably 0.1 to 10% by mass.

The bluing agent contains a resin component contained in the layer, and is not particularly limited as long as it can form a film-like layer and can disperse the bluing agent.

Examples of the resin component include a polymer compound similar to the polymer compound constituting the polymer layer, an energy ray-curable resin such as a UV curable resin, and a thermosetting resin. The UV curable resin may be a resin having a polymerizable functional group such as a (meth) acrylonitrile group. These resin components may be used alone or in combination of two or more.

Among these, the resin component contained in the bluing agent-containing layer is preferably an energy ray-curable resin or a thermosetting resin such as a UV-curable resin.

The energy ray-curable resin may, for example, be a compound having one or two or more unsaturated bonds, and the one or more unsaturated bonds may be one of a compound having an acrylate functional group or the like. More than two unsaturated bonds. For example, ethyl (meth) acrylate, ethyl hexyl (meth) acrylate, styrene, methyl styrene, n-vinyl decyl ketone, etc. are mentioned. As a compound having two or more unsaturated bonds, for example, poly Hydroxymethylpropane tri(meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol bis(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tri Polyfunctional compounds such as methyl acrylate, dipentaerythritol hexa(meth) acrylate, 1,6-hexanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate, and the like A reaction product such as a methyl acrylate (for example, a poly(meth) acrylate of a polyhydric alcohol) or the like.

Here, "(meth) acrylate" means methacrylate and acrylate (the same applies hereinafter).

In the case where the energy ray-curable resin is an ultraviolet curable resin, it is preferred to use a photopolymerization initiator. Specific examples of the photopolymerization initiator include acetophenones, diphenylketones, milazene benzoyl benzoate, and α-aminoxime ester. ), thioxanthone, acetophenone, enzyl, benzoin, decylphosphine oxide, and the like. Further, it is preferred to use a mixed light sensitizer, and specific examples thereof include n-butylamine, triethylamine, and poly-n-butylphosphine.

Further, a light sensitizer and a photopolymerization accelerator which are known to the public may be added as needed.

The amount of the photopolymerization initiator to be added is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the energy ray-curable composition.

Examples of the thermosetting resin include a phenol resin, a urea resin, a diallyl citrate resin, a melanin resin, a guanamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin, and an amine. Base alkyd resin, melanin-urea co-condensation resin, enamel resin, polydecane resin, and the like. Make When a thermosetting resin is used, a curing agent such as a crosslinking agent or a polymerization initiator, a polymerization accelerator, a solvent, a viscosity adjuster, or the like may be used in combination as needed.

The bluing agent contains a layer and may also have a crosslinked structure.

When a crosslinked structure is formed in the bluing agent-containing layer, a publicly known method for forming a crosslinked structure such as an adhesive can be used.

For example, when a resin having a hydroxyl group or a carboxyl group is used, a crosslinking agent such as an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, or a metal chelate crosslinking agent may be used. A crosslinked structure is formed.

The isocyanate crosslinking agent is a compound having an isocyanate group as a crosslinking group.

Examples of the isocyanate-based crosslinking agent include aromatic polyisocyanates such as trimethylolpropane-modified toluene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; and hexamethylene diisocyanate. Aliphatic polyisocyanates; alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate; biuret bodies of these compounds, isocyanuric acid, and ethylene glycol, The low molecular weight active hydrogen such as propylene glycol, neopentyl glycol, trimethylolpropane or castor oil contains an adduct of a reactant of the compound and the like.

The epoxy-based crosslinking agent is a compound having an epoxy group as a crosslinking group.

Examples of the epoxy-based crosslinking agent include 1,3-bis(N,N'-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropane. Base-m-phenyleneamine, ethylene glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, trimethylolpropane diepoxypropyl ether, diepoxypropyl Aniline, diepoxypropylamine, and the like.

The aziridine-based crosslinking agent is a compound having an aziridine group as a crosslinking group.

Examples of the aziridine-based crosslinking agent include diphenylmethane-4,4′-bis(1-aziridine carboxamide) and trimethylolpropane tri-β-aziridine propionate. Tetramethylolethanetris-β-aziridine propionate, toluene-2,4-bis(1-aziridinecarboxamide), tri-extension melamine, diisodecyl-1-(2- Methyl aziridine), indole-1-(2-methylaziridine)phosphine, trimethylolpropane tri-β-(2-methylaziridine) propionate, and the like.

The metal chelate crosslinking agent may, for example, be a chelate compound in which the metal atom is aluminum, zirconium, titanium, zinc, zinc, iron, tin or the like, and particularly preferably an aluminum chelate compound.

Examples of the aluminum chelate compound include diisopropoxy aluminum monooleylacetate acetate, monoisopropoxy aluminum bis-indoleacetic acid acetate, and monoisopropoxy aluminum monooleic acid. Ester monoethyl acetonitrile acetate, aluminum dilaurate monolaurate acetate, diisopropoxy aluminum monooctadecyl acetate, diisopropoxide aluminum Octaethyleneacetate acetate and the like.

These crosslinking agents may be used alone or in combination of two or more.

When these cross-linking agents are used to form a crosslinked structure, the amount used is: a crosslinkable group of a crosslinking agent (in the case of a metal chelate crosslinking agent, a metal chelate crosslinking agent) relative to a hydroxyl group of a polymer compound The carboxyl group is preferably 0.1 to 5 equivalents, more preferably 0.2 to 3 equivalents.

Further, when a resin having a polymerizable functional group such as a (meth) acrylonitrile group is used, a photopolymerization initiator, a thermal polymerization initiator is used. Etc., a crosslinked structure can be formed.

Examples of the photopolymerization initiator include diphenyl ketone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, and benzoin acetone. 2,4-diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethylsulfanyl monosulfide, azobis Isobutyronitrile, 2-chloroindole, diphenyl (2,4,6-trimethylbenzylidene)phosphine oxide, bis(2,4,6-trimethylbenzylidene)-benzene Base-phosphine oxide.

Examples of the thermal polymerization initiator include hydrogen peroxide; peroxodisulfate of ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxydisulfate; and 2,2'-azobis(2- Mercaptopropane) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobisisobutyronitrile, 2,2'-azobis (4 Azo compound such as -methoxy-2,4-dimethylvaleronitrile; benzamidine peroxide, lauryl peroxide, peracetic acid, persuccinic acid, di-t-butyl peroxide An organic peroxide such as tertiary peroxybutanol or anisidine hydroperoxide.

These polymerization initiators may be used alone or in combination of two or more.

When the crosslinking reaction structure is formed by using these polymerization initiators, the amount thereof is preferably 0.1 to 100 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass of the polymer compound.

The content of the resin component in the layer containing the bluing agent (the crosslinked structure is formed when the crosslinked structure is formed) is preferably 77 to 99.99% by mass, preferably 80%, based on the total amount of the bluing agent-containing layer. 99.95 mass%, more preferably 90-99.9 mass%.

The bluing agent-containing layer may also contain other components insofar as it does not impair the efficacy of the invention of the present invention.

Examples of other components include additives such as an ultraviolet absorber, a decane coupling agent, an antistatic agent, a photosetter, an antioxidant, a resin stabilizer, a filler, a bulking agent, and a softener.

These components may be used alone or in combination of two or more.

When the bluing agent-containing layer contains other components, the content thereof is preferably 0.01 to 5% by mass, more preferably 0.01 to 2% by mass, based on the total amount of the bluing agent-containing layer.

The thickness of the bluing agent-containing layer is not particularly limited, and can be appropriately determined in accordance with the intended gas-resistance laminate. The thickness of the layer containing the bluing agent is usually 0.1 to 100 μm, preferably 0.2 to 80 μm, more preferably 0.3 to 50 μm.

The method of forming the bluing agent-containing layer is not particularly limited. For example, a resin composition containing a bluing agent and a resin component (hereinafter referred to as a "bluening agent-containing composition") is prepared, and then a bluing agent-containing composition is applied on a predetermined surface. The obtained coating film is dried and, if necessary, subjected to a crosslinking reaction to form a bluing agent-containing layer.

The preparation method, the coating method, the drying method, and the like of the composition containing the bluing agent are the same as those described above as the method of forming the polymer layer.

(4) Gas barrier laminate

The gas barrier laminate of the present invention has a substrate, a gas barrier layer, and a bluing agent-containing layer.

In the gas barrier laminate of the present invention, the gas barrier layer, the bluing agent-containing layer, and the like may each have one layer, or may have two or more layers.

As the gas barrier laminate of the present invention, as long as it has a substrate, The gas barrier layer and the bluing agent contain layers, and the layer constitution thereof is not particularly limited. Examples of the layer constitution of the gas-retardant laminate of the present invention include the following examples, but are not limited to these examples.

(i) Blue agent containing layer / gas barrier layer / substrate

(ii) Gas barrier layer/blue agent containing layer/substrate

(iii) gas barrier layer / substrate / bluing agent containing layer

The gas barrier laminate of the present invention may have a layer other than the substrate, the gas barrier layer, and the bluing agent-containing layer.

Examples of the layer other than the substrate, the gas barrier layer, and the bluing agent-containing layer include a primer layer, a conductor layer, an impact absorbing layer, an adhesive layer, and a process sheet for improving the adhesion between the layers and the substrate. The laminated position of these layers is not particularly limited. The laminated position of these layers is not particularly limited. Further, the process sheet has a function of protecting the laminate when the laminate is stored and conveyed, and is peeled off when the laminate is used.

The gas barrier laminate of the present invention can be produced, for example, by the following method.

Gas barrier laminate having a layer of (i) bluing agent containing layer/gas barrier layer/substrate

A gas barrier layer is formed on the substrate using the methods previously described. Next, by forming a bluing agent-containing layer on the obtained gas barrier layer by the method described above, a gas barrier layered body having a layer composed of a bluing agent-containing layer/gas barrier layer/substrate can be obtained. .

A gas barrier laminate having a layer of (ii) a gas barrier layer/blue agent containing layer/substrate

A bluing agent-containing layer is formed on the substrate using the method previously described. Next, by forming a gas barrier layer on the obtained bluing agent-containing layer by the method described above, a gas barrier layer having a gas barrier layer/blue agent-containing layer/substrate layer composition can be obtained. body.

Gas barrier laminate having a layer of (iii) a gas barrier layer/substrate/bluening agent-containing layer

A gas barrier layer is formed on the substrate using the methods previously described. Next, by forming a bluing agent-containing layer on the other surface of the substrate by the method described above, a gas barrier layer having a gas barrier layer/substrate/bluening agent-containing layer can be obtained. body.

When the gas-repellent laminate of the present invention has a layer other than the substrate, the gas barrier layer, and the bluing agent-containing layer, a suitable step is added to the above-described production method, and the desired gas barrier property can be obtained. Laminated body.

The thickness of the gas barrier laminate of the present invention is not particularly limited, and is preferably 1 to 1000 μm, more preferably 10 to 500 μm, still more preferably 50 to 100 μm.

The vapor permeability of the gas barrier laminate of the present invention at a temperature of 40 ° C and a relative humidity of 90% is preferably 0.05 g / (m ² .day) or less, preferably 0.04 g / (m ² . The following is preferably 0.03 g/(m ² .day) or less. There is no particular limit, and the smaller the value, the better, but it is usually 0.001 g/(m ² .day) or more.

In such a range, the gas-vapor permeable layer of the present invention is excellent in gas barrier properties. Such a gas-repellent laminate can be suitably used as an element for an electronic device.

The water vapor transmission rate can be measured by the method described in the examples.

The gas barrier laminate of the present invention is specified in JIS Z The b* value of the CIE L*a*b* colorimetric system of 8729-1994 is preferably -1.2 to 1.2, preferably -1.0 to 1.0, more preferably -0.8 to 0.8.

The b* value is a value indicating the degree of yellowish hue and bluishness of the hue when the color is digitized. If the b* value is positive, the hue is yellowish, and if it is negative, the hue is bluish.

When the value of b* is in the above range, the gas-resistive laminate exhibits a hue which is relatively intermediate between yellow and blue. Such a gas-repellent laminate can be suitably used as an element for an electronic device having a light-emitting element.

According to the nature of the formed gas barrier layer, the b* value can be controlled by the selection of the bluing agent used and the content of the bluing agent in the bluing agent-containing layer.

Further, the a* value of the CIE L*a*b* color system defined in JIS Z 8729-1994 of the gas barrier layer of the present invention is preferably -1.2 to 1.2, more preferably -1.0. ~1.0, preferably -0.8~0.8.

The a* value is a value indicating the degree to which the tone is reddish and the hue is greenish when the color is digitized. A positive value of a * indicates a reddish hue, and a negative value indicates a greenish hue.

When the value of a* is in the above range, the gas-resistive laminate exhibits a hue which is relatively intermediate between red and green. Such a gas-repellent laminate can be suitably used as an element for an electronic device having a light-emitting element.

The a* value can be controlled under the resin, other components, etc., which are appropriately selected for use.

The b* value, the a* value, and the like of the CIE L*a*b* color system defined in JIS Z 8729-1994 can be measured by the method described in the examples.

The gas barrier layer of the present invention has a light transmittance at a wavelength of 370 nm. The rate of overshoot is preferably 1% or less, preferably 0.5% or less. The light transmittance at a wavelength of 550 nm is preferably 85.0% or more, preferably 89.0% or more.

The light transmittance can be measured by the method described in the examples.

When the light transmittance at a wavelength of 370 nm is 1% or less, the gas barrier layer can sufficiently absorb ultraviolet rays and is excellent in light resistance.

The light transmittance at a wavelength of 370 nm can be controlled by containing an appropriate amount of the ultraviolet absorber.

A gas-repellent laminate having a light transmittance of 85% or more at a wavelength of 550 nm is excellent in colorless transparency.

The light transmittance at a wavelength of 550 nm can be controlled to a desired value by appropriately determining the content of each additive and the thickness of the gas barrier laminate.

Due to these characteristics, the gas barrier laminate of the present invention can be suitably used as an element for an electronic device.

2) Components for electronic devices and electronic devices

The device for an electronic device of the present invention is characterized by comprising the gas barrier laminate of the present invention. Therefore, since the element for an electronic device of the present invention has excellent gas barrier properties, deterioration of the element due to gas such as water vapor can be prevented. Further, since it is excellent in colorless transparency, it is used as a display member of a liquid crystal display, an electroluminescence display or the like.

The electronic device of the present invention is an element for an electronic device of the present invention. Specific examples thereof include a liquid crystal display, an organic electroluminescence display, an inorganic electroluminescence display, an electronic paper, a solar cell, and the like.

The electronic device of the present invention has excellent gas barrier properties because it has an element for an electronic device comprising the gas barrier laminate of the present invention.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the following examples.

The parts and % in each case are the quality basis unless otherwise stated in advance.

(compound)

The compounds, materials and the like used in the respective examples are shown below.

. UV-curing resin liquid (1): manufactured by JSR, trade name: OPSTAR Z7530, solid content 73%

. Bluening agent (1): composite oxide-based blue agent (manufactured by CIK NanoTek, trade name: COBMIBK15WT%-NO1, cobalt blue, maximum absorption wavelength: 580 nm, solid content 15%)

. Substrate (1): Polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: COSMOSHINE A4100, thickness 50 μm)

. Polyazide compound coating agent (1): (manufactured by Clariant (Japan), trade name: AQUAMICA NL110-20, solid content 20%)

[Manufacturing Example 1]

To 100 parts of the UV-curable resin liquid (1), 4.8 parts of a bluing agent (1) was added, and the mixture was stirred to prepare a bluing agent containing the composition 1.

[Manufacturing Examples 2 to 6]

In the same manner as in Production Example 1, except that the addition ratio was changed to the first table, the composition bluing agents contained compositions 2 to 6.

[Table 1] Table 1

[Example 1]

The polyazinane compound-based coating agent (1) was applied onto the substrate (1) by a spin coating method, and the obtained coating film was heated at 120 ° C for 1 minute to form a perhydropolypolymer having a thickness of 150 nm. A polyazin layer of decane. Next, plasma ion implantation of argon (Ar) was performed on the surface of the polyazide layer using a plasma ion implantation apparatus under the following conditions to form a gas barrier layer.

The bluing agent-containing composition 1 obtained in Production Example 1 was applied onto the gas barrier layer to have a thickness of 1 μm by a bar coating method, and the obtained coating film was dried at 70° C. for 1 minute, and then UV was used. Light ray was irradiated with UV light (high pressure mercury lamp; linear velocity, 20 m/min; cumulative light amount, 100 mJ/cm ² ; peak intensity, 1.466 W; number of pulses, 2 times) to form a bluing agent-containing layer, and a bluing agent was obtained. Layer containing a layer (hereinafter referred to as "C layer") / a gas barrier layer (hereinafter referred to as "B layer") / a substrate (hereinafter referred to as "S layer") Constructed gas barrier laminate 1.

The plasma ion implantation apparatus and ion implantation conditions used to form the gas barrier layer are as follows.

(plasma ion implantation device)

RF power supply: Japan Electronics Corporation, model "RF" 56000

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

(ion implantation conditions)

Plasma generated gas: Ar

Gas flow: 100sccm

Duty cycle: 0.5%

Applied voltage: -15Kv

RF power supply: frequency 13.56MHz, applied power 1000W

Reaction chamber pressure: 0.2Pa

Pulse width: 5μsec

Processing time (ion implantation time): 200 seconds

[Embodiment 2]

In Example 1, except that the bluing agent-containing composition 2 obtained in Production Example 2 was used instead of the bluing agent-containing composition 1, a layer C layer/B layer/S layer was obtained by the same method as in Example 1. A gas barrier laminate 2 of a layer structure.

[Example 3]

In Example 1, except that the bluing agent-containing composition 3 obtained in Production Example 3 was used instead of the bluing agent-containing composition 1, a composition having a C layer/B layer/S layer was obtained by the same method as in Example 1. A gas barrier laminate 3 of a layer structure.

[Example 4]

In Example 1, except that the bluing agent-containing composition 4 obtained in Production Example 4 was used instead of the bluing agent-containing composition 1, a layer C layer/B layer/S layer was obtained by the same method as in Example 1. A gas barrier laminate 4 of a layer structure.

[Example 5]

In Example 1, except that the bluing agent-containing composition 5 obtained in Production Example 5 was used instead of the bluing agent-containing composition 1, a composition having a C layer/B layer/S layer was obtained by the same method as in Example 1. A gas barrier laminate 5 of a layer structure.

[Embodiment 6]

The bluing agent-containing composition 1 obtained in Production Example 1 was applied onto the substrate (1) to have a thickness of 1 μm by a bar coating method, and the obtained coating film was dried at 70 ° C for 1 minute. UV light irradiation was carried out using UV light rays (high pressure mercury lamp; linear velocity, 20 m/min; cumulative light amount, 100 mJ/cm ² ; peak intensity, 1.466 W; number of pulses, 2 times) to form a bluing agent-containing layer.

The polyazinane compound-based coating agent (1) was applied onto the bluing agent-containing layer by a spin coating method, and the obtained coating film was heated at 120 ° C for 1 minute to form a perhydrogen-containing polymer having a thickness of 150 nm. A polyazin layer of decane.

Next, using a plasma ion implantation apparatus on the surface of the polyazide layer, the above conditions are implanted as plasma ion implantation of argon (Ar) to form a gas barrier layer, and a layer B/C layer/S layer is obtained. The gas barrier laminate 6 of the layer structure.

[Embodiment 7]

In Example 1, except that a gas barrier layer was formed on one surface of the substrate (1), a bluing agent-containing layer was formed on the other surface of the substrate (1), and the same method as in Example 1 was carried out. A gas barrier laminate 7 having a layer structure of a B layer/S layer/C layer was obtained.

[Embodiment 8]

In Example 3, an aluminum oxide layer (thickness: 150 nm) obtained under the following conditions was formed as a gas barrier layer on one surface of the substrate (1), and a layer C/B was obtained by the same method as in Example 3. A gas barrier laminate 8 of a layer structure of a layer/S layer.

<Reactive Sputtering Conditions>

. Plasma generated gas: argon, oxygen

. Gas flow rate: argon 100sccm, oxygen 40sccm

. Target material: aluminum

. Power value: 2500W

. Vacuum tank internal pressure: 0.2Pa

[Embodiment 9]

In Example 3, a layer of C layer was obtained by the same method as in Example 3 except that a tantalum nitride layer (thickness: 150 nm) obtained under the following conditions was formed as a gas barrier layer on one surface of the substrate (1). A gas barrier laminate 9 of a layer structure of a B layer/S layer.

<Reactive Sputtering Conditions>

. Plasma generating gas: argon, nitrogen

. Gas flow rate: argon 100sccm, nitrogen 60sccm

. Target material: 矽

. Power value: 2500W

. Vacuum tank internal pressure: 0.2Pa

[Comparative Example 1]

In Example 1, except that the bluing agent-containing composition 6 obtained in Production Example 6 was used instead of the bluing agent-containing composition 1, a non-containing layer (C' having a bluing agent was obtained by the same method as in Example 1. The gas barrier laminate 10 of the layer structure of the layer / B layer / S layer.

The following measurements were performed on the gas-repellent laminates 1 to 10 obtained in Examples 1 to 9 and Comparative Example 1.

(Measurement of water vapor transmission rate)

The water vapor transmission rate of the gas barrier laminates 1 to 10 at a temperature of 40 ° C and a relative humidity of 90% was measured using a water vapor transmission rate measuring device (manufactured by LYSSY Co., Ltd., L80-5000).

The measurement results are shown in the first table.

(visible light transmittance)

The light transmittance at 550 nm of the gas barrier laminates 1 to 10 was measured using a visible light transmittance measuring device (UV-3101PC manufactured by Shimadzu Corporation).

The measurement results are shown in the first table.

(hue evaluation)

The color value specified by the CIE L * a * b * color system of the gas-resistance laminates 1 to 10 was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3200) in accordance with JIS 8729-1994. *.

The measurement results are shown in the second table.

According to the second table, understand the following.

The gas-resistance laminates of Examples 1 to 9 are excellent in gas barrier properties and excellent in colorless transparency.

On the other hand, the gas-resistance laminate of Comparative Example 1 is excellent in gas barrier properties. However, the color value b* becomes larger, and the color tone is yellowish.

Claims (13)

A gas resistive laminate comprising a substrate, a gas barrier layer, and a resin layer containing a bluing agent. The gas barrier layer according to claim 1, wherein the gas barrier layer is composed of an inorganic vapor deposited film or is subjected to ion implantation treatment on a layer containing the polymer compound. . The gas barrier laminate according to claim 1, wherein the bluing agent has a maximum absorption wavelength in a range of 520 to 600 nm. The gas barrier laminate according to claim 1, wherein the gas barrier laminate has a water vapor transmission rate of 0.05 g/(m ² .day) at a temperature of 40 ° C and a relative humidity of 90%. the following. The gas barrier laminate according to the first aspect of the invention, wherein the b* value of the CIE L*a*b* color system of the gas barrier laminate specified in JIS Z 8729-1994 -1.2~1.2. The gas-resistance laminate according to the first aspect of the invention, wherein the gas barrier layer has a light transmittance of 85% or more at a wavelength of 550 nm. The gas-resistance laminate according to the first aspect of the invention, wherein the content of the bluing agent is 0.01 to 30% by mass based on the entire resin layer containing the bluing agent. The gas barrier laminate according to any one of claims 1 to 7, wherein the resin layer containing the bluing agent has a thickness of 0.1 to 100 μm. The gas barrier laminate according to claim 1, wherein the gas barrier laminate is a layer composed of a bluing agent-containing layer/a gas barrier layer/substrate. The gas barrier laminate according to claim 1, wherein the gas barrier property The laminate is composed of a layer of a gas barrier layer/bluening agent-containing layer/substrate. The gas-resistance laminate according to the first aspect of the invention, wherein the gas-resistive laminate is a layer of a gas barrier layer/substrate/blue agent-containing layer. An element for an electronic device comprising the gas barrier laminate according to claim 1 of the patent application. An electronic device comprising the component for an electronic device according to claim 12 of the patent application.