TW201540522A - Gas barrier laminate, member for electronic device, and electronic device - Google Patents

Abstract

The present invention is: a gas barrier laminate that is formed by laminating a substrate, a gas barrier layer, and an optical adjustment layer in this order, said gas barrier layer being adjacent to said optical adjustment layer, and said gas barrier laminate being characterized in that the refractive index of the gas barrier layer is 1.55-1.81, the refractive index of the optical adjustment layer is 1.20-1.60, and the b* value in the CIE L*a*b* color system specified in JIS Z 8729-1994 is in the range of -1.00 to 1.00; a member for an electronic device, said member comprising the gas barrier laminate; and an electronic device that is provided with said member for an electronic device. The present invention provides a gas barrier laminate having excellent gas barrier properties and colorless transparency, a member for an electronic device, said member comprising the gas barrier laminate, and an electronic device that is provided with said member for an electronic device.

Description

Gas barrier laminated body, member for electronic device, and electronic device

The present invention relates to a gas barrier layered product having excellent gas barrier properties and colorless transparency, and a member for an electronic device comprising the gas barrier layered product, and an electronic device including the member for the electronic device. Device.

In recent years, a display such as a liquid crystal display or an electroluminescence (EL) display has been used to laminate an inorganic compound layer (gas barrier layer) on a transparent plastic film in order to reduce the thickness, weight, and flexibility. A so-called gas barrier film is used instead of a glass plate.

For example, Patent Document 1 describes a transparent gas barrier laminated film in which the value of x of SiO _x is set to be higher than 1.8 on the one or both surfaces of a substrate made of a plastic film by a dry coating method. An oxidation degree ruthenium oxide layer and a low oxidation degree ruthenium oxide layer having an SiO _x x value of 1.0 to 1.6 on the high oxidation degree ruthenium oxide layer, and using oxygen, nitrogen, and argon at the low oxidation degree ruthenium oxide layer After the plasma treatment is performed on one or two or more gases, the polymer layer is laminated on the plasma treatment surface of the low oxidation degree ruthenium oxide layer.

Further, Patent Document 2 describes a transparent gas barrier substrate which is formed by laminating a yttrium oxynitride layer and a tantalum nitride layer on one surface or both surfaces of a transparent resin substrate in this order.

Prior 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, a gas barrier film having an inorganic compound layer has been proposed as a gas barrier layer.

However, since such a gas barrier layer generally has a high refractive index, the refractive index difference with other adjacent layers becomes large, and short-wavelength light is reflected at the interface of the layers, and the gas barrier film is yellow. The problem.

The present invention has been made in view of such actual circumstances. It is an object of the present invention to provide a gas barrier layered product, an electronic device member comprising the gas barrier layered product, and an electronic device including the electronic device member, wherein the gas barrier layered system has excellent properties. Gas barrier and colorless transparency.

In order to solve the above problems, the inventors of the present invention have conceived a gas barrier layered product in which an optical adjustment layer is laminated on a substrate and a gas barrier layer, and has intensively studied the gas barrier layered product. As a result, it has been found that a gas barrier layered body having excellent colorless transparency and gas barrier properties has been completed, wherein the gas barrier layered body, the gas barrier layer and the optical adjustment layer are Formed adjacent to each other, the gas barrier layer and the optical adjustment layer have a layer having a specific refractive index; and the b* value in the CIE L*a*b* color system is a specific range.

As described above, according to the present invention, the gas barrier layered product of the following (1) to (8), the member for an electronic device of (9), and the electronic device of (10) are provided.

(1) A gas barrier layered product in which a substrate, a gas barrier layer, and an optical adjustment layer are laminated in this order, and the gas barrier layer and the optical adjustment layer are adjacent to each other in a gas barrier layer. The body is characterized in that the refractive index of the gas barrier layer is 1.55 to 1.81, the refractive index of the optical adjustment layer is 1.20 to 1.60, and the CIE L*a*b* color specified in JIS Z 8729-1994 The b* value is in the range of -1.00 to 1.00.

(2) The gas barrier layered product according to (1), wherein the gas barrier layer contains a group selected from the group consisting of inorganic oxides, inorganic nitrogen oxides, inorganic carbon oxides, and inorganic nitrogen oxides. At least one of the groups.

(3) The gas barrier layered product according to (1), wherein the gas barrier layer is a layer obtained by modifying a layer containing a polyazide compound.

(4) The gas barrier layered product according to (1), wherein the gas barrier layer has a thickness of from 10 nm to 10 μm.

(5) The gas barrier layered product according to (1), wherein the optical adjustment layer is composed of a cured product of a curable composition.

(6) The gas barrier layered product according to (5), wherein the curable composition contains a curable component and a filler.

(7) The gas barrier layered product according to (1), wherein the optical adjustment layer has a thickness of 5 to 2,500 nm.

(8) The gas barrier layered product according to (1), wherein the optical film thickness (T) of the optical adjustment layer satisfies the following formula (1) or (2), [number 1] 121.43x-100≦T≦115.43x-37.33 (1) 760≦T≦2000 (2)

(x is an integer from 1 to 6).

(9) A member for an electronic device comprising the gas barrier layered product according to (1) above.

(10) An electronic device comprising the member for an electronic device according to (9) above.

According to the present invention, it is possible to provide a gas barrier layered product having excellent gas barrier properties and colorless transparency, a member for an electronic device comprising the gas barrier layered product, and a member for the electronic device. Electronic device.

1‧‧‧Scope 1

2‧‧‧Scope 2

3‧‧‧Scope 3

4‧‧‧Scope 4

5‧‧‧Scope 5

6‧‧‧Scope 6

Fig. 1 is a view showing the relationship between the optical film thickness and b*.

Fig. 2 is a view showing a range of a preferred optical film thickness.

Form for implementing the invention

Hereinafter, the present invention will be described in detail with reference to 1) a gas barrier layered product, and 2) members for an electronic device and an electronic device.

1) Gas barrier laminate

In the gas barrier layered product of the present invention, the substrate, the gas barrier layer and the optical adjustment layer are laminated in this order, and the gas barrier layer and the optical adjustment layer are adjacent to each other. , characterized by: the gas barrier layer The refractive index of the optical adjustment layer is from 1.50 to 1.60, and the b* value of the CIE L*a*b* color system specified in JIS Z 8729-1994 is -1.00 to 1.00. range.

(1) Substrate

The base material constituting the gas barrier layered product of the present invention is not particularly limited as long as it can carry the gas barrier layer and the optical adjustment layer and is transparent.

The transparent substrate refers to a substrate which can pass light rays and can use the gas barrier layered product of the present invention as an optical film. The light transmittance of the substrate at 380 to 780 nm is preferably 80% or more, and more preferably 85% or more.

The thickness of the substrate is not particularly limited, and may be determined in accordance with the purpose of blending the gas barrier layered product. The thickness of the substrate is usually from 0.5 to 500 μm. It is preferably 1 to 100 μm.

As the substrate, a resin film is usually used.

The resin component of the resin film may, for example, be a polyimine, a polyamine, a polyamidene, a polyphenylene ether, a polyether ketone, a polyetheretherketone, a polyolefin, a polyester, or a poly Carbonate, polyfluorene, polyether oxime, polyphenylene sulfide, acrylic resin, cycloolefin polymer, aromatic polymer, and the like.

Among these, polyester, polyamide, polyfluorene, polyether oxime, polyphenylene sulfide or cycloolefin polymer is preferred because of its excellent transparency and versatility. A cycloolefin type polymer is more preferable.

Examples of the polyester include polyethylene terephthalate/polyethylene terephthalate, polybutylene terephthalate/polypair. Polybutylene terephthalate, polyethylene naphthalate, polyarylate, and the like.

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

Examples of the cycloolefin polymer include a norbornene polymer, a monocyclic cyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and These hydrides. Specific examples thereof include APEL (ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals Co., Ltd.), ARTON (northene-based polymer manufactured by JSR Corporation), and ZEONOR (northene-based polymer manufactured by Japan ZEON Co., Ltd.) )Wait.

The resin film may contain various additives insofar as it does not impair the effects of the present invention. Examples of the additive include an ultraviolet absorber, an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, a coloring pigment, and the like. The content of these additives may be appropriately determined depending on the purpose of the compounding.

The resin film can be obtained by preparing a resin composition containing a resin component and various additives as needed, and forming the film into a film shape. The molding method is not particularly limited, and a conventional method such as a casting method or a melt extrusion method can be used.

(2) Gas barrier layer

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

Examples of the gas barrier layer include inorganic compounds such as inorganic oxides, inorganic nitrogen oxides, inorganic carbon oxides, and inorganic nitrogen oxides, and layers containing metals. As a gas barrier layer, especially containing a selected from inorganic oxidation At least one of the group consisting of inorganic nitrogen oxides, inorganic carbon oxides, and inorganic nitrogen oxides is preferred.

Examples of such a gas barrier layer include an inorganic vapor deposition film and a layer obtained by modifying a layer containing a polymer compound (hereinafter referred to as a "polymer layer"). The barrier layer is not only a region that has been modified by ion implantation or the like, but means "a polymer layer containing a modified region"].

As an inorganic vapor deposition film, the vapor deposition film of an inorganic compound and metal is mentioned.

Examples of the raw material of the vapor deposition film of the inorganic compound include inorganic oxides such as cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide; and inorganic nitrogen such as tantalum nitride, aluminum nitride, and titanium nitride. Inorganic carbides; inorganic sulfides; inorganic nitrogen oxides such as bismuth oxynitride; inorganic carbon oxides; inorganic carbonitrides; inorganic nitrogen oxides.

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

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

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

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

The thickness of the inorganic deposited film is based on the inorganic compound used. And different. From the viewpoint of gas barrier properties and handleability, it is preferably from 10 to 2,000 nm, more preferably from 20 to 1,000 nm, more preferably from 30 to 500 nm, still more preferably from 40 to 200 nm.

In the gas barrier layer obtained by modifying the polymer layer, examples of the polymer compound to be used include a polymer compound containing ruthenium, polyimine, polyamine, and polyamidimide. , polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polyfluorene, polyether oxime, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin A polymer, an aromatic polymer, or the like.

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

Among these, a gas barrier layer having more excellent gas barrier properties can be obtained, and as the polymer compound, a polymer compound containing ruthenium is preferred. Examples of the ruthenium-containing polymer compound include a polyazane-based compound, a polycarbodecane-based compound, a polydecane-based compound, and a polyorganosiloxane compound. Since it is possible to form a gas barrier layer which is excellent in gas barrier properties even when it is thin, it is preferable to use a polyazane-based compound. By modifying the layer containing the polyazane-based compound, a layer (barium oxynitride layer) having oxygen, nitrogen, and antimony as main constituent atoms can be formed.

The polyazane-based compound is a polymer compound having a repeating unit containing a -Si-N-bond (indolizane bond) in the molecule. Specifically, it has the formula (1) [Chemical 1]

The compound of the repeating unit represented is preferred. Further, the number average molecular weight of the polyazane-based compound to be used is not particularly limited, and is preferably from 100 to 50,000.

In the above formula (1), n represents an arbitrary natural number. R _x , R _y , and R _z each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, A non-hydrolyzable group which is unsubstituted or has a substituent such as an aryl group or an alkylalkylene group.

Examples of the alkyl group of the unsubstituted or substituted alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, and a third group. A C1-C10 alkyl group such as butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl or n-octyl.

Examples of the cycloalkyl group of the unsubstituted or substituted cycloalkyl group include a cycloalkyl group having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.

Examples of the alkenyl group of the unsubstituted or substituted alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group. An alkenyl group having 2 to 10 carbon atoms.

Examples of the substituent of the alkyl group, the cycloalkyl group and the alkenyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxyl group; a thiol group; an epoxy group; and a glycidoxy group; (methyl) propylene oxime; phenyl, 4-methyl An unsubstituted or substituted aryl group such as a phenyl group or a 4-chlorophenyl group.

Examples of the aryl group which is an unsubstituted or substituted aryl group include an aryl group having 6 to 10 carbon atoms such as a phenyl group, a 1-naphthyl group or a 2-naphthyl group.

Examples of the substituent of the aryl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; and a methoxy group and an ethoxy group. Alkoxy group having 1 to 6 carbon atoms; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloxy group; phenyl group, 4-methylbenzene group An unsubstituted group such as a 4-chlorophenyl group or an aryl group having a substituent.

Examples of the alkyl fluorenyl group include a trimethyl decyl group, a triethyl decyl group, a triisopropyl decyl group, a tri-tert-butyl fluorenyl group, a methyl diethyl decyl group, and a dimethyl decyl group. Diethyl decyl, methyl decyl, ethyl decyl, and the like.

Among these, R _x , R _y , and R _z are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and particularly preferably a hydrogen atom.

As to represent the aforementioned formula (1) having a poly silicon silazane compound repeating units, based R _x, R _y, R _z all poly inorganic hydrogen atom of silicon silazanes, and R _x, R _y, R _z Any one of at least one organic polyazane which is not a hydrogen atom may be used.

Further, in the present invention, a polyazane-modified product can also be used as the polyazane-based compound. For example, JP-A-62-195024, JP-A-2-84437, JP-A-63-81122, JP-A-1-138108, and the like, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is described in the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

Among these, as the polyazane-based compound, all of R _x , R _y , and R _z are used from the viewpoint of easiness of acquisition and formation of an ion-implanted layer having excellent gas barrier properties. It is preferred that the hydrogen atom is a perhydropolyazane.

Further, as the polyazane-based compound, a commercially available product such as a glass coating material can be used.

The polyazane-based compound can 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, without departing from 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, because 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 from 20 nm to 10 μm, preferably from 30 to 500 nm, and more preferably from 40 to 400 nm.

In the present invention, even if the thickness of the polymer layer is on the nanometer scale, a gas barrier film 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 component other than necessary, and a solvent, and the like, and a solution for forming a polymer layer can be applied by a conventional method. The obtained coating film was dried to form a polymer layer.

Examples of the solvent used for the solution for forming a polymer layer include an aromatic hydrocarbon solvent such as benzene or toluene; an ester solvent such as ethyl acetate or butyl acetate; acetone, methyl ethyl ketone, and methyl group. A ketone solvent such as isobutyl 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 can 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, a gravure coating, a doctor blade coating, an air oxygen blade coating, and a roller blade coating. Cloth, die coating, screen printing, spray coating, gravure transfer, and the like.

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

Examples of the modification treatment of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment.

The ion implantation treatment is a method of modifying a polymer layer by implanting ions into a polymer layer as will be described later.

Plasma treatment is a method in which a polymer layer is exposed to a plasma to reform a polymer layer. For example, the plasma treatment can be carried out in accordance with the method described in JP-A-2012-106421.

The ultraviolet irradiation treatment is a method of modifying the polymer layer by irradiating ultraviolet rays to the polymer layer. For example, the ultraviolet modification treatment can be carried out in accordance with the method described in JP-A-2013-226757.

Among these, since the surface of the polymer layer is not roughened and efficiently reformed to the inside thereof, a gas barrier layer having more excellent gas barrier properties can be formed, and ion implantation treatment is preferred. .

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

The plasma system can be used alone or in combination of two or more.

Among these, since it is possible to implant ions more easily and to form 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 beam) accelerated by an electric field, a method of implanting ions in a plasma, and the like. Since the target barrier layer can be easily obtained in the present invention, especially the latter method of implanting plasma ions is preferred.

The plasma ion implantation is, for example, capable of generating a plasma by generating a gas in a plasma containing a rare gas or the like, applying a negative high voltage pulse to the polymer layer, and ion (cation) in the plasma. The surface portion of the polymer layer is implanted.

By ion implantation, the thickness of the region in which the ions are implanted can be controlled by the implantation conditions such as the ion type, the applied voltage, and the processing time, and is determined according to the thickness of the polymer layer, the purpose of use of the laminate, and the like. Yes, usually 10~400nm.

The thickness of the gas barrier layer is usually 10 nm to 10 μm, preferably 10 to 2000 nm, and preferably 20 to 1000 nm.

The refractive index of the gas barrier layer is from 1.55 to 1.81, preferably from 1.60 to 1.67. When the refractive index of the gas barrier layer is less than 1.55, since the problem that the gas barrier laminate is yellow is unlikely to occur, the necessity of utilizing the present invention is lacking. When the refractive index of the gas barrier layer is more than 1.81, it becomes difficult to obtain a gas barrier layered product having b* of 1.00 or less.

Further, the refractive index of the gas barrier layer may be in the above range, and is preferably larger than the refractive index of the optical adjustment layer to be described later. When the refractive index of the gas barrier layer is such a relationship with the refractive index of the optical adjustment layer, a gas barrier layered product having b* of 1.00 or less can be easily obtained.

In the present invention, the refractive index means the refractive index of light having a wavelength of 590 nm measured at 23 °C.

(3) Optical adjustment layer

The optical adjustment layer constituting the gas barrier layered product of the present invention is a layer for adjusting the hue of the gas barrier layered product.

Since the gas barrier layer generally has a high refractive index, the difference in refractive index from the adjacent other layers becomes large and light of a short wavelength easily causes reflection at the interface of the layers. Therefore, the previous gas barrier laminate system has a tendency to appear yellow.

The gas barrier laminate of the present invention has an adjacent gas barrier layer Since the optical adjustment layer is formed, it is possible to suppress the appearance of yellow color and to have excellent colorless transparency.

The optical adjustment layer is not particularly limited as long as it has the characteristics described later, and a conventionally applicable one can be used. Examples of the material of the optical adjustment layer include a cured product of a curable composition, a polyester resin, a polyurethane resin, an acrylic resin, a polycarbonate resin, a vinyl chloride/vinyl acetate copolymer, and a polyvinyl butyl group. A resin such as an acetal resin or a nitrocellulose resin fluorine resin; an inorganic material such as an inorganic oxide, an inorganic nitrogen oxide, an inorganic carbon oxide, or an inorganic nitrogen oxide.

In particular, it is a cured product of a curable composition, a polyester resin, a polyurethane resin, an acrylic resin, a polycarbonate resin, a vinyl chloride/vinyl acetate copolymer, a polyvinyl butyral resin, or a nitro group. A resin such as a cellulose resin fluororesin is preferable, and a layer composed of a cured product of a curable composition is more preferable. When the optical adjustment layer is a layer composed of a cured product of a curable composition, the gas barrier layered body can be further provided with scratch resistance in addition to the function of adjusting the hue of the gas barrier layered product.

The curable composition is a compound containing a curable component and capable of being cured by irradiation with an active energy ray and heating.

A composition which can be cured by irradiation with an active energy ray is a polymerizable prepolymer and a polymerizable monomer as a curable component.

The polymerizable prepolymer includes a polyester acrylate prepolymer obtained by reacting a polyester oligomer having a hydroxyl group at both terminals with (meth)acrylic acid, and a bisphenol ring having a low molecular weight. An epoxy acrylate prepolymer obtained by reacting an oxygen resin and a novolac type epoxy resin with (meth)acrylic acid, by a polyamine A urethane acrylate prepolymer obtained by reacting an ester oligomer with (meth)acrylic acid, a polyol acrylate prepolymer obtained by reacting a polyether polyol with (meth)acrylic acid, or the like.

Examples of the polymerizable monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. , polyethylene glycol di(meth) acrylate, hydroxytrimethyl acetic acid neopentyl glycol di (meth) acrylate, dicyclopentyl di (meth) acrylate, caprolactone modified bicyclic ring Pentene di(meth)acrylate, ethylene oxide modified di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isomeric cyanide di(methyl) Bifunctional (meth) acrylate such as acrylate; trimethylolpropane tri(meth) acrylate, neopentyl alcohol tri(meth) acrylate, propionic acid modified dipentaerythritol tris (A) Acrylate, neopentyl alcohol tri(meth) acrylate, propylene oxide modified trimethylolpropane tri(meth) acrylate, ginseng (propylene oxyethyl) isomeric cyanurate Equivalent trifunctional (meth) acrylate; propionic acid modified dine pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dicotyl More than four functional groups such as hexa (meth) acrylate Acrylate; ethylene glycol divinyl ether, neopentyl alcohol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide modified hydroquinone divinyl ether a vinyl compound such as ethylene oxide-modified bisphenol A divinyl ether, neopentyl alcohol trivinyl ether, dipentaerythritol hexavinyl ether or ditrimethylolpropane polyvinyl ether, but may not necessarily It is limited by these.

These polymerizable compounds can be used alone or in combination of two or more.

Here, the description of the (meth) acrylonitrile group means that the propylene group and the propylene group are contained. Both sides of the methacrylonitrile group.

Further, the curable composition may contain a polymer resin component which does not have reaction-curing property itself, for example, an acrylic resin. The viscosity of the composition can be adjusted by adding a polymer resin component.

Examples of the active energy ray include ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among these, it is possible to use a relatively simple device, and it is preferable to use ultraviolet rays as the active energy ray.

When ultraviolet rays are used as the active energy ray, the curable resin composition preferably contains a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as the polymerization reaction is started by irradiation of ultraviolet rays. Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, and the like. Benzoin polymerization initiator; acetophenone, 4'-dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(A Thio)phenyl]-2-morpholine-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl Acetophenone-based polymerization initiator such as }-2-methyl-propan-1-one; diphenyl ketone, 4-phenyldiphenyl ketone, 4,4'-diethylaminodiphenyl ketone a diphenyl ketone polymerization initiator such as 4,4'-bicyclodiphenyl ketone; 2-methyl oxime (anthraquinone), 2-ethyl hydrazine, 2-tert-butyl fluorene, a lanthanide polymerization initiator of 2-amino guanidine; etc.; 2-methylthioxanthone, 2-ethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthiophene A thioxanthone polymerization initiator such as ketone or 2,4-diethylthioxanthone.

The photopolymerization initiator can be used alone or in combination of two or more. The content of the photopolymerization initiator is not particularly limited, but is usually 0.2 to 30% by mass, preferably 0.5 to 20% by mass based on the curable component.

The composition which can be hardened by heating is a composition containing the polymerizable prepolymer and the polymerizable monomer and further containing a thermal polymerization initiator as a curable component; and a hydrolyzable condensable compound as a hardening Composition of sexual components, etc.

The thermal polymerization initiator is not particularly limited as long as it generates a radical by heating and starts the polymerization reaction. Examples of the thermal polymerization initiator include hydrogen peroxide; peroxodisulfate such as ammonium peroxodisulfate, sodium peroxodisulfate or potassium peroxydisulfate; and 2,2'-azobis (2- Mercaptopropane) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-A An azo compound such as oxy-2,4-dimethylvaleronitrile; benzamidine peroxide, lauric acid peroxide, peracetic acid, persuccinic acid, di-tert-butyl peroxide, third butyl An organic peroxide such as hydrogen peroxide or cumene hydroperoxide.

The thermal polymerization initiator can be used alone or in combination of two or more. The content of the thermal polymerization initiator is not particularly limited, but is usually 0.2 to 30% by mass, preferably 0.5 to 20% by mass based on the curable component.

The hydrolyzable condensable compound may, for example, be a decane compound having a hydrolyzable organic group or an oligomer thereof.

Examples of the decane compound having a hydrolyzable group include tetramethoxynonane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, tetra-n-butoxydecane, and tetraisobenzene. a tetraalkoxy decane such as oxydecane, tetra-second butoxy decane or tetra-butoxy decane; hydrogenated trimethoxy decane, hydrogenated triethoxy A hydrogenated trialkoxy decane such as a decane or a hydrogenated tripropoxy decane.

These decane compounds can be used alone or in combination of two or more. Further, an alkyltrialkoxydecane may be used in combination with the above decane compounds.

The curable composition is preferably a filler in addition to the curable component. The refractive index of the optical adjustment layer can be efficiently controlled by containing a filler.

Examples of the filler include cerium oxide particles, metal oxide particles, polymer particles, and alkylsilicate particles.

Examples of the cerium oxide particles include colloidal cerium oxide, hollow cerium oxide, and a reactive cerium oxide filler.

Examples of the metal oxide particles include particles of titanium oxide, zinc oxide, zirconium oxide, cerium oxide, indium oxide, cerium oxide, tin oxide, and cerium oxide.

Examples of the polymer particles include poly(pentabromophenyl methacrylate), poly(pentabromophenyl acrylate), poly(2,4,6-tribromophenyl methacrylate), and poly( A particle composed of a polymer containing a halogen atom and an aromatic group, such as 1-naphthyl methacrylate), poly(2,6-dichlorostyrene), or poly(2-chlorostyrene).

The alkyl phthalate particles are represented by the formula: R ^a -O[-{Si(OR ^b ) ₂ }-O-] _n -R ^a (wherein R ^a and R ^b represent a carbon number of 1~) The alkyl group of 10, n is an integer of 1 or more and represents the particle of the alkyl phthalate.

Among these, it is preferable that the compatibility with the curable component is excellent and the refractive index of the optical adjustment layer can be efficiently controlled, and cerium oxide particles or alkyl citrate particles are preferable.

The fillers can be used alone or in combination of two or more.

When the filler is a granule, the average particle size is preferably from 2 to 1500 nm.

When the curable composition contains a filler, the content thereof is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass based on the total amount of the solid content of the curable composition.

The curable composition may contain other components insofar as it does not impair the effects of the present invention.

As other components, a leveling agent, an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, etc. are mentioned. These contents may be appropriately determined depending on the purpose of the mixing.

The method of forming the optical adjustment layer is not particularly limited. For example, a coating liquid containing a curable composition and a solvent as needed can be prepared, and then the coating liquid can be applied onto the gas barrier layer by a known method, and the obtained coating film can be cured. An optical adjustment layer is formed. Further, a drying treatment may be performed before the coating film is cured as needed.

Examples of the solvent to be used in the preparation of the coating liquid 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. a ketone solvent such as a ketone; an aliphatic hydrocarbon solvent such as n-pentane, n-hexane or n-heptane; or cyclopentane. An alicyclic hydrocarbon solvent such as cyclohexane or the like.

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

Examples of the coating method include a bar coating method, a spin coating method, a dipping method, a roll coating method, a gravure coating method, a knife coating method, an air oxygen blade coating method, a roll blade coating method, a die coating method, and a net coating method. Printing method, spray coating, gravure transfer method, and the like.

When the coating film is dried, as a drying method, a conventional drying method such as hot air drying, hot roll drying, or infrared irradiation can be employed. Drying temperature The degree is usually in the range of 60 to 130 °C. The drying time is usually from several seconds to several tens of minutes.

The curing of the coating film can be carried out by irradiating the active energy ray or heating by blending the curable composition to be used.

For example, when ultraviolet rays are irradiated, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light, or a metal halide lamp can be used as the ultraviolet light source. The dose of ultraviolet rays is not particularly limited and is usually from 100 mJ/cm ² to 1,000 mJ/cm ² . The irradiation time is usually several seconds to several hours, and the irradiation temperature is usually room temperature to 100 ° C.

The thickness of the optical adjustment layer is usually 5 to 2,500 nm, preferably 10 to 2000 nm.

The refractive index of the optical adjustment layer is from 1.20 to 1.60, preferably from 1.35 to 1.55.

The optical film thickness of the optical adjustment layer is usually 5 to 2,000 nm, preferably 10 to 1,500 nm. The optical film thickness is a value represented by n × d (= nd) when the refractive index of the optical adjustment layer is n and the thickness is d.

By appropriately adjusting the optical film thickness of the optical adjustment layer within the above range, a gas barrier layered product having excellent colorless transparency can be obtained. In general, it is known that the b* is periodically changed with respect to the change in the optical film thickness of the optical adjustment layer. When the inventors of the present invention found that the optical film thickness T of the optical adjustment layer satisfies a specific relationship, it is possible to efficiently obtain a gas barrier layered product having a b* value of -1.00 to 1.00.

The relationship between the optical film thickness of the optical adjustment layer and the b* of the gas barrier layered product when the type of the substrate and the gas barrier layer are constant and the film thicknesses of these are shown in Fig. 1 is shown in Fig. 1.

In the horizontal axis of Fig. 1(a), the optical thickness of the optical adjustment layer is used, and the vertical axis is b* of the gas barrier laminate. When the optical film thickness of the optical adjustment layer is less than 760 nm, the b* system of the gas barrier layered product is increased in accordance with the optical film thickness of the optical adjustment layer, and the periodic variation of the repetition reduction and the addition is exhibited. On the other hand, when the optical thickness of the optical adjustment layer is 760 nm or more, the b* system of the gas barrier laminate falls between -1 and 1, and the b* system of the gas barrier laminate is hardly dependent. The optical film thickness of the optical adjustment layer.

In Fig. 1(b), an enlarged view showing a range in which the optical film thickness in Fig. 1(a) is from 0 to about 900 nm is shown. From the first graph (b), in the range in which the periodic change is displayed (the optical film thickness of the optical adjustment layer is less than 760 nm), the range of the b* of the gas barrier layered product to be -1 to 1 is as follows. . Range 1: 30 ~ 100nm, range 2: 120 ~ 170nm, range 3: 280 ~ 310nm, range 4: 380 ~ 410nm, range 5: 520 ~ 550nm, range 6: 620 ~ 660nm.

Next, the maximum and minimum values of the range 1 to 6 are plotted, and a graph showing the approximate straight line indicating the maximum value and the minimum value is shown in Fig. 2 . The horizontal axis is the number of the range, and the vertical axis is the optical film thickness of the optical adjustment layer.

From Fig. 2, it is found that the approximate straight line at the maximum value of each range becomes y = 115.43x - 37.3, and the approximate straight line of the minimum value becomes y = 12.14x - 100. (x is an integer from 1 to 6, and y is the optical film thickness of the optical adjustment layer).

From the above, in the respective ranges of the range of 1 to 6, as long as the optical film thickness T is in the range between the approximate curve of the maximum value and the approximate curve of the minimum value, the b* value can be efficiently obtained - A gas barrier laminate of 1.00 to 1.00.

That is, by optically conditioning the layer with its optical film thickness T (nm) To satisfy the following formula (1) or (2) [number 2] 121.43x-100≦T≦115.43x-37.33 (1) 760≦T≦2000 (2)

(x is an integer of 1 to 6), and it is possible to efficiently obtain a gas barrier layered product having a b* value of -1.00 to 1.00.

(4) Gas barrier laminate

In the gas barrier layering system of the present invention, the substrate, the gas barrier layer and the optical adjustment layer are laminated in this order, and the gas barrier layer and the optical adjustment layer are adjacent to each other, and the gas barrier layer is adjacent to the gas barrier layer. The gas barrier layer has a refractive index of 1.55 to 1.81, and the optical adjustment layer has a refractive index of 1.20 to 1.60, and the CIE L*a*b* color system defined in JIS Z 8729-1994 *The value is in the range of -1.00 to 1.00.

By using a gas barrier layer and an optical adjustment layer having the above refractive index as appropriate, the reflected light reflected on the surface of the optical adjustment layer and the interface between the optical adjustment layer and the gas barrier layer are reflected. The interference phenomenon of the reflected light can effectively suppress the gas barrier layered body from appearing yellow.

The gas barrier layer and the optical adjustment layer of the gas barrier layered product of the present invention may each have one layer or two or more layers.

The gas barrier layered product of the present invention may have a layer other than the substrate, the gas barrier layer, and the optical adjustment layer.

Examples of the layer other than the substrate, the gas barrier layer, and the optical adjustment layer include a primer layer and a conductor layer for improving the interlayer adhesion to the substrate. Impact absorbing layer, adhesive layer, hard coat layer, process sheet, and the like. 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.

Examples of the layer constitution of the gas barrier layered product of the present invention include the following, but are not limited thereto.

(i) Optical adjustment layer / gas barrier layer / substrate

(ii) Optical adjustment layer / gas barrier layer / substrate / hard coating

(iii) Optical adjustment layer / gas barrier layer / optical adjustment layer / gas barrier layer / substrate

(iv) Optical adjustment layer / gas barrier layer / primer layer / substrate

(v) Optical adjustment layer / gas barrier layer / primer layer / substrate / hard coating

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

On the substrate, a gas barrier layer is formed using the method previously described. Next, by forming an optical adjustment layer on the obtained gas barrier layer by the method described above, a gas barrier layer having a layer of an optical adjustment layer/gas barrier layer/substrate can be obtained. body.

A gas barrier layered product or the like having the layer structure of the above (ii) to (v) can be obtained by performing the same steps as necessary in the same manner.

The thickness of the gas barrier layered product 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 gas barrier layer of the gas barrier laminate of the present invention preferably has a water vapor transmission rate of 40 ° C and a relative humidity of 90%, preferably 0.1 g / (m ² · day) or less, preferably 0.05 g / (m ² . The following is more preferably 0.03 g/(m ² .day) or less. The lower limit is not particularly limited, and is preferably as small as possible, but is usually 0.001 g/(m ² .day) or more.

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

The gas barrier layered system of the present invention has a b* value of the CIE L*a*b* color system specified in JIS Z 8729-1994, preferably -1.00 to 1.00, more preferably -0.80 to 0.80. The b* value indicates the degree to which the color is yellowed and blued. When the b* value is positive, it means yellow, and when it is negative, it means blue. By the b* value being the above range, the gas barrier laminated system exhibits a hue closer to the middle of yellow and blue. The b* value can be controlled by providing an optical adjustment layer of an appropriate optical film thickness in accordance with the refractive index of the formed gas barrier layer.

Further, the gas barrier layered system of the present invention has an a* value of the CIE L*a*b* color system specified in JIS Z 8729-1994, preferably -1.00 to 1.00, preferably -0.80 to 0.80. . The a* value indicates the degree to which the color is digitized to appear red and appear green. When the a* value is positive, it means red, and when it is negative, it means green. By the a* value being in the above range, the gas barrier laminated system exhibits a hue closer to the middle of red and green. Such a gas barrier layered system can be suitably used as a member for an electronic device having a light-emitting element.

The a* value can be controlled by appropriately selecting the resin and other components used.

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

Because of these characteristics, the gas barrier layered system of the present invention can be suitably used as a member for an electronic device.

2) Components and electronic devices for electronic devices

The member for an electronic device of the present invention is characterized by comprising the gas barrier layered product of the present invention. Therefore, since the member for an electronic device of the present invention has excellent gas barrier properties, it is possible to prevent deterioration of components due to gas such as water vapor. Moreover, since it has excellent colorless transparency, it is suitable as a display member of a liquid crystal display, an EL display, etc.

The electronic device of the present invention includes the member for an electronic device of the present invention. Specific examples thereof include a liquid crystal display, an organic EL display, an inorganic EL display, an electronic paper, a solar battery, and the like.

Since the electronic device of the present invention includes the member for an electronic device including the gas barrier layered product of the present invention, it has excellent gas barrier properties.

[Examples]

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

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

(compound)

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

. 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: Aquamika NL110-20, solid content 20%)

. Hardening component (1): urethane acrylate oligomer (Arakawa Industrial Co., Ltd., trade name: Beamset 575VCB)

. Hardening component (2): UV hardening type hard coating agent (Dai Ri Jinghua Industrial Co., Ltd. System, trade name: SEIKABEAM EXF-01L (NS))

. Leveling agent (1): Acrylic copolymer (BYK-Chemie Japan, trade name: BYK 355)

. Filler (1): hollow cerium oxide fine particles (manufactured by Nisshin Chemical Co., Ltd., trade name: Thrulya 4320)

. Filler (2): Zirconia (manufactured by Nissan Chemical Industries, Ltd., trade name: Nano Youth OZ-S 30K)

. Photopolymerization initiator (1): (manufactured by BASF Corporation, trade name: IRGACURE 907)

. Optical adjustment layer forming material (2): UV-curable hard coating agent (curable composition containing a polymerizable component, cerium oxide microparticles as a filler, and a photopolymerization initiator), manufactured by JSR Corporation, trade name: Opstar Z 7530, refractive index of hardened material: 1.49)

. Optical adjustment layer forming material (3): a siloxane-based thermosetting resin (manufactured by COLCOAT, trade name: COLCOAT P. Refractive index: 1.43)

(Measurement of Thickness of Gas Barrier Layer and Optical Adjustment Layer)

The thicknesses of the gas barrier layer and the optical adjustment layer of the gas barrier layered product obtained in the examples and the comparative examples were measured using a stylus type step meter (manufactured by AMBIOS TECNOLOGY, XP-1).

(Measurement of refractive index of gas barrier layer and optical adjustment layer)

The refractive index of the gas barrier layer and the optical adjustment layer of the gas barrier layered product obtained in the examples and the comparative examples was an ellipsometer (manufactured by J.A. Woollam Japan Co., Ltd., trade name: spectroscopic light). Determined by Ellipsometry-2000U).

[Manufacturing Example 1]

10 parts of curable component (1), 0.01 part of leveling agent (1), 49 parts of filler (1), 0.1 part of photopolymerization initiator (1), 1,250 parts of methyl isobutyl ketone, cyclohexanone 1250 parts were uniformly mixed to obtain an optical adjustment layer forming material (1). The cured product of the optical adjustment layer forming material (1) had a refractive index of 1.37.

[Manufacturing Example 2]

10 parts of curable component (2), 0.01 part of leveling agent (1), 133 parts of filler (2), 0.3 parts of photopolymerization initiator (1), 1440 parts of methyl isobutyl ketone, cyclohexanone 1440 parts were uniformly mixed to obtain an optical adjustment layer forming material (4). The cured product of the optical adjustment layer forming material (4) had a refractive index of 1.61.

[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 2 minutes to form a perhydropolyazide nitrogen having a thickness of 150 nm. a polydecazane layer of an alkane. Next, an argon (Ar) plasma was ion-implanted on the surface of the polyazide layer using a plasma ion implantation apparatus under the following conditions to form a gas barrier layer (refractive index: 1.62, thickness 150 nm).

On the gas barrier layer, the optical adjustment layer forming material (1) obtained in Production Example 1 was applied by a bar coating method and the obtained coating film was dried at 70 ° C for 1 minute, and then a UV light irradiation line was used. UV light irradiation (high pressure mercury lamp; production line speed, 20 m/min; cumulative dose, 100 mJ/cm ² ; peak intensity, 1.466 W; number of passes, 2 times) was used to form an optical adjustment layer (film thickness: 20 nm, optical film). Thickness: 28 nm) to obtain a gas barrier layered body 1.

Plasma ion implantation device used to form a gas barrier layer And ion implantation conditions 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.

(plasma ion implantation conditions)

Processing chamber - internal pressure: 0.2Pa

Plasma generating gas: argon

Gas flow: 100sccm

RF output power: 1000W

RF frequency: 1000Hz

RF pulse amplitude: 50μsec

RF delay: 25μsec

DC voltage: -6kV

DC frequency: 1000Hz

DC pulse amplitude: 5μsec

DC delay: 50μsec

Duty ratio: 0.5

Processing time: 200sec

[Embodiment 2]

The optical adjustment layer (film thickness: 50 nm, optical film thickness: 75 nm) was formed by using the optical adjustment layer forming material (2) instead of the optical adjustment layer forming material (1) in Example 1, and was used in the same manner as in Example 1. In the same manner, the gas barrier layered body 2 is obtained.

[Example 3]

The gas barrier layered product 3 was obtained in the same manner as in Example 1 except that the film thickness of the optical adjustment layer in Example 1 was changed to 90 nm (optical film thickness: 124 nm).

[Example 4]

The gas barrier layered product 4 was obtained in the same manner as in Example 1 except that the film thickness of the optical adjustment layer in Example 1 was changed to 120 nm (optical film thickness: 165 nm).

[Example 5]

The optical film was formed by coating the optical adjustment layer forming material (3) instead of the optical adjustment layer forming material (1) in Example 1, and heating the obtained coating film at 100 ° C for 1 minute to form an optical adjustment. The gas barrier layered product 5 was obtained in the same manner as in Example 1 except that the layer (film thickness: 200 nm, optical film thickness: 286 nm).

[Embodiment 6]

The gas barrier layered product 6 was obtained in the same manner as in Example 1 except that the film thickness of the optical adjustment layer in Example 1 was changed to 220 nm (optical film thickness: 302 nm).

[Embodiment 7]

The gas barrier layered product 7 was obtained in the same manner as in Example 1 except that the film thickness of the optical adjustment layer in Example 1 was changed to 280 nm (optical film thickness: 385 nm).

[Embodiment 8]

The same method as in Example 1 was used except that the film thickness of the optical adjustment layer in Example 1 was changed to 295 nm (optical film thickness: 405 nm). The gas barrier layer 8 is obtained by a method.

[Embodiment 9]

The gas barrier layered product 9 was obtained in the same manner as in Example 1 except that the film thickness of the optical adjustment layer in Example 1 was changed to 380 nm (optical film thickness: 522 nm).

[Embodiment 10]

The gas barrier layered product 10 was obtained in the same manner as in Example 1 except that the film thickness of the optical adjustment layer in Example 1 was changed to 390 nm (optical film thickness: 536 nm).

[Example 11]

The gas barrier layered product 11 was obtained in the same manner as in Example 1 except that the film thickness of the optical adjustment layer in Example 1 was changed to 460 nm (optical film thickness: 632 nm).

[Embodiment 12]

The gas barrier layered product 12 was obtained in the same manner as in Example 1 except that the film thickness of the optical adjustment layer in Example 1 was changed to 475 nm (optical film thickness: 652 nm).

[Example 13]

The gas barrier layered product 13 was obtained in the same manner as in Example 1 except that the film thickness of the optical adjustment layer in Example 1 was changed to 555 nm (optical film thickness: 762 nm).

[Comparative Example 1]

The production intermediate of the gas barrier layered product 1 of Example 1 [film composed of the substrate (1) and the gas barrier layer] was used as the gas barrier layer of Comparative Example 1. Body 14.

[Comparative Example 2]

The gas barrier layered product 15 was obtained in the same manner as in Example 5 except that the film thickness of the optical adjustment layer in Example 5 was changed to 70 nm (optical film thickness: 100 nm).

[Comparative Example 3]

The gas barrier layered product 16 was obtained in the same manner as in Example 2 except that the film thickness of the optical adjustment layer in Example 2 was changed to 150 nm (optical film thickness: 224 nm).

[Comparative Example 4]

The gas barrier layered product 17 was obtained in the same manner as in Example 1 except that the film thickness of the optical adjustment layer in Example 1 was changed to 270 nm (optical film thickness: 371 nm).

[Comparative Example 5]

The gas barrier layered product 18 was obtained in the same manner as in Example 2 except that the film thickness of the optical adjustment layer in Example 2 was changed to 300 nm (optical film thickness: 448 nm).

[Comparative Example 6]

The gas barrier layered product 19 was obtained in the same manner as in Example 2 except that the film thickness of the optical adjustment layer in Example 2 was changed to 400 nm (optical film thickness: 597 nm).

[Comparative Example 7]

The same method as in Example 5 was used except that the film thickness of the optical adjustment layer in Example 5 was changed to 505 nm (optical film thickness: 723 nm). The gas barrier layered body 20 is obtained by the method.

[Comparative Example 8]

A barrier layered body was obtained in the same manner as in Example 4 except that the DC voltage at the time of forming the gas barrier layer in Example 4 was changed to -9 kV and a gas barrier layer having a refractive index of 1.82 was formed. twenty one.

[Comparative Example 9]

The optical adjustment layer (film thickness: 178 nm, optical film thickness: 286 nm) was formed by using the optical adjustment layer forming material (4) instead of the optical adjustment layer forming material (3) in Example 5, and was used in the same manner as in Example 5. In the same manner, the barrier laminate 22 is obtained.

[Reference Example 1]

In addition to changing the heating conditions of the coating film of the polyazide compound coating agent (1) in Comparative Example 1 to a gas barrier layer which was heated at 120 ° C for 30 minutes and formed to have a refractive index of 1.54, it was used. The gas barrier layered product 23 was obtained in the same manner as in Comparative Example 1.

The following measurements were performed on the gas barrier laminates 1 to 23.

(Measurement of water vapor transmission rate)

The water vapor transmission rate of the gas barrier laminates 1 to 20 at a temperature of 40 ° C and a relative humidity of 90% was measured using a water vapor transmission rate measuring device (manufactured by Mocon Co., Ltd., PERMATRAN-W3/33).

The measurement results are shown in the first table.

(Hue evaluation)

According to JIS Z 8729-1994 and using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3600), the gas barrier laminates 1 to 23 are measured in accordance with CIE L*a*b* The color value b* specified by the color.

The measurement results are shown in the first table.

From the first table, the following cases are known. The gas barrier laminates 1 to 13 of Examples 1 to 13 have excellent gas barrier properties and can suppress yellow color.

On the other hand, the color value b* of the gas barrier laminates 14 to 22 of Comparative Examples 1 to 9 was less than -1 or greater than +1 and exhibited yellow or blue.

Since the refractive index of the gas barrier layer of the gas barrier layered product 23 of Reference Example 1 is as low as 1.54, yellowing can be suppressed even if the optical adjustment layer is not provided.

On the other hand, the gas barrier layer of the gas barrier layered product 21 of Comparative Example 8 has a relatively high refractive index of 1.82, and it is difficult to set b* to 1.00 or less even if an optical adjustment layer is provided.

In addition, since the refractive index of the optical adjustment layer of the gas barrier layered product 22 of Comparative Example 9 is too high, the function as an optical adjustment layer cannot be sufficiently performed.

1‧‧‧Scope 1

2‧‧‧Scope 2

3‧‧‧Scope 3

4‧‧‧Scope 4

5‧‧‧Scope 5

6‧‧‧Scope 6

Claims (10)

A gas barrier layered product in which a substrate, a gas barrier layer and an optical adjustment layer are laminated in this order, and the gas barrier layer and the optical adjustment layer are adjacent to each other, and the gas barrier layered body is adjacent to the gas barrier layer. The gas barrier layer has a refractive index of 1.55 to 1.81, and the optical adjustment layer has a refractive index of 1.20 to 1.60, and the CIE L*a*b* color system defined in JIS Z 8729-1994 *The value is in the range of -1.00 to 1.00. The gas barrier layered product according to claim 1, wherein the gas barrier layer contains a group selected from the group consisting of inorganic oxides, inorganic nitrogen oxides, inorganic carbon oxides, and inorganic nitrogen oxides. At least one of the groups. The gas barrier layered product according to claim 1, wherein the gas barrier layer is a layer obtained by modifying a layer containing a polyazide compound. The gas barrier laminate according to claim 1, wherein the gas barrier layer has a thickness of from 10 nm to 10 μm. The gas barrier layered product according to claim 1, wherein the optical adjustment layer is composed of a cured product of a curable composition. The gas barrier layered product according to claim 5, wherein the curable composition contains a curable component and a filler. The gas barrier layered product according to claim 1, wherein the optical adjustment layer has a thickness of 5 to 2,500 nm. The gas barrier layered product according to the first aspect of the invention, wherein the optical film thickness (T) of the optical adjustment layer satisfies the following formula (1) or (2), [Equation 3] 121.43x-100≦T≦115.43x-37.33 (1) 760≦T≦2000 (2) (x is an integer from 1 to 6). A member for an electronic device comprising the gas barrier layered product according to claim 1 of the patent application. An electronic device comprising the member for an electronic device according to claim 9 of the patent application.