JPWO2015129626A1 - Gas barrier laminate, electronic device member, and electronic device - Google Patents

Abstract

The present invention has a gas barrier laminate comprising a substrate, a gas barrier layer, and a resin layer containing a bluing agent, an electronic device member comprising the gas barrier laminate, and the electronic device It is an electronic device provided with the member for use. ADVANTAGE OF THE INVENTION According to this invention, the gas barrier laminated body excellent in gas barrier property and colorless transparency, the member for electronic devices consisting of this gas barrier laminated body, and an electronic device provided with this electronic device member are provided.

Description

  The present invention relates to a gas barrier laminate excellent in gas barrier properties and colorless transparency, an electronic device member comprising the gas barrier laminate, and an electronic device including the electronic device member.

  In recent years, displays such as liquid crystal displays and electroluminescence (EL) displays have thin electrodes, light weights, flexible substrates, etc., as a substrate having electrodes, instead of glass plates, on transparent plastic films, A so-called gas barrier film in which an inorganic compound layer (gas barrier layer) is laminated is used.

For example, Patent Document 1 discloses a high-oxidation degree silicon oxide layer having a value of x of SiO _x of 1.8 or more on one side or both sides of a base material made of a plastic film by a dry coating method. On the silicon oxide layer, a low oxide silicon oxide layer having a value of x of SiO _x of 1.0 to 1.6 is provided, and further, oxygen, nitrogen, argon, or helium is formed on the low oxide silicon oxide layer surface. It describes a transparent gas barrier laminate film in which a polymer layer is laminated on the plasma treatment surface of the low-oxidation silicon oxide layer after plasma treatment with one kind or a gas comprising two or more kinds thereof.
Patent Document 2 describes a transparent gas barrier substrate in which a silicon oxynitride layer and a silicon nitride layer are laminated in this order on one surface or both surfaces of a transparent resin substrate.

JP 2004-351832 A JP 2007-062305 A

  As described above, many gas barrier films having an inorganic compound layer as a gas barrier layer have been proposed so far. However, since such a gas barrier layer usually has a high refractive index, a difference in refractive index from other adjacent layers becomes large, light of a short wavelength is reflected at the interface between these layers, and the gas barrier film is yellow. There was a problem of being tinged.

  The present invention has been made in view of the situation of the prior art, and has a gas barrier laminate excellent in gas barrier properties and colorless transparency, an electronic device member comprising the gas barrier laminate, and the electronic device member It is an object to provide an electronic device comprising:

  As a result of intensive studies to solve the above problems, the present inventors have found that a gas barrier laminate having excellent colorless transparency can be obtained by providing a resin layer containing a bluing agent in the gas barrier laminate. The present invention has been completed.

Thus, according to the present invention, there are provided the following gas barrier laminates (1) to (6), an electronic device member (7), and an electronic device (8).
(1) A gas barrier laminate comprising a substrate, a gas barrier layer, and a resin layer containing a bluing agent.
(2) The gas barrier laminate (3) according to (1), wherein the gas barrier layer comprises an inorganic vapor-deposited film or is obtained by subjecting a layer containing a polymer compound to ion implantation treatment. The gas barrier laminate according to (1), wherein the bluing agent has a maximum absorption wavelength within a range of 520 to 600 nm.
(4) The gas barrier laminate according to (1), wherein the water vapor permeability of the gas barrier laminate at a temperature of 40 ° C. and a relative humidity of 90% is 0.05 g / (m ² · day) or less.
(5) In the above (1), the gas barrier laminate has a b ^* value in a CIE L ^* a ^* b ^* color system defined by JIS Z 8729-1994 of −1.2 to 1.2. The gas barrier laminate as described.
(6) The gas barrier laminate according to (1), wherein the gas barrier laminate has a light transmittance of 85% or more at a wavelength of 550 nm.
(7) The gas barrier laminate according to (1), wherein the content of the bluing agent is 0.01 to 30% by mass with respect to the entire resin layer containing the bluing agent.
(8) The gas barrier laminate according to (1), wherein the resin layer containing the bluing agent has a thickness of 0.1 to 100 μm.
(9) The gas barrier laminate according to (1), wherein the gas barrier laminate has a layer configuration of bluing agent-containing layer / gas barrier layer / base material.
(10) The gas barrier laminate according to (1), wherein the gas barrier laminate has a layer configuration of gas barrier layer / bluing agent-containing layer / base material.
(11) The gas barrier laminate according to (1), wherein the gas barrier laminate has a layer configuration of gas barrier layer / base material / bluing agent-containing layer.
(12) A member for an electronic device comprising the gas barrier laminate according to (1).
(13) An electronic device comprising the electronic device member according to (12).

  ADVANTAGE OF THE INVENTION According to this invention, the gas barrier laminated body excellent in gas barrier property and colorless transparency, the member for electronic devices consisting of this gas barrier laminated body, and an electronic device provided with this electronic device member are provided.

  Hereinafter, the present invention will be described in detail by classifying into 1) a gas barrier laminate, and 2) a member for an electronic device and an electronic device.

1) Gas barrier laminate The gas barrier laminate of the present invention has a base material, a gas barrier layer, and a resin layer containing a bluing agent (hereinafter sometimes referred to as a “blueing agent-containing layer”). It is characterized by that.

(1) Substrate The substrate constituting the gas barrier laminate of the present invention is not particularly limited as long as it can carry a gas barrier layer or a bluing agent-containing layer. As the substrate, a film or 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 a base material is 0.5-500 micrometers normally, Preferably it is 1-100 micrometers.

The material of the base material is not particularly limited as long as it matches the purpose of the gas barrier laminate of the present invention.
Base materials include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, acrylic resin, cycloolefin polymer And resin base materials such as aromatic polymers; paper base materials such as glassine paper, coated paper and fine paper; laminated paper obtained by laminating the resin on these paper base materials.

  Among these, since it is excellent in transparency and has versatility, a resin base material is preferable, polyester, polyamide, polysulfone, polyether sulfone, polyphenylene sulfide, or cycloolefin-based polymer is more preferable, and polyester or cycloolefin-based polymer. Is more preferable.

Examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate.
Examples of the polyamide include wholly aromatic polyamide, nylon 6, nylon 66, nylon copolymer, and the like.

  Examples of cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Specific examples thereof include Apel (an ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals), Arton (a norbornene polymer manufactured by JSR), Zeonoa (a norbornene polymer manufactured by Nippon Zeon), and the like. .

(2) Gas barrier layer The gas barrier layer which comprises the gas barrier laminated body of this invention is a layer which has the characteristic (gas barrier property) which suppresses permeation | transmission of gas, such as oxygen and water vapor | steam.

  The gas barrier layer was obtained, for example, by subjecting a layer containing an inorganic vapor deposition film or a polymer compound (hereinafter sometimes referred to as “polymer layer”) to ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, or the like. [In this case, the gas barrier layer does not mean only a region modified by an ion implantation treatment or the like, but a “polymer layer including a modified region”]. ] Etc. are mentioned.

Examples of the inorganic vapor deposition film include vapor deposition films of inorganic compounds and metals.
As the raw material for the vapor-deposited film of the inorganic compound, inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide and tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride and titanium nitride; inorganic carbides; Inorganic sulfides; inorganic oxynitrides such as silicon oxynitride; inorganic oxide carbides; inorganic nitride carbides; inorganic oxynitride carbides and the like.
Examples of the raw material for the metal vapor deposition film include aluminum, magnesium, zinc, and tin.
These can be used singly or in combination of two or more.
Among these, an inorganic vapor-deposited film using an inorganic oxide, inorganic nitride or metal as a raw material is preferable from the viewpoint of gas barrier properties, and further, an inorganic material using an inorganic oxide or inorganic nitride as a raw material from the viewpoint of transparency. A vapor deposition film is preferred.

  As a method of forming an inorganic vapor deposition film, a PVD (physical vapor deposition) method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, a thermal CVD (chemical vapor deposition) method, a plasma CVD method, a photo CVD method, etc. The CVD method is mentioned.

  Although the thickness of an inorganic vapor deposition film changes also with the inorganic compound to be used, from a gas-barrier property and a handleability viewpoint, Preferably it is 10-2000 nm, More preferably, it is 20-1000 nm, More preferably, it is 30-500 nm, Most preferably, it is 40. It is in the range of ~ 200 nm.

In the gas barrier layer obtained by subjecting the polymer layer to ion implantation treatment, the polymer compound used includes silicon-containing polymer compounds such as polyorganosiloxane and polysilazane compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether Examples include ketones, polyether ether ketones, polyolefins, polyesters, polycarbonates, polysulfones, polyether sulfones, polyphenylene sulfides, polyarylates, acrylic resins, cycloolefin polymers, and aromatic polymers.
These polymer compounds can be used alone or in combination of two or more.

  Among these, a silicon-containing polymer compound is preferable as the polymer compound because a gas barrier layer having better gas barrier properties can be formed. Examples of silicon-containing polymer compounds include polysilazane compounds, polycarbosilane compounds, polysilane compounds, and polyorganosiloxane compounds. Among these, a polysilazane compound is preferable because a gas barrier layer having excellent gas barrier properties can be formed. By performing ion implantation treatment on the layer containing the polysilazane compound, a layer having silicon, oxygen, and silicon as main constituent atoms (silicon oxynitride layer) can be formed.

As the polysilazane compound, known compounds such as organic polysilazane, inorganic polysilazane, and modified polysilazane can be used. As the polysilazane compound, a commercially available product as a glass coating material or the like can be used as it is.
The polysilazane compounds can be used alone or in combination of two or more.

The polymer layer may contain other components in addition to the polymer compound described above as long as the object of the present invention is not impaired. Examples of other components include a curing agent, an anti-aging agent, a light stabilizer, 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 better gas barrier properties can be obtained.

The thickness of the polymer layer is not particularly limited, but is usually 20 nm to 10 μm, preferably 30 to 500 nm, more preferably 40 to 200 nm.
In the present invention, a gas barrier film having a sufficient gas barrier property can be obtained even if the layer containing the polymer compound is nano-order.

  The method for forming the polymer layer is not particularly limited. For example, preparing a polymer layer forming solution containing at least one polymer compound, optionally other components, a solvent, etc., and then applying this polymer layer forming solution by a known method, A polymer layer can be formed by drying the obtained coating film.

Solvents used in the polymer layer forming solution include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; n- And aliphatic hydrocarbon solvents such as pentane, n-hexane, and n-heptane; and alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane.
These solvents can be used alone or in combination of two or more.

  Coating methods for the polymer layer forming solution include bar coating, spin coating, dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing, spray coating, and gravure. Examples include an offset method.

  As a method for drying the formed coating film, a conventionally known drying method such as hot air drying, hot roll drying, infrared irradiation or the like can be adopted. The heating temperature is usually in the range of 60 to 130 ° C. The heating time is usually several seconds to several tens of minutes.

As ions implanted into the polymer layer, ions of rare gases such as argon, helium, neon, krypton, and xenon; ions of fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, etc .; methane, ethane, etc. Ion of alkane gases such as ethylene and propylene; Ions of alkadiene gases such as pentadiene and butadiene; Ions of alkyne gases such as acetylene; Aromatic carbonization such as benzene and toluene Examples include ions of hydrogen-based gases; ions of cycloalkane-based gases such as cyclopropane; ions of cycloalkene-based gases such as cyclopentene; ions of metals; ions of organosilicon compounds.
These ions can be used alone or in combination of two or more.
Among these, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferable because ions can be more easily implanted and a gas barrier layer having better gas barrier properties can be obtained.

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

  Examples of the method for implanting ions include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma, and the like. In particular, in the present invention, the latter method of implanting plasma ions is preferable because the desired barrier layer can be easily obtained.

  In the plasma ion implantation, for example, plasma is generated in an atmosphere containing a plasma generation gas such as a rare gas, and a negative high voltage pulse is applied to the polymer layer, whereby ions (positive ions) in the plasma are It can be performed by injecting into the surface portion of the polymer layer.

  By ion implantation, the thickness of the region into which ions are implanted can be controlled by implantation conditions such as ion type, applied voltage, and processing time, and is determined according to the thickness of the polymer layer, the purpose of use of the laminate, etc. Usually, it is 10 to 400 nm. The region into which ions are implanted preferably has a thickness of 10 to 400 nm in the depth direction from the surface portion of the polymer layer.

(3) Blueing agent-containing layer The blueing agent-containing layer constituting the gas barrier laminate of the present invention is a layer containing a blueing agent and a resin component.
In general, since the gas barrier layer has a high refractive index, a difference in refractive index from other adjacent layers becomes large, and light having a short wavelength is easily reflected at the interface between these layers. For this reason, the conventional gas barrier laminate has a tendency to be yellowish.
On the other hand, since the gas barrier laminate of the present invention has a bluing agent-containing layer together with the gas barrier layer, yellowing is suppressed and the colorless transparency is excellent.

The bluing agent is a colorant that exhibits a blue or purple color by absorbing orange or yellow light and has a function of adjusting the hue of the resin.
The bluing agent preferably has a maximum absorption wavelength in the range of 520 to 600 nm, and more preferably has a maximum absorption wavelength in the range of 540 to 580 nm.

The kind of bluing agent is not particularly limited, and known organic colorants and inorganic colorants can be used.
As an organic colorant, as a chromophore, there is a monoazo dye having one azo group (—N═N—) in the molecule, and three aromatic amines (including aromatic heterocycles) centering on methane. Examples thereof include triarylmethane dyes having a molecular structure linked in a point-symmetric manner, phthalocyanine dyes having a phthalocyanine skeleton in the molecule, anthraquinone dyes that are derivatives of anthraquinone, and the like.
Inorganic colorants include iron blue, Prussian blue, Berlin blue, turn bull blue, milory blue, Chinese blue, Paris blue and other bitumen (iron cyano complex colorants); ultramarine blue, ultramarine violet and other ultramarine blue; cobalt Examples include blue (CoO.Al ₂ O ₃ ).

Among these, as the bluing agent, anthraquinone dyes, ultramarine blue, and cobalt blue are preferable.
A blueing agent can be used individually by 1 type or in combination of 2 or more types.

  The content of the bluing agent in the bluing agent-containing layer is preferably 0.01 to 30% by mass with respect to the entire bluing agent-containing layer, from the viewpoint of obtaining the better effect of the present invention. 05-20 mass% is more preferable, and 0.1-10 mass% is further more preferable.

The resin component contained in the bluing agent-containing layer is not particularly limited as long as it can form a thin film-like layer and can disperse the bluing agent.
Examples of the resin component include polymer compounds that constitute the polymer layer, polymer compounds similar to those shown above, energy ray curable resins such as UV curable resins, thermosetting resins, and the like. Examples of the UV curable resin include a resin having a polymerizable functional group such as a (meth) acryloyl group. These resin components can be used alone or in combination of two or more.
Among these, as the resin component contained in the bluing agent-containing layer, energy ray curable resins such as UV curable resins and thermosetting resins are preferable.

Examples of the energy beam curable resin include compounds having one or more unsaturated bonds, such as a compound having an acrylate functional group. For example, ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone, etc. can be mentioned. Examples of the compound having two or more unsaturated bonds include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri ( Reaction products such as (meth) allyllate and polyfunctional compounds such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate And poly (meth) acrylate esters of polyhydric alcohols).
Here, “(meth) acrylate” means methacrylate and acrylate (the same applies hereinafter).

When the energy beam curable resin is an ultraviolet curable resin, it is preferable to use a photopolymerization initiator. Specific examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoyl benzoate, α-amino oxime esters, thioxanthones, propiophenones, benzyls, benzoins, acylphosphine oxides, and the like. Further, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine and the like.
Moreover, you may add a well-known photosensitizer and a photoinitiator as needed.
It is preferable that the addition amount of a photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of energy-beam curable compositions.

  Thermosetting resins include phenolic resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin, polysiloxane Examples thereof include resins. When a thermosetting resin is used, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, and the like can be used in combination as necessary.

The bluing agent-containing layer may have a crosslinked structure.
When forming a crosslinked structure in the bluing agent-containing layer, a known method for forming a crosslinked structure in an adhesive or the like can be used.

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

The isocyanate-based crosslinking agent is a compound having an isocyanate group as a crosslinkable group.
Isocyanate-based crosslinking agents include trimethylolpropane-modified tolylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, etc .; aliphatic polyisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Alicyclic polyisocyanates of these compounds; biurets, isocyanurates of these compounds, and also reactants with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil Adduct body; and the like.

The epoxy-based crosslinking agent is a compound having an epoxy group as a crosslinkable group.
Epoxy crosslinking agents include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl ether 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.

An aziridine-based crosslinking agent is a compound having an aziridine group as a crosslinkable group.
Examples of the aziridine-based crosslinking agent include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane tri-β-aziridinylpropionate, tetramethylolmethanetri-β-aziridinylpro Pionate, toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1- (2-methylaziridine), tris-1- (2-methylaziridine) phosphine, tri And methylolpropane tri-β- (2-methylaziridine) propionate.

Examples of the metal chelate-based crosslinking agent include chelate compounds in which the metal atom is aluminum, zirconium, titanium, zinc, iron, tin, etc. Among them, aluminum chelate compounds are preferable.
Aluminum chelate compounds include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, diisopropoxy aluminum mono Examples include stearyl acetoacetate and diisopropoxyaluminum monoisostearyl acetoacetate.

These crosslinking agents can be used alone or in combination of two or more.
When a crosslinked structure is formed using these crosslinking agents, the amount used is that the crosslinking group of the crosslinking agent (in the case of a metal chelate crosslinking agent, the metal chelate crosslinking agent) is the hydroxyl group and carboxyl of the polymer compound. The amount of 0.1 to 5 equivalents relative to the group is preferred, and the amount of 0.2 to 3 equivalents is more preferred.

  Moreover, when using resin which has polymerizable functional groups, such as a (meth) acryloyl group, a crosslinked structure can be formed by using a photoinitiator, a thermal polymerization initiator, etc.

  Examples of the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl, benzoin dimethyl ketal, 2,4-diethylthioxanthone, 1 -Hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, 2-chloroanthraquinone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,4,6 -Trimethylbenzoyl) -phenyl-phosphine oxide.

  Examples of the thermal polymerization initiator include hydrogen peroxide; peroxodisulfates such as ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate; 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4 Azo compounds such as' -azobis (4-cyanovaleric acid), 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide , Organic peroxides such as lauroyl peroxide, peracetic acid, persuccinic acid, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and the like.

These polymerization initiators can be used singly or in combination of two or more.
When using these polymerization initiators to form a crosslinked structure, the amount used is preferably from 0.1 to 100 parts by weight, more preferably from 1 to 100 parts by weight, based on 100 parts by weight of the polymer compound.

  The content of the resin component in the bluing agent-containing layer (including a cross-linked structure when a cross-linked structure is formed) is preferably 70 to 99.99% by mass with respect to the entire bluing agent-containing layer. 80 to 99.95% by mass is more preferable, and 90 to 99.9% by mass is more preferable.

The bluing agent-containing layer may contain other components as long as the effects of the present invention are not hindered.
Examples of other components include additives such as ultraviolet absorbers, silane coupling agents, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, extenders, and softeners.
These can be used singly 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 and more preferably 0.01 to 2% by mass with respect to the whole bluing agent-containing layer. preferable.

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

The method for forming the bluing agent-containing layer is not particularly limited. For example, a resin composition containing a bluing agent and a resin component (hereinafter sometimes referred to as a “bluing agent-containing composition”) is prepared, and then the bluing agent-containing composition is formed on a predetermined surface. The bluing agent-containing layer can be formed by coating, drying the obtained coating film, and performing a crosslinking reaction as necessary.
Examples of the method for preparing the bluing agent-containing composition, the coating method, and the drying method include the same methods as described above as the method for 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.
The gas barrier laminate of the present invention may have one gas barrier layer or one bluing agent-containing layer, or two or more layers.

The gas barrier laminate of the present invention is not particularly limited as long as it has a substrate, a gas barrier layer, and a bluing agent-containing layer. Examples of the layer structure of the gas barrier laminate of the present invention include, but are not limited to, the following.
(I) Blueing agent-containing layer / gas barrier layer / base material (ii) Gas barrier layer / blueing agent-containing layer / base material (iii) Gas barrier layer / base material / blueing agent-containing layer

The gas barrier laminate of the present invention may have a layer other than the base material, the gas barrier layer, and the bluing agent-containing layer.
Examples of layers other than the base material, gas barrier layer, and bluing agent-containing layer include a primer layer, a conductor layer, a shock absorbing layer, a pressure-sensitive adhesive layer, and a process sheet for improving interlayer adhesion with the base material. . The stacking position of these layers is not particularly limited. The stacking position of these layers is not particularly limited. In addition, a process sheet | seat has a role which protects a laminated body, when a laminated body is preserve | saved, conveyed, etc., and is peeled when a laminated body is used.

The gas barrier laminate of the present invention can be produced, for example, by the following method.
(I) Gas barrier laminate having a layer structure of bluing agent-containing layer / gas barrier layer / base material A gas barrier layer is formed on the base material using the method described above. Next, by forming the bluing agent-containing layer on the obtained gas barrier layer using the method described above, a gas barrier laminate having a layer structure of bluing agent-containing layer / gas barrier layer / base material is obtained. Can be obtained.

(Ii) Gas barrier laminate having a gas barrier layer / blueing agent-containing layer / base material layer structure A blueing agent-containing layer is formed on a base material using the method described above. Next, a gas barrier layer having a gas barrier layer / blueing agent-containing layer / base material layer structure is formed by forming a gas barrier layer on the obtained bluing agent-containing layer using the method described above. Can be obtained.

(Iii) Gas barrier layered product having a gas barrier layer / base material / bluing agent-containing layer layer A gas barrier layer is formed on a base material using the method described above. Next, a gas barrier layer having a layer structure of gas barrier layer / base material / blueing agent-containing layer is formed on the other surface of the base material by forming the blueing agent-containing layer using the method described above. You can get a body.

  When the gas barrier laminate of the present invention has a layer other than the base material, the gas barrier layer, and the bluing agent-containing layer, the target gas barrier property can be obtained by appropriately adding necessary steps in the above production method. A laminate can be obtained.

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

The gas barrier layered product of the present invention, the temperature 40 ° C., 90% relative humidity, the water vapor permeability is preferably 0.05g ^/ (m 2 · day) or less, more preferably 0.04g ^/ (m 2 · day ) Or less, and more preferably 0.03 g / (m ² · day) or less. There is no particular lower limit, and the lower the better, the better, but it is usually 0.001 g / (m ² · day) or more.
When the water vapor transmission rate is in such a range, the gas barrier laminate of the present invention is excellent in gas barrier properties. Such a gas barrier laminate is suitably used as an electronic device member.
The water vapor transmission rate can be measured by the method described in the examples.

The b ^* value in the CIE L ^* a ^* b ^* color system defined by JIS Z 8729-1994 of the gas barrier laminate of the present invention is preferably −1.2 to 1.2, more preferably, It is -1.0-1.0, More preferably, it is -0.8-0.8.
The b ^* value represents the degree of yellow and blue when the color is digitized. If the b ^* value is positive, it is yellowish, and if it is negative, it is bluish.
When the b ^* value is in the above range, the gas barrier laminate exhibits a hue that is more intermediate between yellow and blue. Such a gas barrier laminate is suitably used as an electronic device member having a light emitting element.
The b ^* value can be controlled by selecting the bluing agent to be used and appropriately determining the content of the bluing agent in the bluing agent-containing layer according to the properties of the gas barrier layer to be formed.

Further, the a ^* value in the CIE L ^* a ^* b ^* color system defined by JIS Z 8729-1994 of the gas barrier laminate of the present invention is preferably -1.2 to 1.2, more preferably. Is -1.0 to 1.0, more preferably -0.8 to 0.8.
The a ^* value represents the degree of redness and greenness when the color is digitized. If the a ^* value is positive, it is reddish, if it is negative, This means that it is greenish.
When the a ^* value is in the above range, the gas barrier laminate exhibits a hue between red and green. Such a gas barrier laminate is suitably used as an electronic device member having a light emitting element.
The a ^* value can be controlled by appropriately selecting the resin to be used and other components.
The b ^* value and the a ^* value in the CIE L ^* a ^* b ^* color system defined in JIS Z 8729-1994 can be measured by the method described in the examples.

The light transmittance at a wavelength of 370 nm of the gas barrier laminate of the present invention is preferably 1% or less, and more preferably 0.5% or less. The light transmittance at a wavelength of 550 nm is preferably 85.0% or more, more preferably 89.0% or more.
The light transmittance can be measured by the method described in Examples.

A gas barrier laminate having a light transmittance of 1% or less at a wavelength of 370 nm can sufficiently absorb ultraviolet rays and has excellent light resistance.
The light transmittance at a wavelength of 370 nm can be controlled by containing an appropriate amount of an ultraviolet absorber.

A gas barrier 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 various additives and the thickness of the gas barrier laminate.

  Since it has these characteristics, the gas-barrier laminated body of this invention is used suitably as a member for electronic devices.

2) Electronic device member and electronic device The electronic device member of the present invention comprises the gas barrier laminate of the present invention. Therefore, since the electronic device member of the present invention has excellent gas barrier properties, it is possible to prevent deterioration of the element due to gas such as water vapor. Moreover, since it is excellent in colorless transparency, it is suitable as a display member such as a liquid crystal display or an EL display.

The electronic device of the present invention includes the electronic device member of the present invention. Specific examples include a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, and a solar battery.
Since the electronic device of the present invention includes the electronic device member comprising the gas barrier laminate of the present invention, it has excellent gas barrier properties.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Unless otherwise indicated, the part and% in each example are based on mass.

(Compound)
The compounds and materials used in each example are shown below.
UV curable resin liquid (1): manufactured by JSR, trade name: OPSTAR Z7530, solid content 73%
Blueing agent (1): Complex oxide-based bluing agent (manufactured by CIK Nanotech Co., Ltd., trade name: COBMIBK15WT% -NO1, cobalt blue, maximum absorption wavelength: 580 nm, solid content 15%)
Base material (1): Polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine A4100, thickness 50 μm)
Polysilazane compound coating agent (1): (manufactured by Clariant Japan, trade name: Aquamica NL110-20, solid content 20%)

[Production Example 1]
The blueing agent-containing composition 1 was prepared by adding 4.8 parts of the blueing agent (1) to 100 parts of the UV curable resin liquid (1) and stirring.

[Production Examples 2 to 6]
Blueing agent-containing compositions 2 to 6 were prepared in the same manner as in Production Example 1 except that the blending ratio was changed to that shown in Table 1.

[Example 1]
A polysilazane compound coating agent (1) is applied onto the substrate (1) by a spin coating method, and the resulting coating film is heated at 120 ° C. for 1 minute to have a thickness of 150 nm and a polysilazane containing perhydropolysilazane. A layer was formed. Next, argon (Ar) was plasma ion-implanted on the surface of the polysilazane layer using a plasma ion implantation apparatus under the following conditions to form a gas barrier layer.
On the gas barrier layer, the bluing agent-containing composition 1 obtained in Production Example 1 was applied by a bar coating method so as to have a thickness of 1 μm, and the obtained coating film was dried at 70 ° C. for 1 minute. UV light irradiation using a UV light irradiation line (high pressure mercury lamp; line speed, 20 m / min; integrated light quantity, 100 mJ / cm ² ; peak intensity, 1.466 W; number of passes, twice), bluing agent-containing layer And bluing agent-containing layer (hereinafter also referred to as “C layer”) / gas barrier layer (hereinafter also referred to as “B layer”) / base material (hereinafter referred to as “S layer”) There was obtained a gas barrier laminate 1 having a layer structure.

The plasma ion implantation apparatus and ion implantation conditions used for forming the gas barrier layer are as follows.
(Plasma ion implantation equipment)
RF power source: JEOL Ltd., model number “RF” 56000
High-voltage pulse power supply: “PV-3-HSHV-0835” manufactured by Kurita Manufacturing Co., Ltd.
(Plasma ion implantation conditions)
Plasma generation gas: Ar
Gas flow rate: 100sccm
Duty ratio: 0.5%
Applied voltage: -15 kV
RF power supply: frequency 13.56 MHz, applied power 1000 W
Chamber internal pressure: 0.2 Pa
Pulse width: 5μsec
Processing time (ion implantation time): 200 seconds

[Example 2]
In Example 1, in place of the bluing agent-containing composition 1, the C layer / B layer was prepared in the same manner as in Example 1 except that the bluing agent-containing composition 2 obtained in Production Example 2 was used. A gas barrier laminate 2 having a layer structure of / S layer was obtained.

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

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

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

Example 6
On the base material (1), the bluing agent-containing composition 1 obtained in Production Example 1 was applied by a bar coating method to a thickness of 1 μm, and the resulting coating film was dried at 70 ° C. for 1 minute. After that, UV light irradiation was performed using a UV light irradiation line (high pressure mercury lamp; line speed, 20 m / min; integrated light quantity, 100 mJ / cm ² ; peak intensity, 1.466 W; number of passes, twice), bluing An agent-containing layer was formed.
A polysilazane compound-based coating material (1) is applied onto the bluing agent-containing layer by a spin coating method, and the resulting coating film is heated at 120 ° C. for 1 minute to have a thickness of 150 nm and a polysilazane containing perhydropolysilazane. A layer was formed.
Next, argon (Ar) is ion-implanted into the surface of the polysilazane layer using the plasma ion implantation apparatus under the above conditions to form a gas barrier layer, and a layer structure of B layer / C layer / S layer A gas barrier laminate 6 having the following was obtained.

Example 7
In Example 1, after forming a gas barrier layer on one surface of the substrate (1), and then forming a bluing agent-containing layer on the other surface of the substrate (1), Example 1 By the same method, a gas barrier laminate 7 having a layer structure of B layer / S layer / C layer was obtained.

Example 8
In Example 3, the same method as in Example 3 except that 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). A gas barrier laminate 8 having a layer structure of C layer / B layer / S layer was obtained.
<Reactive sputtering conditions>
-Plasma generation gas: argon, oxygen-Gas flow rate: argon 100 sccm, oxygen 40 sccm
・ Target material: Aluminum ・ Power value: 2500W
・ Vacuum chamber pressure: 0.2Pa

Example 9
In Example 3, the same method as in Example 3 except that a silicon 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 having a layer structure of C layer / B layer / S layer was obtained.
<Reactive sputtering conditions>
-Plasma generation gas: Argon, nitrogen-Gas flow rate: Argon 100 sccm, Nitrogen 60 sccm
・ Target material: Silicon ・ Power value: 2500W
・ Vacuum chamber pressure: 0.2Pa

[Comparative Example 1]
In Example 1, in place of the bluing agent-containing composition 1, the bluing agent-containing composition 6 obtained in Production Example 6 was used, except that the bluing agent was not contained in the same manner as in Example 1. A gas barrier laminate 10 having a layer structure of layer (C ′ layer) / B layer / S layer was obtained.

The following measurements were performed on the gas barrier laminates 1 to 10 obtained in Examples 1 to 9 and Comparative Example 1.
(Water vapor transmission rate measurement)
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 (L80-5000, manufactured by LYSSY).
The measurement results are shown in Table 1.

(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 (manufactured by Shimadzu Corporation, UV-3101PC).
The measurement results are shown in Table 1.

(Hue evaluation)
According to JIS Z 8729-1994, the spectrophotometer (UV-3200 manufactured by Shimadzu Corporation) is used for the color value b ^* defined by the CIE 1976 L * a * b * color system of the gas barrier laminates 1-10. It measured using.
The measurement results are shown in Table 2.

Table 2 shows the following.
The gas barrier laminates of Examples 1 to 9 are excellent in gas barrier properties and are also excellent in colorless transparency.
On the other hand, although the gas barrier laminate of Comparative Example 1 is excellent in gas barrier properties, the color value b ^* is large and yellowish.

Claims (13)

  A gas barrier laminate comprising a substrate, a gas barrier layer, and a resin layer containing a bluing agent.   2. The gas barrier laminate according to claim 1, wherein the gas barrier layer is made of an inorganic vapor-deposited film or is obtained by subjecting a layer containing a polymer compound to ion implantation treatment.   The gas barrier laminate according to claim 1, wherein the bluing agent has a maximum absorption wavelength within 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) or less at a temperature of 40 ° C and a relative humidity of 90%. 2. The gas barrier according to claim 1, wherein the gas barrier laminate has a b ^* value in a CIE L ^* a ^* b ^* color system defined by JIS Z 8729-1994 of −1.2 to 1.2. Laminate.   The gas barrier laminate according to claim 1, wherein the gas barrier laminate has a light transmittance of 85% or more at a wavelength of 550 nm.   2. The gas barrier laminate according to claim 1, wherein the content of the bluing agent is 0.01 to 30 mass% with respect to 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 has a layer structure of bluing agent-containing layer / gas barrier layer / base material.   The gas barrier laminate according to claim 1, wherein the gas barrier laminate has a layer configuration of gas barrier layer / bluing agent-containing layer / base material.   The gas barrier laminate according to claim 1, wherein the gas barrier laminate has a layer configuration of gas barrier layer / base material / bluing agent-containing layer.   An electronic device member comprising the gas barrier laminate according to claim 1.   An electronic device comprising the electronic device member according to claim 12.