TWI667135B - Gas barrier laminated body, member for electronic device, and electronic device - Google Patents

Abstract

The present invention provides 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 layering system has a substrate, The gas barrier layered product in which the smoothing layer and the gas barrier layer are laminated in this order, wherein the substrate is composed of a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm, and the smoothing layer based ultraviolet-curing resin composition cured product formed, the thickness (T ₁₎ of the base material, the thickness of the smoothing layer (T _2), thickness of the gas barrier layer (T ₃₎ lines meet Formula (1): T ₁ > T ₂ > T ₃ , Formula (2): T ₁ + T ₂ + T ₃ < 30 μm. According to the present invention, it is possible to provide a gas barrier layered product having a small thickness, excellent ultraviolet barrier property and gas barrier property, a member for an electronic device comprising the gas barrier layered product, and the electronic device. Electronic device for components of the device.

Description

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

The present invention relates to a gas barrier layered product having a thin thickness and excellent ultraviolet shielding property and gas barrier property, a member for an electronic device comprising the gas barrier layered product, and the electronic device. An electronic device using components.

A gas barrier film is widely used in liquid crystal displays, electroluminescence (EL) displays, and the like.

In recent years, there has been proposed a method as a gas barrier film which is characterized in that it has ultraviolet ray barrier properties and can reduce deterioration of components and the like due to ultraviolet rays. For example, Patent Document 1 discloses a gas barrier film comprising a substrate, an organic layer provided on the substrate, and an inorganic layer provided on the organic layer, wherein the organic layer contains an electron beam curing resin and ultraviolet rays. Absorbent and light stabilizer.

Further, in recent years, electronic devices have been progressing toward reduction in weight and thickness, and gas barrier laminates used in electronic devices are also required to have a small thickness.

Prior technical literature

Patent literature

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-154584

As described above, in the gas barrier film described in Patent Document 1, an electron beam curing resin is used as a material for forming an organic layer containing an ultraviolet absorber or the like. In the literature, it is described that when an ultraviolet curable resin composition is used as a material for forming an organic layer, the ultraviolet ray is absorbed by the ultraviolet ray absorbing agent, so that the organic layer cannot be sufficiently cured. .

On the other hand, in order to form an organic layer having excellent ultraviolet absorbing ability by using a highly versatile ultraviolet curable resin, it is necessary to increase the thickness of the organic layer or to increase the concentration of the ultraviolet absorbing agent contained in the organic layer. . However, in the former case, a gas barrier layered product having a small thickness cannot be obtained, and in the latter case, since the ultraviolet ray is absorbed by the ultraviolet absorbing agent, the organic layer cannot be sufficiently cured.

The present invention has been made in view of such circumstances, and an object thereof is to provide a gas barrier layered product having a thin thickness and excellent ultraviolet shielding property and gas barrier property, and comprising the gas barrier layered product. A member for an electronic device and an electronic device including the member for the electronic device.

In order to solve the problem, the inventors of the present invention have found that the substrate, the smoothing layer, and the gas barrier layer are laminated in the gas barrier layered product in this order. a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm, and the smoothing layer is composed of a cured product of an ultraviolet curable resin composition, and the thickness (T ₁ ) of the base material and the smoothing layer are When the thickness (T ₂ ) and the thickness (T ₃ ) of the gas barrier layer satisfy a predetermined relationship, a gas barrier layer having a small thickness and excellent ultraviolet ray barrier property and gas barrier property can be obtained. The invention has been completed.

As described above, according to the present invention, it is possible to provide the gas barrier layered product of the following (1) to (9), the member for an electronic device of (10), and the electronic device of (11).

(1) A gas barrier layered product, which is a gas barrier layered product in which a substrate, a smoothing layer, and a gas barrier layer are laminated in this order, wherein the substrate is at a wavelength The 360 nm light transmittance is 3.0% or less, and the smoothing layer is composed of a cured product of the ultraviolet curable resin composition, and the thickness (T ₁ ) of the substrate and the thickness of the smoothing layer ( T ₂ ), the thickness (T ₃ ) of the gas barrier layer satisfies the formulas (1) and (2), and [number 1] T ₁ > T ₂ > T ₃ . . . (1) T ₁ + T ₂ + T ₃ <30 μm. . . (2).

(2) The gas barrier layered product according to (1), wherein the resin film is a resin film containing an ultraviolet absorber.

(3) The gas barrier layered product according to (1), wherein an arithmetic mean roughness (Ra) of the interface between the smoothing layer and the gas barrier layer is 5 nm or less, and a maximum profile height of the roughness curve ( Rt) is 100 nm or less.

(4) 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.

(5) The gas barrier layered product according to (1), wherein the thickness (T ₁ ) of the substrate is 5 to 28 μm, and the thickness (T ₂ ) of the smoothing layer is 0.5 to 3 μm, and the gas barrier layer is The thickness (T ₃ ) is 0.05 to 0.3 μm.

(6) The gas barrier layered product according to (1), which is a gas barrier layered product further having a hard coat layer, having a layer layer of a hard coat layer/substrate/smooth layer/gas barrier layer .

(7) The gas barrier layered product according to (1), wherein the gas barrier layered product has a thickness of 5 to 35 μm.

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

(9) The gas barrier layered product according to (1), wherein the gas barrier layered product has a light transmittance of 3.0% or less at a wavelength of 360 nm.

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

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

According to the present invention, it is possible to provide a gas barrier layered product having a thin thickness and excellent ultraviolet barrier property and gas barrier property, a member for an electronic device comprising the gas barrier layered product, and the electronic device. Electronic device for components of the device.

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

The gas barrier layered product of the present invention is a gas barrier layered product in which a base material, a smoothing layer and a gas barrier layer are laminated in this order, wherein the substrate is composed of a wavelength of 360 nm. The light-transmitting layer is composed of a resin film having a light transmittance of 3.0% or less, and the smoothing layer is composed of a cured product of the ultraviolet curable resin composition, and the thickness (T ₁ ) of the substrate and the thickness of the smoothing layer (T) ₂ ) The thickness (T ₃ ) of the gas barrier layer satisfies the above formulas (1) and (2).

(1) Substrate

The base material constituting the gas barrier layered product of the present invention is composed of a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm. One of the features of the present invention is to use a resin film having excellent ultraviolet ray barrier properties, that is, a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm. The resin film to be used preferably has a light transmittance of 2.5% at a wavelength of 360 nm and preferably 2.0% or less.

The light transmittance at a wavelength of 360 nm can be measured using an ultraviolet spectrophotometer.

A resin film containing a resin component and an ultraviolet absorber is exemplified as the resin film having ultraviolet ray barrier properties.

Examples of the resin component of the resin film include polyimide, polyamine, polyamidoximine, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, and polyester. Polycarbonate, polyfluorene, polyether oxime, polyphenylene sulfide, acrylic resin, cycloolefin polymer, aromatic A fragrance-based polymer or the like.

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

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, and polybutylene terephthalate. Polyethylene naphthalate, polyarylate, and the like.

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.

The ultraviolet absorber is not particularly limited as long as it can obtain a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm.

Examples of the ultraviolet absorber include a salicylic acid-based ultraviolet absorber such as p-tert-butylphenyl phthalate or p-octylphenyl sulfate; 2,4-dihydroxydiphenyl ketone and 2-hydroxy-4. -Methoxydiphenyl ketone, 2-hydroxy-4-methoxy-5-sulfodiphenyl ketone, 2,2'-4,4'-tetrahydroxydiphenyl ketone, bis (2-A Diphenyl ketone ultraviolet absorber such as oxy-4-hydroxy-5-benzhydrylphenyl)methane; 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2 -(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-( a benzotriazole-based ultraviolet absorber such as 2H-benzotriazol-2-yl)phenol; a cyanoacrylate-based ultraviolet absorber such as ethyl-2-cyano-acrylic acid 3,3'-diphenyl ester 2-p-nitrophenyl-3,1-benzoxazine-4-one, 2-(p-benzylidenephenyl)-3,1-benzoxazin-4-one, 2-(2-naphthyl)-3,1-benzoxazin-4-one, 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2 Benzoxazines such as '-(2,6-anthracenyl)bis (3,1-benzoxazin-4-one) are ultraviolet absorbers; titanium dioxide, cerium oxide, zinc oxide, iron oxide, An inorganic ultraviolet absorber such as barium sulfate.

These ultraviolet absorbers can be used singly or in combination of two or more.

The content of the ultraviolet absorber is preferably 0.1 to 10% by mass, and preferably 0.5 to 5% by mass based on the resin component.

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

A resin film having ultraviolet ray barrier properties 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 film formation method such as a casting method or a melt extrusion method can be used.

(2) Smoothing layer

The smoothing layer constituting the gas barrier layered product of the present invention is composed of a cured product of an ultraviolet curable resin composition. The smoothing layer reduces the unevenness on the surface of the substrate and improves the interlayer adhesion of the gas barrier layered product. Further, when the substrate contains an additive such as an ultraviolet absorber, by providing the smoothing layer, it is possible to prevent the additives from oozing out and diffusing into the gas barrier layer, so that the performance of the gas barrier layer can be prevented from being lowered.

The ultraviolet curable resin composition usually contains polymerizable And photopolymerization initiator.

The polymerizable compound includes a polymerizable prepolymer and a polymerizable monomer.

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 low molecular weight bisphenol ring. An epoxy acrylate prepolymer obtained by reacting an oxygen resin and a novolac type epoxy resin with (meth)acrylic acid, and a urethane acrylate preliminarily obtained by reacting a polyurethane oligomer with (meth)acrylic acid A polymer, a polyol acrylate-based 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, pentaerythritol divinyl ether new, 1,6-ethylene Ether, trimethylolpropane divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified bisphenol A divinyl ether, neopentyl alcohol trivinyl ether, dipentaerythritol A vinyl compound such as vinyl ether or ditrimethylolpropane polyvinyl ether, but is not necessarily limited to these.

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

Here, the description of the (meth)acryl fluorenyl group means both an acryl fluorenyl group and a methacryl fluorenyl group.

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

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 hydrazine or the like; 2-methylthioxanthone Thioxanthone (methylthioxanthone), 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone ) is a polymerization initiator or the like.

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 polymerizable compound.

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

Examples of other components include an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, a filler, an inorganic filler, and a coloring pigment. The content of these may be appropriately determined depending on the purpose.

The method of forming the smoothing layer is not particularly limited. For example, a coating liquid containing a UV curable resin composition and a solvent as needed is prepared, and then the coating liquid is applied onto a substrate by a conventional method, and the obtained coating film is cured. A smoothing layer composed of a cured product of the ultraviolet curable resin composition can be formed. Further, a drying treatment may be performed before the coating film is cured as needed.

Examples of the solvent of the coating liquid include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; and acetone, methyl ethyl ketone, and methyl isobutyl ketone. A ketone solvent; 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 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. The drying temperature is usually in the range of 60 to 130 °C. The drying time is usually from several seconds to several tens of minutes.

The hardening of the coating film can be carried out by irradiating ultraviolet rays from the surface of the coating film (the side where the substrate is not present).

As the ultraviolet light source, 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. 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 from several seconds to several hours, and the irradiation temperature is usually room temperature (20 ° C) to 100 ° C.

The arithmetic mean roughness (Ra) of the surface of the smoothing layer is preferably 5 nm or less, preferably 0.1 to 4 nm, and the maximum profile height (Rt) of the roughness curve is preferably 100 nm or less, preferably 1 to 1. 100 nm, more preferably 20 to 80 nm, and particularly preferably 30 to 65 nm.

When Ra and Rt are in the above range, the adhesion to the gas barrier layer is more excellent, and pinholes can be prevented from occurring in the gas barrier layer, so that a gas barrier having more excellent gas barrier properties can be obtained. Sexual laminate.

Ra and Rt can be measured by the method described in the examples.

(3) 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 or water vapor.

Examples of the gas barrier layer include an inorganic deposited film and a layer containing a polymer compound (hereinafter referred to as a "polymer layer"). In the case of the reforming treatment, the gas barrier layer is not only a region that has been modified by ion implantation treatment, but also means a polymer layer containing the modified region. "]Wait.

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 carbon nitrides; inorganic nitrogen oxides.

Examples of the raw material of the vapor deposited film of the 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 oxidation is performed. An inorganic vapor-deposited film containing a substance 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 varies depending on the inorganic compound to be used, and is preferably 50 to 300 nm, more preferably 50 to 200 nm from the viewpoint of gas barrier properties and handleability.

In the gas barrier layer obtained by modifying the polymer layer, examples of the polymer compound to be used include a ruthenium-containing polymer compound such as a polyorganosiloxane or a polyazane compound.醯imine, polyamine, polyamidoximine, polyphenylene ether, polyether ketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polyfluorene, polyether oxime, poly Phenyl sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, and 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 formed, and a polymer compound containing ruthenium is preferable as the polymer compound. 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) containing 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 (azepine bond) in the molecule. Specifically, it has the meaning of (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 100~50,000 is preferred.

In the above (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.

A cycloalkyl group which is an unsubstituted or substituted cycloalkyl group. A cycloalkyl group having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group may be mentioned.

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; (Meth)acryloxycarbonyl; unsubstituted or substituted aryl group such as phenyl, 4-methylphenyl or 4-chlorophenyl.

The aryl group which is an unsubstituted or substituted aryl group may, for example, be 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; and an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group. Alkoxy group having a carbon number of 1 to 6 such as a methoxy group or an ethoxy group; a nitro group; a cyano group; a hydroxyl group; a thiol group; an epoxy group; a glycidoxy group; An unsubstituted or substituted aryl group such as a phenyl group, a 4-methylphenyl group or a 4-chlorophenyl group.

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 a hydrogen atom is particularly preferred.

As to the technology (1) of having a poly silicon silazane compound repeating units, based all poly silicon polysilazane R _x, R _y, R _z are inorganic hydrogen atoms, 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. No. Hei. It is described in Japanese Laid-Open Patent Publication 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. As other components, a hardener anti-aging agent, a light stabilizer, a flame retardant, etc. are mentioned.

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 preferably 50 to 300 nm, more preferably 50 to 200 nm.

In the present invention, even if the thickness of the polymer layer is on the nanometer scale, a gas barrier layered product 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 of a polymer compound, and other components as necessary, and a solvent, and the like, may be prepared, and then the solution for forming a polymer layer may 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 several seconds to several tens of minutes.

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

The ion implantation treatment is a method in which ions are implanted into a polymer layer to modify a polymer layer as will be described later.

The 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 in which the polymer layer is irradiated with ultraviolet rays to modify 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 to be implanted into the polymer layer include ions of a rare gas such as argon, helium, neon, krypton or xenon; fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, Ions such as chlorine, fluorine, and sulfur; ions of an alkane gas such as methane or ethane; ions of an olefinic gas such as ethylene or propylene; and ions of a diene-based gas such as pentadiene or butadiene. An ion of an acetylene-based gas such as acetylene; an ion of an aromatic hydrocarbon-based gas such as benzene or toluene; an ion of a naphthenic gas such as cyclopropane; and an ion of a cycloolefin-based gas such as cyclopentene; Metal ions; ions of organic germanium compounds, etc.

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 obtain a gas barrier layer having more excellent gas barrier properties, it is preferable to use ions of a rare gas such as argon, helium, neon, krypton or xenon.

The amount of ions to be implanted can be appropriately determined in accordance with the purpose of use of the gas barrier layered product (required 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.

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

By ion implantation, the thickness of the ion implantation region can be controlled by the implantation conditions such as the type of ions, 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 10~300nm.

(4) Gas barrier laminate

Gas barrier layered product of the present invention, the base system, the smoothing layer and a gas barrier layer are laminated in this order, a thickness (T ₁₎ of the base material, the thickness of the smoothing layer (T ₂₎ The thickness (T ₃ ) of the gas barrier layer satisfies the following formulas (1) and (2).

[Number 2] T ₁ > T ₂ > T ₃ . . . (1) T ₁ + T ₂ + T ₃ <30 μm. . . (2)

In the gas barrier layered product of the present invention, since a resin film having ultraviolet ray barrier properties is used as the substrate, it is not necessary to include the ultraviolet absorbing agent in the smoothing layer. Therefore, since it is not necessary to increase the thickness of the smoothing layer to obtain sufficient ultraviolet ray barrier properties, the thickness of the smoothing layer can be sufficiently reduced. In addition, since it is not necessary to additionally laminate a layer containing the ultraviolet absorber in addition to the substrate, the smoothing layer, and the gas barrier layer, it is possible to prevent the thickness of the gas barrier layered product from being excessively thick. Therefore, it is possible to easily obtain a gas barrier layered product that satisfies the requirements specified in the formulas (1) and (2).

Further, in the gas barrier layered product of the present invention, since the smoothing layer does not need to contain the ultraviolet absorber, there is no possibility that the smoothing layer is hardened by the ultraviolet light being absorbed by the ultraviolet absorber, and the ultraviolet ray can be irradiated. The smoothing layer is sufficiently cured, and as a result, a gas barrier layered product having excellent gas barrier properties can be obtained.

In the gas barrier layered product of the present invention, the lower limit of T ₁ + T ₂ + T ₃ is usually 5 μm.

The thickness (T ₁₎ of the substrate, the thickness of the smoothing layer (T _2), thickness of the gas barrier layer (T ₃₎ lines are each 5 ~ 28μm, 0.5 ~ 3μm, 0.05 ~ 0.3μm preferably, T ₁ is 20 to 28 μm, T ₂ is 0.5 to 2 μm, and T ₃ is preferably 0.05 to 0.2 μm.

The thickness of each layer can be measured using the method described in the examples.

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

Examples of the layer other than the substrate, the smoothing layer, and the gas barrier layer include a hard coat layer, a conductor layer, an impact absorbing layer, an adhesive layer, and a process sheet. In addition, the process sheet has a function of protecting the gas barrier layered product when the layered body is stored and conveyed, and is peeled off when the gas barrier layered product is used. The arrangement of the layers is not particularly limited as long as the layer constitution of the substrate/smoothing layer/gas barrier layer can be maintained.

Specific examples of the layer constitution of the gas barrier layered product of the present invention include the following layer constitutions.

(i) Substrate/smoothing layer/gas barrier layer

(ii) Hard coating/substrate/smoothing layer/gas barrier layer

The gas barrier layered system of (ii) has a hard coat layer on the surface opposite to the side on which the smoothing layer of the substrate is formed. By providing a hard coat layer, it is possible to prevent the ultraviolet absorber from oozing out, and by imparting scratch resistance, it is possible to prevent the ultraviolet ray barrier property from being lowered due to damage of the substrate.

When the gas barrier layered product of the present invention has a hard coat layer, the thickness of the hard coat layer is preferably 0.5 to 3 μm, preferably 0.5 to 2.5 μm.

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

(i) Gas barrier layered body composed of a layer of a substrate/smoothing layer/gas barrier layer

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

(ii) a gas barrier layered body composed of a layer having a hard coat layer/substrate/smooth layer/gas barrier layer

First, a hard coat layer is formed on one side of the substrate, and second, a smoothing layer is formed on the other side of the substrate using the method disclosed above. Next, by forming a gas barrier layer on the obtained smoothing layer using the method described above, a gas having a layer of a hard coat layer/substrate/smooth layer/gas barrier layer can be obtained. Barrier laminate.

Further, each layer may be formed in the order of the smoothing layer, the hard coat layer, and the gas barrier layer, or each layer may be formed in the order of the smoothing layer, the gas barrier layer, and the hard coat layer to obtain a gas barrier layered body. .

The hard coat layer can be formed using the same material as the material of the smoothing layer and using the same method as the method of forming the smoothing layer.

When the gas barrier layered product of the present invention has a substrate, a smoothing layer, a gas barrier layer, or a layer other than the hard coat layer, the target gas is obtained by applying a necessary and necessary step in the above-described production method. Barrier laminate.

The thickness of the gas barrier layered product of the present invention is not particularly limited, and is preferably 5 to 35 μm, more preferably 10 to 34 μm, still more preferably 20 to 33 μm.

The gas barrier layer of the gas barrier laminate of the present invention has a water vapor transmission rate of at least 40 ° C and a relative humidity of 90%, preferably 0.05 g/(m ² .day) or less, preferably 0.04 g / (m ² .day). Hereinafter, it 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, and 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 product of the present invention preferably has a light transmittance of 3.0% or less at a wavelength of 360 nm, preferably 2.5% or less and 2.0% or less. The lower limit of the light transmittance is usually 0.01% or more.

Because of these characteristics, the gas barrier layered system of the present invention has excellent gas barrier properties and ultraviolet barrier properties, and thus 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 in that it is composed of the gas barrier layered product of the present invention. The member for an electronic device of the present invention has excellent gas barrier properties and can prevent deterioration of the element due to gas such as water vapor. Further, since it has excellent ultraviolet ray barrier properties, it is possible to prevent deterioration of the element due to ultraviolet ray irradiation. Therefore, the member for an electronic device of the present invention can be suitably used as a display member such as a liquid crystal display or an EL display.

The electronic device of the present invention has 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 is thin, lightweight, and excellent in durability against water vapor and ultraviolet rays.

[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 materials used in each example are as follows.

. Substrate (1): Polyethylene terephthalate film (Resin Dupont, resin film containing UV absorber, trade name: Teijin Tetoron Film HB3, thickness: 25 μm, light transmittance at a wavelength of 360 nm: 1.6%) )

. Substrate (2): Polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., trade name: PET25 T-100, thickness: 25 μm, light transmittance at a wavelength of 360 nm: 89%)

[Manufacturing Example 1]

As a polymerizable compound, 20 parts of dipentaerythritol hexaacrylate (trade name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) was dissolved in 100 parts of methyl isobutyl ketone, and then a photopolymerization initiator was added ( 3 parts of a product manufactured by BASF Corporation, trade name: Irgacure 127), and a resin layer formation solution was prepared.

In the following, the resin layer forming solution is used as a smoothing layer forming solution (1) and a hard coat layer forming solution.

[Manufacturing Example 2]

As a polymerizable compound, 20 parts of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH) was dissolved in 100 parts of methyl isobutyl ketone, and then a photopolymerization initiator was added ( 3 parts of a UV absorber (manufactured by BASF Corporation, trade name: TINVIN477) was prepared in three parts by a BASF company, trade name: Irgacure 127, and a solution for forming a smoothing layer (2) was prepared.

[Manufacturing Example 3]

In addition to changing the blending amount of the ultraviolet absorber in Production Example 2 to 8 parts The smoothing layer forming solution (3) was prepared in the same manner as in Production Example 2.

[Example 1]

On the substrate (1), the coating film obtained by applying the smoothing layer forming solution (1) obtained in Production Example 1 by a bar coating method was dried by heating at 70 ° C for 1 minute, and then UV light was used. The smoothing layer (1) having a thickness of 1 μm was formed by irradiating a production line and irradiating with UV light (high pressure mercury lamp, line speed, 20 m/min, cumulative dose of 100 mJ/cm ² , peak intensity of 1.466 W, and number of passes twice).

Next, on the smoothing layer (1), the perhydropolyazide (AZ Electronic Materials, trade name: AZNL110A-20) was spin-coated, and the obtained coating film was heated at 120 ° C for 2 minutes. To form a perhydropolyazide layer. Subsequently, as a modification treatment, a plasma ion implantation apparatus is used to perform plasma ion implantation of argon (Ar) on the surface of the perhydropolyazide layer to form a gas barrier layer, thereby obtaining a substrate. (1) / Gas barrier layered body 1 composed of a layer of the smoothing layer (1) / gas barrier layer.

The plasma ion implantation apparatus and plasma ion implantation conditions for forming a gas barrier layer are as follows.

(plasma ion implantation device)

RF power supply: Model "RF" 56000, manufactured by Japan Electronics Co., Ltd.

High-voltage pulse power supply: "PV-3-HSHV-0835", manufactured by Kurita Manufacturing Co., Ltd. (plasma ion implantation conditions)

. Plasma generated gas: Ar

. Gas flow: 100sccm

. Duty ratio: 0.5%

Repeat frequency: 1000Hz

. Applied voltage: -10kV

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

. Processing chamber pressure: 0.2Pa

. Pulse amplitude: 5 μsec.

. Processing time (ion implantation time): 5 minutes

. Handling speed: 0.2m/min

[Embodiment 2]

The surface of the base material (1) of the gas barrier layered product 1 obtained by the method described in the first embodiment was applied by a bar coating method using the solution for forming a hard coat layer obtained in Production Example 1. After the obtained coating film was dried by heating at 70 ° C for 1 minute, UV light irradiation was performed using a UV light irradiation line (high pressure mercury lamp, line speed, 20 m/min, cumulative dose 100 mJ/cm ² , peak intensity 1.466 W, number of passes 2 Next, a hard coat layer having a thickness of 2 μm was formed, and a gas barrier layered product 2 composed of a layer of a hard coat layer/substrate (1)/smooth layer (1)/gas barrier layer was obtained.

[Comparative Example 1]

A substrate (2) / smoothing layer (1) / gas barrier was obtained by the same method as in Example 1 except that the substrate (2) was used instead of the substrate (1) in Example 1. A gas barrier laminate 3 composed of layers of layers.

[Comparative Example 2]

In the same manner as in Comparative Example 1, except that the smoothing layer forming solution (2) obtained in Production Example 2 was used instead of the smoothing layer forming solution (1) in Comparative Example 1, a base was obtained. A gas barrier layered product 4 composed of a layer of the material (2)/smoothing layer (2)/gas barrier layer.

[Comparative Example 3]

In the same manner as in Comparative Example 1, except that the smoothing layer forming solution (1) obtained in Production Example 3 was used instead of the smoothing layer forming solution (1) in Comparative Example 1, a base was obtained. A gas barrier layered product 5 composed of a layer of the material (2)/smoothing layer (3)/gas barrier layer.

[Comparative Example 4]

The substrate (2) / smoothing layer (2) / gas barrier was obtained by the same method as in Comparative Example 2 except that the thickness of the smoothing layer (2) in Comparative Example 2 was changed to 10 μm. A gas barrier layered body 6 composed of layers of layers.

The following measurements were carried out on the gas barrier laminates 1 to 6 obtained in Examples 1 and 2 and Comparative Examples 1 to 4.

(thickness of each layer of the gas barrier laminate)

The thickness of each layer of the gas barrier laminate was measured using a stylus type step meter (manufactured by AMBIOS TECNOLOGY, XP-1).

(smoothness of smoothing layer)

Using a light interference microscope ("NT1100" manufactured by Veeco Co., Ltd.), the smoothing layer was observed in a region of 250,000 μm ² (500 μm × 500 μm), and the arithmetic mean roughness (Ra) and the maximum profile height of the roughness curve (Rt) were obtained. ).

(Measurement of water vapor transmission rate)

The water vapor transmission rate of the gas barrier laminates 1 to 6 at a temperature of 40 ° C and a relative humidity of 90% was measured using a water vapor transmission rate measuring device (manufactured by LYSSY Co., Ltd., L80-5000).

The measurement results are shown in the first table.

(UV transmittance)

Use ultraviolet light. Visible light. The near-infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-3600) measures the light transmittance of the gas barrier laminates 1 to 6 at 360 nm.

The measurement results are shown in the first table.

(scratch resistance evaluation)

The scratch resistance test was performed on the gas barrier laminates 1 to 6 and the scratch resistance was evaluated.

Specifically, it is measured on the opposite side to the side where the smoothing layer and the gas barrier layer are laminated on the gas barrier layer according to JIS K5600-5-4 (the substrate surface in the first embodiment, and the second embodiment in the second embodiment). The pencil hardness of the surface of the hard coat layer was evaluated and the scratch resistance was evaluated by the following criteria.

A: pencil hardness is above HB

B: pencil hardness is less than HB

The evaluation results are shown in the first table.

From the first table, the following cases are known.

The gas barrier layered laminates of Examples 1 and 2 are thin and have excellent gas barrier properties and ultraviolet barrier properties, which satisfy the above formulas (1) and (2).

Further, the gas barrier layered product of Example 2 has such characteristics and also has excellent scratch resistance.

On the other hand, although the gas barrier layered systems of Comparative Examples 1 and 2 satisfy the above formulas (1) and (2), since the substrate does not have ultraviolet ray barrier properties, the ultraviolet ray barrier property is poor. Further, in the gas barrier layered product of Comparative Example 2, although the smoothing layer contains the ultraviolet absorber, the thickness of the smoothing layer is thin, and the ultraviolet barrier property is inferior.

The gas barrier layered product of Comparative Example 3 is a result of containing a large amount of the ultraviolet absorbing agent in the smoothing layer, and has excellent ultraviolet ray barrier properties, but the water vapor transmission rate is high.

The gas barrier layered product of the comparative example 4 is a gas barrier layered product which does not satisfy the above formula (2) because it has excellent ultraviolet ray barrier properties as a result of thickening the smoothing layer containing the ultraviolet ray absorbing agent. The thickness is increased. In such a gas barrier layered product, since the thickness of the smoothing layer with respect to the substrate is too thick, there is a possibility that the gas barrier layered body is curled.

Claims (11)

A gas barrier layered product comprising at least a gas barrier layered product in which a substrate, a smoothing layer and a gas barrier layer are laminated in this order, wherein the substrate is at a wavelength of 360 nm. The light-transmitting layer is composed of a resin film having a light transmittance of 3.0% or less, and the smoothing layer is composed of a cured product of the ultraviolet curable resin composition, and the thickness (T ₁ ) of the substrate and the thickness of the smoothing layer (T) ₂ ), the thickness (T ₃ ) of the gas barrier layer satisfies the formula (1), (2), [number 3] T ₁ > T ₂ > T ₃ . . . (1) T ₁ + T ₂ + T ₃ <30 μm. . . (2), and T ₁ is 20 to 28 μm, and T ₂ is 0.5 to 2 μm. The gas barrier layered product according to claim 1, wherein the resin film is a resin film containing an ultraviolet absorber. The gas barrier layered product according to claim 1, wherein an arithmetic mean roughness (Ra) of the interface between the smoothing layer and the gas barrier layer is 5 nm or less, and a maximum profile height of the roughness curve ( Rt) is 100 nm or less. 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 layered product according to claim 1, wherein the thickness (T ₁ ) of the substrate is 20 to 28 μm, and the thickness (T ₂ ) of the smoothing layer is 0.5 to 2 μm, and the gas barrier layer is The thickness (T ₃ ) is 0.05 to 0.3 μm. The gas barrier layered product according to claim 1 is a gas barrier layered laminate further comprising a hard coat layer/substrate/smooth layer/gas barrier layer. . The gas barrier layered product according to claim 1, wherein the gas barrier layered product has a thickness of 5 to 35 μm. The gas barrier layered product according to claim 1, wherein the gas barrier layer has a water vapor transmission rate of 0.05 g/(m ² .day) at a temperature of 40 ° C and a relative humidity of 90%. the following. The gas barrier layered product according to claim 1, wherein the gas barrier layer has a light transmittance of 3.0% or less at a wavelength of 360 nm. 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 10 of the patent application.