JP6544832B2 - Gas barrier laminate, member for electronic device and electronic device - Google Patents

Description

  The present invention relates to a gas barrier laminate having a thin thickness and being excellent in ultraviolet ray blocking properties and gas barrier properties, a member for an electronic device comprising the gas barrier laminate, and an electronic device comprising the member for an electronic device.

Gas barrier films are widely used in liquid crystal displays, electroluminescent (EL) displays, and the like.
In recent years, as this gas barrier film, one having ultraviolet blocking properties and capable of reducing deterioration of elements and the like due to ultraviolet rays has been proposed. For example, Patent Document 1 includes a substrate, an organic layer provided on the substrate, and an inorganic layer provided on the organic layer, and the organic layer is an electron beam curable resin, ultraviolet light A gas barrier film containing an absorber and a light stabilizer has been described.
Further, in recent years, weight reduction and thickness reduction of electronic devices have been advanced, and thin gas barrier laminates used for electronic devices are also required.

JP, 2013-154584, A

As described above, in the gas barrier film described in Patent Document 1, an electron beam curable resin is used as a material for forming an organic layer containing an ultraviolet absorber and the like. In this document, as a reason for using an electron beam curable resin, when an ultraviolet ray curable resin composition is used as a material for forming an organic layer, ultraviolet rays are absorbed by an ultraviolet ray absorber, so the organic layer is sufficiently cured. It is stated that it can not be done.
On the other hand, in order to form an organic layer having excellent ultraviolet absorptivity by using a highly versatile ultraviolet curable resin, the thickness of the organic layer may be increased, or the concentration of the ultraviolet absorber to be contained in the organic layer may be I needed to raise it. However, in the case of the former, a thin gas barrier laminate can not be obtained, and in the case of the latter, since the ultraviolet ray is absorbed by the ultraviolet ray absorber, the organic layer may not be sufficiently cured.

  The present invention has been made in view of such circumstances, and has a thin gas barrier laminate excellent in ultraviolet shielding properties and gas barrier properties, a member for an electronic device comprising the gas barrier laminate, and the electronic device It aims at providing an electronic device provided with a member.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining that the present inventors solved the said subject, a base material, a smoothing layer, and a gas barrier layer are laminated in this order, and the gas-barrier laminated body of this The smoothing layer is made of a cured product of a UV curable resin composition using a resin film of 3.0% or less, and the thickness of the substrate (T ₁ ) and the thickness of the smoothing layer (T) ₂ ), It has been found that when the laminate is formed so as to satisfy the predetermined relational expression of the thickness (T ₃ ) of the gas barrier layer, a gas barrier laminate having a thin thickness and excellent in ultraviolet ray blocking properties and gas barrier properties can be obtained. We came to complete the invention.

  Thus, according to the present invention, the following gas barrier laminates (1) to (9), a member for an electronic device of (10), and an electronic device of (11) are provided.

(1) A gas barrier laminate comprising a substrate, a smoothing layer and a gas barrier layer laminated in this order, wherein the substrate comprises a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm. the smoothing layer is a cured product of the ultraviolet-curable resin composition, the thickness of the substrate (T _1), the thickness of the smoothing layer (T _2), the thickness of the gas barrier layer (T ₃₎ is a compound represented by the following formula A gas barrier laminate characterized by satisfying (1) and (2).

(2) The gas barrier laminate according to (1), wherein the resin film is a resin film containing an ultraviolet absorber.
(3) The arithmetic average roughness (Ra) of the interface between the smoothing layer and the gas barrier layer is 5 nm or less, and the maximum cross-sectional height (Rt) of the roughness curve is 100 nm or less. Gas barrier laminate.
(4) The gas barrier laminate according to (1), wherein the gas barrier layer is a layer obtained by modifying a layer containing a polysilazane compound.
(5) The thickness (T ₁ ) of the substrate is 5 to 28 μm, the thickness (T ₂ ) of the smoothing layer is 0.5 to ₃ μm, and the thickness (T ₃ ) of the gas barrier layer is 0.05 to 0.3 μm And (1).
(6) The gas barrier laminate according to (1), which is a gas barrier laminate having a hard coat layer, and has a layer structure of hard coat layer / substrate / smoothing layer / gas barrier layer.
(7) The gas barrier laminate according to (1), wherein the thickness of the gas barrier laminate is 5 to 35 μm.
(8) The gas barrier laminate according to (1), wherein the water vapor transmission rate at a temperature of 40 ° C. and a relative humidity of 90% of the gas barrier laminate is 0.05 g / (m ² · day) or less.
(9) The gas barrier laminate according to (1), wherein the light transmittance of the gas barrier laminate at a wavelength of 360 nm is 3.0% or less.
(10) A member for an electronic device, comprising the gas barrier laminate according to (1).
(11) An electronic device comprising the member for an electronic device according to (10).

  According to the present invention, a gas barrier laminate having a thin thickness and excellent in ultraviolet ray shielding properties and gas barrier properties, a member for an electronic device comprising the gas barrier laminate, and an electronic device comprising the member for an electronic device are provided. .

  Hereinafter, the present invention will be described in detail in terms of 1) a gas barrier laminate, and 2) an electronic device member and an electronic device.

1) Gas-barrier laminate The gas-barrier laminate of the present invention is a gas-barrier laminate comprising a substrate, a smoothing layer and a gas barrier layer laminated in this order, and the substrate has a light transmittance at a wavelength of 360 nm. Of the resin film is 3.0% or less, the smoothing layer is a cured product of the ultraviolet curable resin composition, the thickness of the substrate (T ₁ ), the thickness of the smoothing layer (T ₂ ), It is characterized in that the thickness (T ₃ ) of the gas barrier layer satisfies the formulas (1) and (2).

(1) Substrate The substrate constituting the gas barrier laminate of the present invention is made of a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm. One feature of the present invention is to use a resin film having excellent ultraviolet blocking properties, that is, a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm. 2.5% or less is preferable and, as for the light transmittance in wavelength 360 nm of the resin film to be used, 2.0% or less is more preferable.
The light transmittance at a wavelength of 360 nm can be measured using an ultraviolet spectrophotometer.

As a resin film which has an ultraviolet-ray blocking property, the resin film containing a resin component and a ultraviolet absorber is mentioned.
The resin component of the resin film may be polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, acrylic resin, cycloolefin Examples include system polymers and aromatic polymers.
These resin components can be used singly or in combination of two or more.

  Among these, polyester, polyamide, polysulfone, polyether sulfone, polyphenylene sulfide or cycloolefin-based polymer is more preferable, and polyester or cycloolefin-based polymer is further preferable because of excellent transparency and versatility.

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

  Examples of cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated products thereof.

The ultraviolet absorber is not particularly limited as long as a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm can be obtained.
Examples of UV absorbers include salicylic acid UV absorbers such as p-t-butylphenyl salicylate and p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy Benzophenone ultraviolet absorbers such as -5-sulfobenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane; 2- (2'-) Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) Benzotriols such as -6- (2H-benzotriazol-2-yl) phenol] Azole-based ultraviolet absorbers; cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3'-diphenylacrylate; 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2- (2-) p-Benzoylphenyl) -3,1-benzoxazin-4-one, 2- (2-naphthyl) -3,1-benzoxazin-4-one, 2,2'-p-phenylenebis (3,1-) Benzoxazinone ultraviolet absorbers such as benzoxazin-4-one), 2,2 '-(2,6-naphthylene) bis (3,1-benzoxazin-4-one); titanium dioxide, cerium oxide, zinc oxide And inorganic ultraviolet absorbers such as iron oxide and barium sulfate.
These ultraviolet absorbers can be used alone or in combination of two or more.

  0.1-10 mass% is preferable with respect to the resin component, and, as for content of a ultraviolet absorber, 0.5-5 mass% is more preferable.

  In the range which does not prevent the effect of this invention, the resin film which has an ultraviolet-ray blocking property may contain various additives. The additives include antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, fillers, color pigments and the like. The content of these additives may be appropriately determined in accordance with the purpose.

  The resin film having an ultraviolet blocking property can be obtained by preparing a resin composition containing a resin component and, if desired, various additives, and forming it into a film. The forming method is not particularly limited, and a known film forming method such as a casting method or a melt extrusion method can be used.

(2) Smoothing layer The smoothing layer which comprises the gas-barrier laminated body of this invention consists of hardened | cured material of an ultraviolet curable resin composition. The smoothing layer is to reduce unevenness on the surface of the base material and to improve interlayer adhesion of the gas barrier laminate. In addition, when the base material contains an additive such as an ultraviolet light absorber, by providing a smoothing layer, these additives can be prevented from bleeding out and diffusing into the gas barrier layer, so that the gas barrier layer Performance degradation can be avoided.

The ultraviolet curable resin composition usually contains a polymerizable compound and a photopolymerization initiator.
Examples of the polymerizable compound include polymerizable prepolymers and polymerizable monomers.
As the polymerizable prepolymer, a polyester acrylate prepolymer obtained by reacting a polyester oligomer having hydroxyl groups at both ends with (meth) acrylic acid, a low molecular weight bisphenol epoxy resin, a novolac epoxy resin, ) Epoxy acrylate-based prepolymer obtained by reaction with acrylic acid, Urethane acrylate-based prepolymer obtained by reaction of polyurethane oligomer and (meth) acrylic acid, polyether polyol with (meth) acrylic acid The obtained polyol acrylate type prepolymer etc. are mentioned.

As a polymerizable monomer, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid Neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanate Bifunctional (meth) acrylates such as nurate di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propionic acid modified dipentaeriol Trifunctional (meth) acrylates such as tritol (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate; propionic acid modified dipentaerythritol penta (Meth) acrylates such as (meth) acrylates, dipentaerythritol hexa (meth) acrylates, caprolactone-modified dipentaerythritol hexa (meth) acrylates or more (meth) acrylates; ethylene glycol divinyl ether, pentaerythritol divinyl ether, 1,6-hexane Diol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide Side-modified bisphenol A divinyl ether, pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, vinyl compounds such as ditrimethylolpropane polyvinyl ether; and others as mentioned, is not necessarily limited thereto.
These polymerizable compounds can be used alone or in combination of two or more.
Here, the expression "(meth) acryloyl group" is meant to include both an acryloyl group and a methacryloyl group.

  In addition, the active energy ray-curable resin composition may contain a polymer resin component such as an acrylic resin, which itself does not have reaction curability. The viscosity of the composition can be adjusted by the addition of a polymeric resin component.

The photopolymerization initiator is not particularly limited as long as the polymerization reaction is initiated by the irradiation of ultraviolet light. Examples of photopolymerization initiators include benzoin polymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether and benzoin isobutyl ether; 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- [2 4- (Methylthio) phenyl] -2-morpholino-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl -Propane-1 Acetophenone-based polymerization initiators such as -one; benzophenone-based polymerization initiators such as benzophenone, 4-phenylbenzophenone, 4,4'-diethylaminobenzophenone, 4,4'-dichlorobenzophenone; 2-methylanthraquinone, 2-ethylanthraquinone, Anthraquinone polymerization initiators such as 2-t-butyl anthraquinone and 2-aminoanthraquinone; 2-methyl thioxanthones, 2-ethyl thioxanthones, 2-chloro thioxanthones, 2,4- dimethyl thioxanthones, thio xanthones such as 2,4-diethyl thioxanthone And a system polymerization initiator.
Although content of a photoinitiator is not specifically limited, Usually, 0.2-30 mass% with respect to the said polymeric compound, Preferably it is 0.5-20 mass%.

The ultraviolet curable resin composition may contain other components as long as the effects of the present invention are not impaired.
As other components, antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, fillers, inorganic fillers, color pigments and the like can be mentioned. The content of these may be appropriately determined in accordance with the purpose.

  The method for forming the smoothing layer is not particularly limited. For example, a coating liquid containing an ultraviolet-curable resin composition and, if necessary, a solvent is prepared, and then the coating liquid is coated on a substrate by a known method, and a coating film obtained By curing the resin, it is possible to form a smoothed layer composed of a cured product of the ultraviolet curable resin composition. Moreover, you may give a drying process before hardening a coating film as needed.

As a solvent for the coating liquid, 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-pentane, n- Aliphatic hydrocarbon solvents such as hexane and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and the like.
These solvents may be used alone or in combination of two or more.

  The coating method may, for example, be a bar coating method, a spin coating method, a dipping method, a roll coating, a gravure coating, a knife coating, an air knife coating, a roll knife coating, a die coating, a screen printing method, a spray coating or a gravure offset method.

  In the case of drying the coating film, conventionally known drying methods such as hot air drying, heat roll drying, infrared irradiation, etc. can be adopted as the drying method. The drying temperature is usually in the range of 60 to 130 ° C. The drying time is usually several seconds to several tens of minutes.

Curing of the coated film can be carried out by irradiating ultraviolet light from the surface of the coated film (the side where the substrate is not present).
As the ultraviolet light source, light sources such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp and a metal halide lamp can be used. No particular restrictions on the quantity of ultraviolet light, it is usually ^{100mJ / cm 2 ~1,000mJ / cm 2} . The irradiation time is usually 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, more preferably 0.1 to 4 nm, and the maximum cross-sectional height (Rt) of the roughness curve is preferably 100 nm or less Preferably, it is 1 to 100 nm, more preferably 20 to 80 nm, and particularly preferably 30 to 65 nm.
When Ra and Rt are in the above ranges, adhesion to the gas barrier layer is excellent, and generation of pinholes in the gas barrier layer can be prevented, so a gas barrier laminate excellent in gas barrier properties can be obtained. it can.
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 laminate of the present invention is a layer having a characteristic (gas barrier property) to suppress permeation of gas such as oxygen and water vapor.

  As the gas barrier layer, for example, a layer obtained by subjecting a layer containing an inorganic vapor deposition film or a polymer compound (hereinafter sometimes referred to as “polymer layer”) to a modification treatment [in this case, It does not mean only the region modified by the ion implantation process or the like, but means the “polymer layer containing the modified region”. Etc. can be mentioned.

Examples of the inorganic vapor deposition film include vapor deposition films of inorganic compounds and metals.
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 sulfide; inorganic oxynitride such as silicon oxynitride; inorganic oxide carbide; inorganic nitride carbide; inorganic oxide nitride carbide and the like.
As a raw material of a vapor deposition film of metal, aluminum, magnesium, zinc, tin, etc. are mentioned.
These can be used singly or in combination of two or more.
Among these, from the viewpoint of gas barrier properties, an inorganic vapor deposition film using an inorganic oxide, inorganic nitride or metal as a raw material is preferable, and from the viewpoint of transparency, an inorganic oxide or inorganic nitride as a raw material The vapor deposition film is preferable.

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

  The thickness of the inorganic vapor deposition film varies depending on the inorganic compound to be used, but is preferably in the range of 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 subjecting the polymer layer to a modification treatment, examples of the polymer compound to be used include silicon-containing polymer compounds such as polyorganosiloxanes and polysilazane compounds, polyimides, polyamides, polyamide imides, polyphenylene ethers, polyethers Ketones, polyetheretherketones, polyolefins, polyesters, polycarbonates, polysulfones, polyethersulfones, polyphenylene sulfides, polyarylates, acrylic resins, cycloolefin polymers, aromatic polymers and the like can be mentioned.
These high molecular compounds can be used singly 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 more excellent gas barrier properties can be formed. Examples of the silicon-containing polymer compound include polysilazane compounds, polycarbosilane compounds, polysilane compounds, and polyorganosiloxane compounds. Among them, polysilazane compounds are preferable because they can form a gas barrier layer having excellent gas barrier properties even if thin. By subjecting the layer containing the polysilazane compound to a modification treatment, a layer (silicon oxynitride layer) containing oxygen, nitrogen, and silicon as main constituent atoms can be formed.

  The polysilazane compound is a polymer compound having a repeating unit containing -Si-N- bond (silazane bond) in the molecule. Specifically, equation (1)

The compound which has a repeating unit represented by is preferable. In addition, the number average molecular weight of the polysilazane compound to be used is not particularly limited, but it is preferably 100 to 50,000.

In said Formula (1), n represents arbitrary natural numbers.
Each of Rx, Ry and Rz independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted Represents a non-hydrolyzable group such as an aryl group having a group or an alkylsilyl group.

  Examples of the alkyl group of the unsubstituted or substituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. C1-C10 alkyl groups, such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc. are mentioned.

  As a cycloalkyl group of the unsubstituted or substituted cycloalkyl group, a cycloalkyl group having a carbon number of 3 to 10, such as cyclobutyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group can be mentioned.

  The alkenyl group of the unsubstituted or substituted alkenyl group is, for example, a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, etc. Ten alkenyl groups can be mentioned.

  As a substituent of the said alkyl group, a cycloalkyl group, and an alkenyl group, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group And aryl groups having unsubstituted or substituted groups such as phenyl group, 4-methylphenyl group and 4-chlorophenyl group; and the like.

  As an aryl group of the aryl group which is unsubstituted or has a substituent, C6-C10 aryl groups, such as a phenyl group, 1-naphthyl group, 2-naphthyl group, are mentioned, for example.

  As a substituent of the aryl group, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; carbon number such as methoxy group and ethoxy group 1 to 6 alkoxy groups; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group; phenyl group, 4-methylphenyl group, 4-chlorophenyl group, etc. Aryl groups having a substituent; and the like.

  Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, trit-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group and ethylsilyl group.

  Among these, as Rx, Ry and Rz, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is particularly preferable.

  As the polysilazane compound having a repeating unit represented by the above formula (1), any of inorganic polysilazane wherein Rx, Ry and Rz are all hydrogen atoms, and organic polysilazane wherein at least one of Rx, Ry and Rz is not a hydrogen atom It may be

In the present invention, a polysilazane modified product can also be used as the polysilazane compound. As modified polysilazanes, for example, JP-A-62-195024, JP-A-2-84437, JP-A-63-81122, JP-A-1-138108, etc., JP-A-2-175726. JP-A-5-238827, JP-A-5-238827, JP-A-6-122852, JP-A-6-306329, JP-A-6-299118, JP-A-9-31333, and the like Those described in JP-A-5-345826, JP-A-4-63833 and the like can be mentioned.
Among these, perhydropolysilazane in which all of Rx, Ry and Rz are hydrogen atoms is preferable as the polysilazane compound from the viewpoint of being able to form an ion implanted layer having easy availability and excellent gas barrier properties.
Moreover, as a polysilazane type-compound, the commercial item marketed as a glass coating material etc. can also be used as it is.
The polysilazane compounds can be used singly or in combination of two or more.

The polymer layer may contain other components in addition to the above-described polymer compound as long as the object of the present invention is not impaired. Other components include curing agents, antiaging agents, light stabilizers, flame retardants and the like.
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, but is preferably in the range of 50 to 300 nm, more preferably 50 to 200 nm.
In the present invention, a gas barrier laminate having sufficient gas barrier properties can be obtained even if the thickness of the polymer layer is nano-order.

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

Examples of the solvent used for the solution for forming a polymer layer include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, n-hexane and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and the like.
These solvents may be used alone or in combination of two or more.

  The coating method of the solution for forming a polymer layer includes bar coating, spin coating, dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing, spray coating, gravure An offset method etc. are mentioned.

  As a method of drying the formed coating film, conventionally known drying methods such as hot air drying, heat roll drying, infrared irradiation, etc. 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.

Examples of the modification treatment of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet radiation treatment and the like.
The ion implantation process is a method of modifying the polymer layer by implanting ions into the polymer layer, as described later.
Plasma treatment is a method of exposing a polymer layer to plasma to modify the polymer layer. For example, plasma treatment can be performed according to the method described in JP-A-2012-106421.
The ultraviolet irradiation treatment is a method of irradiating the polymer layer with ultraviolet light to modify the polymer layer. For example, an ultraviolet-ray modification process can be performed according to the method as described in Unexamined-Japanese-Patent No. 2013-226757.
Among these, the ion implantation treatment is preferable because the inside of the polymer layer can be efficiently reformed without roughening the surface and the gas barrier layer having more excellent gas barrier properties can be formed.

As ions to be injected into the polymer layer, ions of a rare gas such as argon, helium, neon, krypton, xenon, etc .; ions of fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur etc .; methane, ethane etc. Ions of alkane-based gases; ions of alkenes such as ethylene and propylene; ions of alkadiene-based gases such as pentadiene and butadiene; ions of alkyne-based gases such as acetylene; aromatic carbonization such as benzene and toluene 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; and the like.
These ions can be used singly or in combination of two or more.
Among these, ions of a rare gas such as argon, helium, neon, krypton, and xenon are preferable because ions can be more easily injected and a gas barrier layer having more excellent gas barrier properties can be obtained.

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

  As a method of implanting ions, a method of irradiating ions (ion beam) accelerated by an electric field, a method of implanting ions in plasma, etc. may be mentioned. Among them, in the present invention, the latter method of implanting plasma ions is preferable because the target barrier layer can be easily obtained.

  In plasma ion implantation, for example, ions (positive ions) in the plasma are generated by generating plasma in an atmosphere containing plasma generating gas such as a rare gas and applying a negative high voltage pulse to the polymer layer. It can be injected into the surface of the polymer layer.

  By ion implantation, the thickness of the region into which ions are implanted can be controlled by the type of ions, the applied voltage, the implantation conditions such as the treatment time, and is determined according to the thickness of the polymer layer, the use purpose of the laminate, etc. Although it may be sufficient, it is usually 10 to 300 nm.

(4) Gas-barrier laminate The gas-barrier laminate of the present invention is formed by laminating the substrate, the smoothing layer and the gas barrier layer in this order, the thickness of the substrate (T ₁ ), the thickness of the smoothing layer ( T ₂ ) and the thickness (T ₃ ) of the gas barrier layer satisfy the following formulas (1) and (2).

In the gas barrier laminate of the present invention, since a resin film having an ultraviolet blocking property is used as a substrate, it is not necessary to include an ultraviolet absorber in the smoothing layer. Therefore, the thickness of the smoothing layer can be made sufficiently thin because it is not necessary to increase the thickness of the smoothing layer in order to obtain sufficient ultraviolet blocking properties. In addition to the base material, the smoothing layer, and the gas barrier layer, since it is not necessary to separately stack an ultraviolet absorber-containing layer, it is possible to prevent the thickness of the gas barrier laminate from being excessively thick. For this reason, the gas-barrier laminated body which satisfy | fills the requirements prescribed by Formula (1), (2) can be obtained easily.
Further, in the gas barrier laminate of the present invention, since it is not necessary to incorporate an ultraviolet absorber in the smoothing layer, the curing property of the smoothing layer is not deteriorated by absorption of ultraviolet rays by the ultraviolet absorber. By irradiating an ultraviolet ray, the smoothing layer can be sufficiently cured, and as a result, a gas barrier laminate having excellent gas barrier properties can be obtained.
In the gas barrier laminate of the present invention, the lower limit value of T ₁ + T ₂ + T ₃ is usually 5 μm.

The thickness of the substrate _(T 1), the thickness of the smoothing layer _(T 2), the thickness of the gas barrier layer _{(T 3),} respectively, 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 more preferably 0.05 to 0.2 μm.
The thickness of each layer can be measured by the method described in the examples.

The gas barrier laminate of the present invention may have a layer other than the substrate, the smoothing layer, and the gas barrier layer.
As layers other than a base material, a smoothing layer, and a gas barrier layer, a hard cord layer, a conductor layer, an impact absorption layer, an adhesive layer, a process sheet etc. are mentioned. In addition, when a process sheet preserve | saves, conveys a laminated body, etc., it has a role which protects a gas-barrier laminated body, and when a gas-barrier laminated body is used, it peels. The arrangement of these layers is not particularly limited as long as the layer configuration of the substrate / smoothing layer / gas barrier layer is maintained.

The following may be mentioned as specific examples of the layer configuration of the gas barrier laminate of the present invention.
(I) Base material / smoothing layer / gas barrier layer (ii) hard coat layer / base material / smoothing layer / gas barrier layer The gas barrier laminate of (ii) is the side on which the smoothing layer of the base material is formed And a hard coat layer on the opposite side. By providing the hard coat layer, it is possible to prevent the ultraviolet absorber from bleeding out, and by providing scratch resistance, it is possible to avoid the reduction of the ultraviolet blocking property due to the substrate being damaged. .
When the gas barrier laminate of the present invention has a hard coat layer, the thickness of the hard coat layer is preferably 0.5 to 3 μm, more preferably 0.5 to 2.5 μm.

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

(Ii) Gas-barrier laminate having a layer configuration of hard coat layer / substrate / smoothing layer / gas barrier layer First, a hard coat layer is formed on one side of the substrate, and then the other side of the substrate The smoothing layer is formed using the method described above. Then, a gas barrier laminate having a layer structure of hard coat layer / substrate / smoothing layer / gas barrier layer is formed on the obtained smoothing layer by forming the gas barrier layer using the method described above. You can get it.
Alternatively, 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 laminate.
The hard coat layer can be formed by the same method as forming the smoothing layer, using the same material as the material of the smoothing layer.

  In the case where the gas barrier laminate of the present invention has a layer other than the substrate, the smoothing layer, the gas barrier layer, and the hard coat layer, an objective process can be performed by appropriately adding necessary steps in the above manufacturing method. A gas barrier laminate can be obtained.

  The thickness of the gas barrier laminate of the present invention is not particularly limited, but is preferably 5 to 35 μm, more preferably 10 to 34 μm, and still more preferably 20 to 33 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, more preferably 0.03 g / (m ² · day) or less. The lower limit is not particularly limited and is preferably as small as possible, but is usually 0.001 g / (m ² · day) or more.
The water vapor transmission rate can be measured by the method described in the examples.

The light transmittance at a wavelength of 360 nm of the gas barrier laminate of the present invention is preferably 3.0% or less, preferably 2.5% or less, and more preferably 2.0% or less. The lower limit of the light transmittance is usually 0.01% or more.
Because of these properties, the gas barrier laminate of the present invention is excellent in gas barrier properties and ultraviolet blocking properties, and is suitably used as a member for electronic devices.

2) Electronic Device Member and Electronic Device The electronic device member of the present invention is characterized by comprising the gas barrier laminate of the present invention. The member for an electronic device of the present invention has excellent gas barrier properties, so that deterioration of the element due to a gas such as water vapor can be prevented. Moreover, since it is excellent in ultraviolet-ray blocking property, deterioration of the element by ultraviolet irradiation can be prevented. Therefore, the member for electronic devices of the present invention is suitable as a display member such as a liquid crystal display, an EL display, or the like.

The electronic device of the present invention comprises the member for an electronic device of the present invention. As a specific example, a liquid crystal display, an organic electroluminescent display, an inorganic electroluminescent display, electronic paper, a solar cell etc. are mentioned.
The electronic device of the present invention is thin, lightweight, and excellent in the resistance to water vapor and ultraviolet rays, since it comprises the member for an electronic device comprising the gas barrier laminate of the present invention.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.
Parts and% in each example are based on mass unless otherwise noted.

(Compound)
The materials used in each example are shown below.
Base material (1): polyethylene terephthalate film (made by Teijin DuPont, resin film containing an ultraviolet absorber, trade name: Teijin Tetron film HB3, thickness: 25 μm, light transmittance at a wavelength of 360 nm: 1.6%)
Base material (2): polyethylene terephthalate film (manufactured by Mitsubishi Plastics, trade name: PET 25 T-100, thickness: 25 μm, light transmittance at a wavelength of 360 nm: 89%)

Production Example 1
After dissolving 20 parts of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH) as a polymerizable compound in 100 parts of methyl isobutyl ketone, a photopolymerization initiator (manufactured by BASF, trade name: 3 parts of Irgacure 127 was added to prepare a resin layer forming solution.
In the following, this resin layer forming solution was used as a smoothing layer forming solution (1) or a hard coat layer forming solution.

Production Example 2
After dissolving 20 parts of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH) as a polymerizable compound in 100 parts of methyl isobutyl ketone, a photopolymerization initiator (manufactured by BASF, trade name: 3 parts of Irgacure 127 and 1 part of an ultraviolet absorber (manufactured by BASF, trade name: TINVIN 477) were added to prepare a smoothing layer forming solution (2).

Production Example 3
A smoothed layer forming solution (3) was prepared in the same manner as in Production Example 2 except that the blending amount of the ultraviolet light absorber was changed to 8 parts in Production Example 2.

Example 1
The solution (1) for forming a smoothed layer obtained in Production Example 1 is coated on a substrate (1) by a bar coat method, and the obtained coated film is dried by heating at 70 ° C. for 1 minute, and then irradiated with UV light. UV light irradiation using a line (high-pressure mercury lamp, line speed, 20 m / min, integrated light quantity 100 mJ / cm ² , peak intensity 1.466 W, 2 passes), smoothing layer 1 μm thick It formed.
Next, perhydropolysilazane (manufactured by AZ Electronic Materials, trade name: AZNL110A-20) is applied on the smoothing layer (1) by spin coating, and the obtained coating is heated at 120 ° C. for 2 minutes. The perhydropolysilazane layer was formed. Thereafter, as a modification treatment, argon (Ar) is plasma ion implanted into the surface of the perhydropolysilazane layer using a plasma ion implantation apparatus to form a gas barrier layer, and base material (1) / smoothing layer (1) A gas barrier laminate 1 having a layer structure of

The plasma ion implantation apparatus and plasma ion implantation conditions used to form the gas barrier layer are as follows.
(Plasma ion implantation system)
RF power supply: Model No. “RF” 56000, high voltage pulse power supply manufactured by Nippon Denshi Co., Ltd. “PV-3-HSHV-0835” manufactured by Kurita Mfg. Co., Ltd. (plasma ion implantation conditions)
Plasma generated gas: Ar
Gas flow rate: 100 sccm
・ Duty ratio: 0.5%
・ Repetition frequency: 1000 Hz
・ Applied voltage: -10kV
・ RF power supply: Frequency 13.56 MHz, applied power 1000 W
・ Chamber internal pressure: 0.2Pa
・ Pulse width: 5 μsec
Processing time (ion implantation time): 5 minutes Transfer speed: 0.2 m / min

Example 2
The solution for forming a hard coat layer obtained in Production Example 1 was applied by a bar coat method to the surface of the base material (1) of the gas barrier laminate 1 obtained by the method described in Example 1. The coated film is dried by heating at 70 ° C. for 1 minute and then irradiated with UV light 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, pass A hard coat layer having a thickness of 2 μm was formed twice, twice to obtain a gas barrier laminate 2 having a layer structure of hard coat layer / base material (1) / smoothing layer (1) / gas barrier layer.

Comparative Example 1
Substrate (2) / Smoothing layer (1) / Gas barrier layer in the same manner as in Example 1 except that the substrate (2) was used instead of the substrate (1) in Example 1. The gas barrier laminate 3 having a layer structure of

Comparative Example 2
In Comparative Example 1, the same procedure as in Comparative Example 1 was repeated except that the smoothing layer forming solution (2) obtained in Production Example 2 was used instead of the smoothing layer forming solution (1). A gas barrier laminate 4 having a layer configuration of material (2) / smoothing layer (2) / gas barrier layer was obtained.

Comparative Example 3
In Comparative Example 1, the procedure of Comparative Example 1 was repeated except that the smoothing layer forming solution (3) obtained in Production Example 3 was used instead of the smoothing layer forming solution (1). A gas barrier laminate 5 having a layer configuration of material (2) / smoothing layer (3) / gas barrier layer was obtained.

Comparative Example 4
Layer structure of base material (2) / smoothing layer (2) / gas barrier layer, in the same manner as in Comparative Example 2 except that the thickness of the smoothing layer (2) is changed to 10 μm in Comparative Example 2 The gas barrier laminate 6 having the

The following measurements were performed 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 gas barrier laminate)
The thickness of each layer of the gas barrier laminate was measured using a stylus profilometer (manufactured by AMBIOS TECNOLOGY, XP-1).

(Smoothness of smoothing layer)
The smoothing layer is observed for a region of 250000 μm ² (500 μm × 500 μm) using an optical interference microscope (“NT1100” manufactured by Veeco), and the arithmetic average roughness (Ra) and the maximum cross-sectional height of the roughness curve It asked for (Rt).

(Water vapor permeability measurement)
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 apparatus (manufactured by LYSY, L80-5000).
The measurement results are shown in Table 1.

(UV transmittance)
The light transmittance at 360 nm of the gas barrier laminates 1 to 6 was measured using an ultraviolet / visible / near infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-3600).
The measurement results are shown in Table 1.

(Abrasion resistance evaluation)
The scratch resistance test was performed on the gas barrier laminates 1 to 6 to evaluate the scratch resistance.
Specifically, the pencil hardness of the surface of the gas barrier laminate on the side opposite to the side on which the smoothing layer and the gas barrier layer are laminated (the substrate surface in Example 1 and the hard coat layer surface in Example 2) is JIS It measured according to K5600-5-4 and the following references | standards evaluated abrasion resistance.
A: Pencil hardness is HB or more B: Pencil hardness is less than HB The evaluation results are shown in Table 1.

Table 1 shows the following.
The gas barrier laminates of Examples 1 and 2 satisfy the formulas (1) and (2) described above, are thin, and are excellent in gas barrier properties and ultraviolet blocking properties.
Furthermore, the gas barrier laminate of Example 2 has these characteristics, and is excellent in abrasion resistance.
On the other hand, although the gas barrier laminates of Comparative Examples 1 and 2 satisfy the formulas (1) and (2) described above, the base materials do not have the ultraviolet shielding property, and thus the ultraviolet shielding properties are inferior. . Furthermore, in the gas barrier laminate of Comparative Example 2, although the smoothing layer contains the ultraviolet absorber, the thickness of the smoothing layer is thin, and therefore the ultraviolet shielding properties are inferior.
In the gas barrier laminate of Comparative Example 3, as a result of a large amount of the ultraviolet absorber contained in the smoothing layer, the water vapor transmission rate is high although the ultraviolet ray blocking property is excellent.
As a result of thickening the smoothing layer containing the ultraviolet light absorber, the gas barrier laminate of Comparative Example 4 is excellent in ultraviolet ray blocking property, but does not satisfy the above-mentioned formula (2), and the thickness of the gas barrier laminate increases. There is. In such a gas barrier laminate, since the smoothing layer is excessively thick relative to the thickness of the substrate, curl may occur in the gas barrier laminate.

Claims (11)

A gas barrier laminate comprising only a substrate, a smoothing layer and a gas barrier layer, wherein the substrate, the smoothing layer and the gas barrier layer are laminated in this order , or
A substrate, a smoothing layer comprising only one or more layers selected from the group consisting of a hard coat layer, a conductor layer, an impact absorbing layer, an adhesive layer and a process sheet, a substrate, a smoothing layer and a gas barrier layer A gas barrier laminate having a layer structure in which a gas barrier layer is laminated in this order (base material / smoothing layer / gas barrier layer) ,
The substrate is made of a resin film having a light transmittance of 3.0% or less at a wavelength of 360 nm,
The smoothing layer is made of a cured product of a UV curable resin composition,
The thickness of the substrate _(T 1), the thickness of the smoothing layer _(T 2), the thickness of the gas barrier layer _{(T 3)} is a compound represented by the following formula (1), characterized in, that satisfies the (2) Gas barrier laminate.

  The gas barrier laminate according to claim 1, wherein the resin film is a resin film containing an ultraviolet absorber.   The gas barrier laminate according to claim 1, wherein the arithmetic average roughness (Ra) of the interface between the smoothing layer and the gas barrier layer is 5 nm or less, and the maximum cross sectional height (Rt) of the roughness curve is 100 nm or less. body.   The gas barrier laminate according to claim 1, wherein the gas barrier layer is a layer obtained by modifying a layer containing a polysilazane compound. The substrate has a thickness (T ₁ ) of 5 to 28 μm, a thickness of the smoothing layer (T ₂ ) of 0.5 to ₃ μm, and a thickness of the gas barrier layer (T ₃ ) of 0.05 to 0.3 μm. The gas barrier laminate according to 1. A gas barrier laminate having a hard Dokoto layer, a hard coat layer / substrate / smoothing layer / gas barrier layer has a layer structure of gas barrier laminate according to claim 1. The gas barrier laminate, a hard coat layer, the conductive layer, the shock-absorbing layer include those having one or more layers selected from the group consisting of pressure-sensitive adhesive layer and process sheet, the thickness of that is 5 The gas barrier laminate according to claim 1, which is 35 μm. The gas barrier laminate according to claim 1, wherein a water vapor transmission rate at a temperature of 40 ° C and a relative humidity of 90% of the gas barrier laminate is 0.05 g / (m ² · day) or less.   The gas barrier laminate according to claim 1, wherein the light transmittance of the gas barrier laminate at a wavelength of 360 nm is 3.0% or less.   An electronic device member comprising the gas barrier laminate according to claim 1.   The electronic device provided with the member for electronic devices of Claim 10.