WO2015146886A1 - Film de barrière contre des gaz, procédé pour sa fabrication, et dispositif électronique l'utilisant - Google Patents

Film de barrière contre des gaz, procédé pour sa fabrication, et dispositif électronique l'utilisant Download PDF

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Publication number
WO2015146886A1
WO2015146886A1 PCT/JP2015/058684 JP2015058684W WO2015146886A1 WO 2015146886 A1 WO2015146886 A1 WO 2015146886A1 JP 2015058684 W JP2015058684 W JP 2015058684W WO 2015146886 A1 WO2015146886 A1 WO 2015146886A1
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Prior art keywords
gas barrier
layer
group
film
barrier film
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PCT/JP2015/058684
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English (en)
Japanese (ja)
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後藤　良孝
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コニカミノルタ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32082—Radio frequency generated discharge
    • H01J37/32091—Radio frequency generated discharge the radio frequency energy being capacitively coupled to the plasma
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

Definitions

  • the present invention relates to a gas barrier film, a manufacturing method thereof, and an electronic device using the same. More specifically, the present invention relates to a gas barrier film having high gas barrier properties and excellent stability under a high temperature and high humidity environment, a method for producing the same, and an electronic device using the same.
  • a gas barrier layer is formed on a substrate such as a film by a plasma CVD method (Chemical Vapor Deposition). And a method of forming a gas barrier layer by applying a surface treatment (modification treatment) after applying a coating liquid containing polysilazane as a main component on a substrate (Japanese Patent Application Laid-Open No. 2009-255040). No., JP 2012-148416 A).
  • Japanese Patent Laid-Open No. 2009-255040 discloses polysilazane for the purpose of achieving both a thick gas barrier layer and a suppression of cracks in the thick gas barrier layer in order to obtain high gas barrier properties.
  • Japanese Patent Laid-Open No. 2012-148416 discloses a gas barrier property by covering a defect of a gas barrier layer formed by vapor deposition by laminating a polysilazane film having a transition metal compound on the gas barrier layer formed by vapor deposition. It is described to improve.
  • JP-A-63-191832 describes a method for obtaining polyaluminosilazane by heat-reacting polysilazane and aluminum alkoxide as a film material having high hardness and excellent heat resistance and oxidation resistance.
  • Japanese Patent Application Laid-Open No. 2012-56101 discloses a gas barrier film having a gas barrier layer produced using a polysilazane compound on both surfaces of a base material.
  • JP-A-63-191832 also requires performance stability in a high-temperature and high-humidity environment when applied to a gas barrier film having a gas barrier layer on a substrate.
  • gas barrier films that require high barrier properties such as sealing materials for electronic devices such as organic EL elements, are exposed to harsh environments.
  • the stability of the gas barrier performance before and after was not sufficient.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a gas barrier film having high gas barrier properties and excellent stability under high temperature and high humidity conditions.
  • the present inventor conducted intensive research to solve the above problems.
  • at least one of the gas barrier layers is at least one element selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table (however, silicon and
  • the present inventors have found that the above problems can be solved by a gas barrier film containing (except for carbon) and have completed the present invention.
  • At least one gas barrier layer obtained by applying a coating solution containing polysilazane on both surfaces of the substrate to obtain a coating layer and then performing a modification treatment by irradiating the coating layer with active energy rays.
  • a gas barrier film each having At least one of the gas barrier layers is at least one element selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table (however, excluding silicon and carbon) Containing a gas barrier film.
  • At least one element selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table is aluminum (Al), indium (In), gallium (Ga), The above-mentioned 1. which is at least one selected from the group consisting of magnesium (Mg), calcium (Ca), germanium (Ge), and boron (B).
  • At least one gas barrier layer containing at least one element selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table is formed on both surfaces of the base material. Having 1 above. Or 2.
  • a gas barrier layer formed by a vapor deposition method is further included. After the gas barrier layer formed by the vapor deposition method has applied the coating liquid containing the polysilazane to obtain a coating layer, active energy rays are applied to the coating layer. Are formed adjacent to the gas barrier layer obtained by performing the modification treatment by irradiation ⁇ 3.
  • the gas barrier film according to any one of the above.
  • the gas barrier layer formed by the vapor deposition method is formed between the base material and the coating film layer.
  • the active energy ray is a vacuum ultraviolet ray, ⁇ 5.
  • the gas barrier film according to any one of the above.
  • the thickness of the base material is 125 ⁇ m or less. ⁇ 6.
  • the gas barrier film according to any one of the above.
  • a gas barrier layer is formed on both surfaces of the substrate by applying a coating liquid containing polysilazane to obtain a coating layer, and applying a modification treatment by irradiating the coating layer with active energy rays to obtain a gas barrier layer.
  • Forming a gas barrier film comprising: At least one of the coating layers is at least one element selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table (excluding silicon and carbon) ) Containing a gas barrier film.
  • An electronic device body 1 above. ⁇ 7. 7.
  • a gas barrier layer containing at least one element selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table is opposite to the electronic device body of the substrate. 8. provided on the side surface.
  • FIG. 101 is a plasma CVD apparatus
  • 102 is a vacuum chamber
  • 103 is a cathode electrode
  • 105 is a susceptor
  • 106 is a heat medium circulation system
  • 107 is a vacuum exhaust system
  • 108 is a gas introduction system
  • 109 is a high-frequency power source
  • 110 is a base material
  • 160 is a heating / cooling device.
  • It is a schematic diagram which shows an example of the other manufacturing apparatus used for formation of a vapor deposition gas barrier.
  • 1 is a gas barrier film
  • 2 is a substrate
  • 3 is a vapor deposition gas barrier layer
  • 31 is a manufacturing apparatus
  • 32 is a delivery roller
  • 33, 34, 35, and 36 are transport rollers
  • 39 and 40 are film forming rollers
  • 41 is a gas supply pipe
  • 42 is a power source for generating plasma
  • 43 and 44 are magnetic field generators
  • 45 is a winding roller.
  • 21 is an apparatus chamber
  • 22 is a Xe excimer lamp
  • 23 is an excimer lamp holder that also serves as an external electrode
  • 24 is a sample stage
  • 25 is a sample on which a layer is formed
  • 26 is a light shielding plate It is.
  • the present invention provides a gas barrier layer obtained by applying a coating solution containing polysilazane on both surfaces of a substrate to obtain a coating layer, and then subjecting the coating layer to irradiation with active energy rays to perform a modification treatment.
  • the coating layer is formed. Since it is modified from the surface of the layer, oxygen and moisture do not enter the coating layer, and oxidation to the inside of the coating layer and the interface between the coating layer and the substrate is difficult to proceed. Therefore, the unmodified coating layer remains unstable, and there is a problem that the performance such as gas barrier properties after storing under high temperature and high humidity is deteriorated.
  • the layer that does not contain (element) is irradiated with energy rays as a modification treatment, the dangling bond increases as described above, or the absorbance at 250 nm or less increases, and the layer reaches the inside. The energy rays gradually become difficult to penetrate and only the layer surface is modified.
  • the reason is not clear, when an additive element is contained, the absorbance on the low wavelength side decreases as the energy beam is irradiated.
  • the coating layer contains an additive element, irradiation with active energy rays such as vacuum ultraviolet rays improves not only the surface layer portion of the coating layer but also the inside of the coating layer in the film thickness direction. Is performed uniformly. As a result, it is considered that not only the gas barrier property is improved, but also a highly stable gas barrier film is formed which is not easily modified in a high-temperature and high-humidity environment and hardly changes in the film composition.
  • active energy rays such as vacuum ultraviolet rays
  • the gas barrier layer is not formed by providing the gas barrier layer on both surfaces of the substrate as compared with the gas barrier film having the gas barrier layer provided on only one surface of the substrate. Since the gas barrier property does not deteriorate due to the permeation of water vapor from the side surface, a higher gas barrier property can be obtained. In particular, in applications that require extremely high gas barrier properties, such as a sealing material for electronic devices, the influence of water vapor transmission from the side of the base material on which the gas barrier layer is not formed becomes large.
  • the gas barrier layer containing the additive element when the gas barrier layer containing the additive element is provided on at least one surface, the gas barrier layer is formed only on one surface, or on both surfaces. It has been found that the performance is dramatically improved as compared with the case where a gas barrier layer containing no additive element is formed.
  • the curl balance can be improved by providing a coating layer on both sides of the substrate, thereby suppressing deterioration of the support and curling of the film even if the substrate is thinned. It is possible to obtain a gas barrier film excellent in gas barrier properties, bending resistance after storage under high temperature and high humidity conditions, and the like. Therefore, the gas barrier film of the present invention can contribute to weight reduction and thinning of electronic devices.
  • X to Y indicating a range means “X or more and Y or less”.
  • operations and physical properties are measured under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.
  • the gas barrier film of the present invention is obtained by applying a coating liquid containing polysilazane on both the base material and both surfaces of the base material to obtain a coating film layer, and then irradiating the coating film layer with an active energy ray to modify the film. It has at least one gas barrier layer obtained by carrying out.
  • the gas barrier film of the present invention may further contain other members.
  • the gas barrier film of the present invention may have other members on any gas barrier layer between the base material and any gas barrier layer, for example.
  • the other members are not particularly limited, and members used for conventional gas barrier films can be used similarly or appropriately modified.
  • a gas barrier layer a smooth layer, an anchor coat layer, an intermediate layer, a protective layer, a desiccant layer (moisture absorbing layer) and a functionalized layer of an antistatic layer formed by a vapor deposition method.
  • These other members may be used alone or in combination of two or more.
  • the other member may exist as a single layer or may have a laminated structure of two or more layers.
  • a plurality of gas barrier layers may be formed on the same surface. That is, the gas barrier film of the present invention includes both a form in which a plurality of gas barrier layers are formed on one side of the substrate and a form in which a plurality of gas barrier layers are formed on both sides of the substrate.
  • the substrate of the gas barrier film of the present invention (hereinafter also referred to as a substrate) is not particularly limited as long as it can hold a gas barrier layer having gas barrier properties.
  • the said base material may exist as a single layer, or may have a laminated structure of two or more layers.
  • poly (meth) acrylic acid ester polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP ), Polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, cycloolefin polymer, cycloolefin copolymer, and other resin films, organic-inorganic hybrid structures
  • a heat-resistant transparent film product name: Sila-DEC, manufactured by Chisso Corporation having a silsesquioxane having a basic skeleton, and a resin film formed by laminating two or more layers of the above resin It can gel.
  • polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN) and the like are preferably used.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • a heat resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used.
  • polyimide or the like as the heat-resistant substrate.
  • thermoelectric substrate ex.Tg> 200 ° C.
  • heating at a temperature of 200 ° C. or higher is possible in the device manufacturing process, which is necessary for increasing the area of the device and improving the operating efficiency of the device.
  • the resistance of the patterned layer can be reduced by using a transparent conductive layer or metal nanoparticles. That is, the initial characteristics of the device can be greatly improved.
  • the thickness of the substrate is not particularly limited, but is preferably 125 ⁇ m or less, and more preferably 50 ⁇ m or less. By setting the thickness of the substrate to 125 ⁇ m or less, a gas barrier film excellent in flexibility can be obtained. Thus, the base material according to the present invention can be thinner than the conventional one, which can contribute to weight reduction and thinning of the electronic device.
  • the lower limit of the thickness of the substrate is not particularly limited, but is preferably 6 ⁇ m or more, more preferably 12 ⁇ m or more from the viewpoint of the physical strength of the substrate.
  • the substrate may have a functional layer such as a transparent conductive layer, a primer layer, or a clear hard coat layer. As the functional layer, in addition to those described above, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably used.
  • the base material is transparent. Since the base material is transparent and the layer formed on the base material is also transparent, it becomes possible to make a transparent gas barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. It is.
  • the substrate preferably has a high surface smoothness.
  • the surface smoothness those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, the surface of the base material on which the gas barrier layer is provided may be polished to improve smoothness.
  • the base material using the above-described resins or the like may be an unstretched film or a stretched film.
  • the base material used for the gas barrier film of the present invention can be produced by a conventionally known general method.
  • an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.
  • the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc.
  • a stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis).
  • the draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.
  • the surface of the base material may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and laminating a smooth layer described later. Accordingly, it is preferable to perform a combination of the above processes.
  • the gas barrier film according to the present invention is obtained by applying a coating liquid containing polysilazane on both sides of a substrate and drying to obtain a coating layer, and then irradiating with active energy rays to perform a modification treatment. It has a gas barrier layer. And at least one layer of the gas barrier layer has at least one element selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table as an additive element (however, (Except silicon and carbon).
  • the number of the gas barrier layers is not particularly limited as long as at least one gas barrier layer is provided on both surfaces of the base material. However, from the viewpoint of gas barrier properties, the total number is preferably 3 to 10 layers, more preferably 3 layers in total. Layer to 6 layers.
  • the gas barrier layer containing an additive element may be at least one layer, but it is preferable that two or more gas barrier layers are contained.
  • the gas barrier layer containing the additive element is at least on both sides of the substrate.
  • One layer is preferably included.
  • the position in the stacking direction of the gas barrier layer containing the additive element is not particularly limited, but is preferably present in the outermost layer farthest from the substrate.
  • the coating layer containing the additive element before the modification treatment is present in the outermost layer, and by irradiating active energy rays such as vacuum ultraviolet rays from the outermost layer side, The effect of modifying the layer in the same way is obtained. Therefore, a gas barrier film that is almost uniformly modified in the film thickness direction and that is superior in gas barrier properties and bending resistance even after being stored under high temperature and high humidity conditions can be obtained.
  • the gas barrier layers containing each additive element may have the same composition or different compositions.
  • the gas barrier layer containing an additive element is formed by subjecting a coating layer containing a compound containing an additive element (hereinafter also simply referred to as an additive compound) to a modification treatment by active energy ray irradiation.
  • a coating layer containing a compound containing an additive element hereinafter also simply referred to as an additive compound
  • the gas barrier layer that does not contain the additive element is subjected to, for example, a modification process by irradiation with active energy rays on a coating layer that does not contain the additive element. It is formed by.
  • the additive element is not particularly limited as long as it is an element belonging to Group 2, Group 13, and Group 14 (except silicon and carbon) of the long-period periodic table, but examples of the additive element include beryllium ( Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), boron (B), aluminum (Al), gallium (Ga), indium (In), thallium ( Tl), germanium (Ge), tin (Sn), lead (Pb).
  • Be beryllium
  • Mg magnesium
  • Ca calcium
  • Ba barium
  • Ra radium
  • boron aluminum
  • Al aluminum
  • Ga gallium
  • Tl germanium
  • germanium (Ge), tin (Sn), lead (Pb) at least one selected from the group consisting of aluminum, indium, gallium, magnesium, calcium, germanium, and boron is preferable. More preferred is aluminum or boron, and further
  • the content of the additive element in the gas barrier film of the present invention is preferably 0.001 to 50% by mass, more preferably 0.1 to 40% by mass with respect to the mass of the entire gas barrier layer.
  • the gas barrier film of the present invention has two or more gas barrier layers containing an additive element, the total content of the additive elements in each layer is taken as the additive element content in the gas barrier film.
  • Polysilazane is a polymer having a silicon-nitrogen bond, such as SiO 2 , Si 3 N 4 having a bond such as Si—N, Si—H, or N—H, and ceramics such as both intermediate solid solutions SiO x N y. It is a precursor inorganic polymer.
  • the polysilazane preferably has the following structure.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. .
  • R 1 , R 2 and R 3 may be the same or different.
  • examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms.
  • the aryl group include aryl groups having 6 to 30 carbon atoms.
  • non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc.
  • non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, nap
  • the (trialkoxysilyl) alkyl group includes an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specific examples include 3- (triethoxysilyl) propyl group and 3- (trimethoxysilyl) propyl group.
  • the substituent optionally present in R 1 to R 3 is not particularly limited, and examples thereof include an alkyl group, a halogen atom, a hydroxyl group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO 3 H), a carboxyl group (—COOH), a nitro group (—NO 2 ) and the like. Note that the optionally present substituent is not the same as R 1 to R 3 to be substituted. For example, when R 1 to R 3 are alkyl groups, they are not further substituted with an alkyl group.
  • R 1 , R 2 and R 3 are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.
  • n is an integer
  • the polysilazane having the structure represented by the general formula (I) may be determined to have a number average molecular weight of 150 to 150,000 g / mol. preferable.
  • one of preferred embodiments is perhydropolysilazane (PHPS) in which all of R 1 , R 2 and R 3 are hydrogen atoms.
  • PHPS perhydropolysilazane
  • the specific compound of polysilazane that can be used in the present invention the content of polysilazane in the coating layer before the modification treatment, the inorganic precursor compound other than polysilazane contained in the coating liquid containing polysilazane, for example,
  • the forms described in paragraphs “0050” to “0075” of Japanese Patent Application Laid-Open No. 2015-033764 can be appropriately employed.
  • a coating layer formed by applying and drying a coating layer forming coating solution to which an additive compound has been added may be formed.
  • the additive compound include a metal alkoxide compound.
  • metal alkoxide compounds include, for example, beryllium acetylacetonate, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert borate.
  • a compound having a branched alkoxy group is preferable from the viewpoint of reactivity and solubility, and a compound having a 2-propoxy group or a sec-butoxy group is more preferable.
  • metal alkoxide compounds having an acetylacetonate group are also preferred.
  • the acetylacetonate group is preferable because it has an interaction with the central element of the alkoxide compound due to the carbonyl structure, so that handling is easy.
  • a compound having a plurality of alkoxide groups or acetylacetonate groups is more preferable from the viewpoint of reactivity and film composition.
  • the central element of the metal alkoxide compound an element that easily forms a coordinate bond with a nitrogen atom in polysilazane is preferable, and Al or B having a high Lewis acidity is more preferable.
  • More preferred metal alkoxide compounds are, specifically, magnesium ethoxide, triisopropyl borate, aluminum trisec-butoxide, aluminum ethyl acetoacetate diisopropylate, calcium isopropoxide, indium isopropoxide, gallium isopropoxide.
  • metal alkoxide compound a commercially available product or a synthetic product may be used.
  • commercially available products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH-TR (aluminum tris).
  • Ethyl acetoacetate Ethyl acetoacetate
  • aluminum chelate M aluminum alkyl acetoacetate / diisopropylate
  • aluminum chelate D aluminum chelate
  • aluminum chelate A W
  • AL-M acetoalkoxy aluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.
  • Moth Chicks series manufactured by Matsumoto Fine Chemical Co., Ltd.
  • the coating liquid containing polysilazane inert gas atmosphere. This is to prevent the metal alkoxide compound from reacting with moisture and oxygen in the atmosphere and causing intense oxidation.
  • the following compounds can be used.
  • Boron compounds Boron oxide, boron tribromide, boron trifluoride, boron triiodide, sodium cyanoborohydride, diborane, boric acid, trimethyl borate, borax, borazine, borane, boronic acid and the like.
  • Indium compounds Indium oxide, indium chloride, etc.
  • the solvent for preparing the coating liquid for forming a coating layer is not particularly limited as long as it can dissolve or disperse polysilazane and an additive compound, but water and reactive groups that easily react with polysilazane (for example, An organic solvent that does not contain a hydroxyl group or an amine group and is inert to polysilazane is preferred, and an aprotic organic solvent is more preferred.
  • the solvent includes an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben.
  • an aprotic solvent for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben.
  • Hydrogen solvents Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like.
  • the said solvent may be used independently or may be used with the form of a 2 or more types of mixture.
  • the concentration of polysilazane in the coating solution for forming a coating layer is not particularly limited, and is preferably about 0.2 to 35% by mass, although it varies depending on the film thickness of the gas barrier layer and the pot life of the coating solution.
  • the amount of the additive compound used in the coating layer forming coating solution when the additive compound is used is not particularly limited, but is preferably 0.01 to 10 times the mass of the solid content of the polysilazane. The mass is more preferably 0.06 to 6 times.
  • the coating layer forming coating solution preferably contains a catalyst in order to promote modification.
  • a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds.
  • the concentration of the catalyst added at this time is preferably 0.01 to 2% by mass with respect to polysilazane.
  • the following additives can be used in the coating layer forming coating solution as necessary.
  • cellulose ethers, cellulose esters for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc.
  • natural resins for example, rubber, rosin resin, etc., synthetic resins
  • Aminoplasts especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.
  • the method for applying the coating liquid for forming a coating layer is not particularly limited, and a conventionally known appropriate wet coating method can be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
  • the coating thickness can be appropriately set according to the purpose of use of the gas barrier film.
  • the coating thickness per gas barrier layer is preferably 0.01 to 1 ⁇ m, more preferably 0.02 to 0.6 ⁇ m, and more preferably 0.04 to 0.00 ⁇ m after drying. More preferably, it is 4 ⁇ m.
  • each coating thickness of a some coating film layer may be the same, and may differ.
  • the coating film After applying the coating solution, it is preferable to dry the coating film.
  • the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable gas barrier layer can be obtained. The remaining solvent can be removed later.
  • the drying temperature of the coating layer varies depending on the substrate to be applied, but is preferably 30 to 200 ° C.
  • the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat.
  • the temperature can be set by using a hot plate, oven, furnace or the like.
  • the drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes.
  • the drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.
  • the coating film layer obtained by applying the coating liquid containing polysilazane may include a step of removing moisture before or during the modification treatment.
  • a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature.
  • the preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), the more preferable dew point temperature is ⁇ 5 ° C. (temperature 25 ° C./humidity 10%) or less, and the maintaining time depends on the thickness of the gas barrier layer. It is preferable to set appropriately.
  • the dew point temperature is ⁇ 5 ° C. or less and the maintaining time is 1 minute or more.
  • the lower limit of the dew point temperature is not particularly limited, but is usually ⁇ 50 ° C. or higher, and preferably ⁇ 40 ° C. or higher. This is a preferred form from the viewpoint of promoting the dehydration reaction of the gas barrier layer converted to silanol by removing water before or during the reforming treatment.
  • the coating layer modification treatment in the present invention refers to a reaction in which part or all of the polysilazane contained in the coating layer obtained above is converted into silicon oxide, silicon nitride, silicon oxynitride, etc. Specifically, it refers to a reaction in which the gas barrier film of the present invention forms an inorganic thin film at a level that can contribute to the development of gas barrier properties as a whole.
  • the reforming treatment in the present invention is performed by irradiating the coating layer with active energy rays after forming the coating layer.
  • Ozone and active oxygen atoms generated by active energy rays, especially vacuum ultraviolet rays (synonymous with vacuum ultraviolet light) have high oxidation ability, and have high density and insulating properties at low temperatures, silicon nitride, silicon nitride A film, a silicon oxynitride film, or the like can be formed.
  • the substrate is heated, and O 2 , H 2 O contributing to ceramics (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated, so that polysilazane is excited, The conversion of polysilazane into ceramic is promoted, and the resulting gas barrier layer becomes denser.
  • the modification is uniformly performed in the film thickness direction not only on the surface layer portion but also inside the coating layer. Therefore, even after storage under high temperature and high humidity conditions, it is possible to obtain a gas barrier film that hardly generates cracks, has excellent interlayer adhesion and bending resistance, and hardly deteriorates gas barrier properties.
  • the active energy ray for example, infrared ray, visible ray, ultraviolet ray, vacuum ultraviolet ray, X ray, electron beam, ⁇ ray, ⁇ ray, ⁇ ray and the like can be used, but electron beam, ultraviolet ray, vacuum ultraviolet ray are preferable, Ultraviolet rays and vacuum ultraviolet rays are more preferred, and vacuum ultraviolet rays are particularly preferred.
  • the vacuum ultraviolet ray referred to in the present invention generally means ultraviolet light containing electromagnetic waves having a wavelength of 10 to 200 nm.
  • the irradiation intensity and the irradiation time are set within a range in which the substrate carrying the coating layer to be irradiated is not damaged.
  • a 2 kW (80 W / cm ⁇ 25 cm) lamp is used, and the strength of the base material surface is 20 to 300 mW / cm 2 , preferably 50 to 200 mW / cm.
  • the distance between the base material and the ultraviolet irradiation lamp is set so as to be 2, and irradiation can be performed for 0.1 seconds to 10 minutes.
  • the time required for irradiation with ultraviolet rays or vacuum ultraviolet rays is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate and gas barrier layer used.
  • the treatment by vacuum ultraviolet irradiation uses light energy having a wavelength larger than the interatomic bonding force in polysilazane, preferably 100 to 200 nm, more preferably 100 to 180 nm, and bonds the atoms by the action of only photons called photon processes.
  • an inorganic thin film is formed at a relatively low temperature (about 200 ° C. or lower) by proceeding an oxidation reaction with active oxygen or ozone while directly cutting.
  • Examples of such means for generating vacuum ultraviolet rays include, but are not limited to, metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers.
  • the vacuum ultraviolet ray from the source is reflected by the reflector. It is desirable to apply to the polysilazane coating layer before modification.
  • a rare gas excimer lamp is preferably used as the vacuum ultraviolet ray source in the present invention.
  • Oxygen is required for the reaction at the time of vacuum ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease.
  • it is preferably performed in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 300 to 10,000 volume ppm (1 volume%), more preferably 500 to 5,000 volume ppm.
  • the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.
  • the illuminance of the vacuum ultraviolet ray on the coating film surface received by the coating film layer is preferably 1 mW / cm 2 to 10 W / cm 2 , more preferably 30 mW / cm 2 to 200 mW / cm 2. and further preferably 50mW / cm 2 ⁇ 160mW / cm 2. If it is 1 mW / cm 2 or more, high reforming efficiency can be obtained. Moreover, if it is 10 W / cm ⁇ 2 > or less, possibility that ablation will be produced in a coating film or a base material will be damaged is low.
  • Irradiation energy amount of the VUV in coating layer is preferably 10 ⁇ 20000mJ / cm 2, more preferably 20 ⁇ 10000mJ / cm 2, 100 ⁇ 8000mJ / cm 2 More preferably. If the irradiation energy amount is 10 mJ / cm 2 or more, the modification can proceed sufficiently. Moreover, if the irradiation energy amount is 20000 mJ / cm 2 or less, cracks due to over-reformation and thermal deformation of the substrate are unlikely to occur.
  • heating the coating layer simultaneously with vacuum ultraviolet irradiation is also preferably used to promote the modification treatment.
  • the heating method is a method of heating the coating layer by heat conduction by bringing the substrate into contact with a heating element such as a heat block, a method of heating the atmosphere with an external heater such as a resistance wire, and an infrared region such as an IR heater.
  • a heating element such as a heat block
  • an external heater such as a resistance wire
  • an infrared region such as an IR heater.
  • the irradiation temperature (heating temperature) of vacuum ultraviolet rays is preferably 50 to 200 ° C., more preferably 80 to 150 ° C. It is preferable for the irradiation conditions to be within the above-mentioned range since deformation of the substrate and deterioration of strength are unlikely to occur, and the properties of the substrate are not impaired.
  • the irradiation time (heating time) is preferably in the range of 1 second to 10 hours, and more preferably in the range of 10 seconds to 1 hour.
  • the vacuum ultraviolet light used for reforming may be generated by plasma formed in a gas containing at least one of CO 2 and CH 4.
  • the gas containing at least one of CO, CO 2 and CH 4 hereinafter also referred to as carbon-containing gas
  • the carbon-containing gas may be used alone, but carbon containing rare gas or H 2 as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.
  • the silica conversion rate ( x in SiO x ) for example, it can be measured using an XPS method.
  • the chemical composition in the gas barrier layer can be measured by measuring the atomic composition ratio using an XPS surface analyzer.
  • the gas barrier layer can be cut and the cut surface can be measured by measuring the atomic composition ratio with an XPS surface analyzer.
  • the chemical composition in the gas barrier layer can be controlled by the types and amounts of polysilazane and additive compounds used when forming the gas barrier layer, conditions for modifying the coating layer, and the like.
  • the thickness per gas barrier layer is preferably from 0.01 to 1 ⁇ m, more preferably from 0.02 to 0.6 ⁇ m, from the viewpoint of achieving both gas barrier properties and flexibility. More preferably, the thickness is 04 to 0.4 ⁇ m.
  • the thickness of the gas barrier layer is 0.01 ⁇ m or more, high gas barrier properties can be obtained. Moreover, if it is 1 micrometer or less, sufficient flexibility will be acquired and the crack of a film
  • the thickness per gas barrier layer is a thickness measured by a transmission electron microscope JEM-2000FX manufactured by JEOL.
  • the polysilazane is modified in the step of irradiating the coating layer with active energy rays such as vacuum ultraviolet rays, so that the layer as a whole is SiO x N y M w (M is an additive element)
  • a gas barrier layer containing silicon oxynitride having a composition of x, y, and w is an atomic ratio of oxygen, nitrogen, and M, respectively, with respect to silicon is formed.
  • active energy rays such as vacuum ultraviolet rays
  • the distribution of the composition SiO x N y M w is a predetermined condition, that is, 0.25 ⁇ x ⁇ 1.1 and 0.4 ⁇ y ⁇ 0.75, and 0 ⁇ w ⁇ 0. It is preferable to satisfy the condition of having a region of .5 in the thickness direction of 50 nm or more.
  • x and y are basically in the range of 2x + 3y ⁇ 4.
  • the coating film contains silanol groups, and there are cases where 2 ⁇ x ⁇ 2.5.
  • the values of x, y, z, and w described above are determined by measuring the element ratio (atomic ratio) in the film thickness direction of each constituent element using, for example, the following apparatus and method. be able to.
  • XPS analysis conditions Apparatus QUANTERASXM (manufactured by ULVAC-PHI Co., Ltd.)
  • X-ray source Monochromatic Al-K ⁇ Measurement area: Si2p, C1s, N1s, O1s, Al Sputtering ion: Ar (2 keV)
  • Depth profile repeat measurement after 1 minute sputtering. One measurement corresponds to a thickness of about 5 nm in terms of a SiO 2 thin film standard sample.
  • the background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.
  • MultiPak manufactured by ULVAC-PHI
  • the first measurement data is excluded because of the influence of surface adsorbed water and organic contamination.
  • the film density of the gas barrier layer of the present invention can be appropriately set according to the purpose.
  • the film density of the gas barrier layer is preferably in the range of 1.5 to 2.6 g / cm 3 . Within this range, the density of the film is improved, so that deterioration of the film under high-temperature and high-humidity conditions and accompanying gas barrier properties can be prevented.
  • the gas barrier film of the present invention preferably further has a gas barrier layer (hereinafter also simply referred to as a vapor deposition gas barrier layer) formed by a vapor deposition method.
  • a gas barrier layer By having a vapor deposition gas barrier layer, a gas barrier film having higher gas barrier properties can be obtained.
  • the vapor deposition gas barrier layer may form only one layer or a plurality of layers.
  • a vapor deposition gas barrier layer may be formed in the one surface side of a base material, and can also be formed in both surfaces.
  • the position in the stacking direction of the vapor deposition gas barrier layer in the gas barrier film of the present invention is not particularly limited, but after applying a coating liquid containing polysilazane to obtain a coating layer, the coating layer is irradiated with active energy rays. It is preferably formed adjacent to the gas barrier layer obtained by performing the modification treatment. By doing in this way, since the defect of a vapor deposition gas barrier layer can be repaired and the adhesiveness of the interface with a vapor deposition gas barrier layer is improved, a higher performance gas barrier layer can be obtained. In addition, a gas barrier film that is difficult to break can be obtained.
  • the coating layer is irradiated with active energy rays for modification treatment. It is preferable to form one or a plurality of gas barrier layers obtained by performing.
  • the film thickness of the vapor deposition gas barrier layer described here is not particularly limited, but is preferably 50 to 600 nm, and more preferably 100 to 500 nm. If it is such a range, it will be excellent in gas barrier performance, bending resistance, cutting process aptitude, etc.
  • the elastic modulus of the vapor deposition gas barrier layer is preferably 15 to 45 GPa, more preferably 20 to 40 GPa. If it is this range, gas-barrier performance, bending tolerance, and cutting processability will be obtained.
  • the elastic modulus can be measured by a nanoindentation method.
  • the vapor deposition method is not particularly limited, and a known thin film deposition technique can be used.
  • vapor deposition, reactive vapor deposition, sputtering, reactive sputtering, chemical vapor deposition, and the like can be given.
  • FIG. 1 is a schematic diagram showing an example of a vacuum plasma CVD apparatus used for forming a vapor deposition gas barrier layer.
  • the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface side inside the vacuum chamber 102. Further, a cathode electrode 103 is disposed on the ceiling side inside the vacuum chamber 102 at a position facing the susceptor 105.
  • a heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102.
  • a heat medium is disposed in the heat medium circulation system 106.
  • the heat medium circulation system 106 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium.
  • a heating / cooling device 160 having a storage device is provided.
  • the vapor deposition gas barrier layer is preferably formed on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity.
  • an apparatus that can be used when producing a vapor deposition gas barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and the pair of components. It is preferable that the apparatus has a configuration capable of discharging between film rollers. For example, when the manufacturing apparatus shown in FIG. 2 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible to do.
  • FIG. 3 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the vapor deposition gas barrier layer.
  • the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.
  • the manufacturing apparatus 31 shown in FIG. 2 includes a delivery roller 32, transport rollers 33, 34, 35, and 36, film formation rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a film formation roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45.
  • a vacuum chamber (not shown).
  • the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.
  • a raw material gas, a reactive gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more.
  • the source gas in the film forming gas used for forming the vapor deposition gas barrier layer 3 can be appropriately selected and used according to the material of the vapor deposition gas barrier layer 3 to be formed.
  • a source gas for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used.
  • organosilicon compounds examples include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane.
  • HMDSO hexamethyldisiloxane
  • HMDS hexamethyldisilane
  • 1,1,3,3-tetramethyldisiloxane vinyltrimethylsilane
  • methyltrimethylsilane hexamethyldisilane.
  • Methylsilane dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • Examples include silane and octamethylcyclotetrasiloxane.
  • organosilicon compounds hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferred from the viewpoints of handling properties of the compound and gas barrier properties of the obtained vapor deposition gas barrier layer.
  • organosilicon compounds can be used alone or in combination of two or more.
  • the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene.
  • an appropriate source gas is selected according to the kind of the vapor deposition gas barrier layer 3.
  • a reactive gas may be used in addition to the raw material gas.
  • a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • a reactive gas for forming nitride nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.
  • a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • carrier gas and discharge gas known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.
  • the ratio of the raw material gas and the reactive gas is a reaction that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive as compared with the ratio of the amount of gas. It is excellent in that excellent barrier properties and flex resistance can be obtained by the vapor deposition gas barrier layer 3 formed by not excessively increasing the ratio of the reaction gas. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.
  • the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.
  • an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used.
  • the power applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed, and if it is 10 kW or less, the amount of heat generated during film formation can be suppressed, and the substrate during film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.
  • the conveyance speed (line speed) of the base material 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is in the range of 5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient thickness as a gas barrier layer, without impairing productivity.
  • the vapor deposition gas barrier layer is formed by the plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG.
  • This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode.
  • Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.
  • the formed film may be subjected to excimer treatment (modification treatment).
  • excimer treatment vacuum ultraviolet treatment
  • a known method can be used, but vacuum ultraviolet treatment as described in the above-mentioned section “ ⁇ Coating layer reforming treatment>” is preferable, and further 100 to 180 nm. Vacuum ultraviolet treatment with light energy of a wavelength of is preferred.
  • the gas barrier film of the present invention has a smooth layer (underlying layer, primer layer, hard coat layer) between the surface of the base material having the gas barrier layer, preferably between the base material and the first gas barrier layer. May be.
  • the smooth layer is provided in order to flatten the rough surface of the base material on which protrusions and the like exist, or to fill the unevenness and pinholes generated in the gas barrier layer with the protrusions on the base material.
  • Such a smooth layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, the gas barrier film of the present invention preferably further has a smooth layer containing a carbon-containing polymer between the base material and the first gas barrier layer.
  • the smooth layer also contains a carbon-containing polymer, preferably a curable resin.
  • the curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material or the like with an active energy ray such as an ultraviolet ray to be cured is heated. And thermosetting resins obtained by curing. These curable resins may be used alone or in combination of two or more.
  • the smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less.
  • the surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of ⁇ m many times.
  • AFM Anamic Force Microscope
  • the thickness of the smooth layer is not particularly limited, but is preferably in the range of 0.1 to 10 ⁇ m.
  • an anchor coat layer On the surface of the base material, an anchor coat layer may be formed as an easy-adhesion layer for the purpose of improving adhesiveness (adhesion).
  • the anchor coat agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene / vinyl alcohol resin, vinyl-modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Can be used alone or in combination of two or more.
  • a commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” in 3% isopropyl alcohol) can be used.
  • the gas barrier film of the present invention can be continuously produced and wound into a roll form (so-called roll-to-roll production). In that case, it is preferable to stick and wind up a protective sheet on the surface in which the gas barrier layer was formed.
  • a protective sheet is applied in a place with a high degree of cleanliness. It is very effective to prevent the adhesion of dust. In addition, it is effective in preventing scratches on the gas barrier layer surface that enters during winding.
  • the protective sheet is not particularly limited, and general “protective sheet” and “release sheet” having a configuration in which a weakly adhesive layer is provided on a resin substrate having a thickness of about 100 ⁇ m can be used.
  • the water vapor transmission rate of the gas barrier film of the present invention is preferably as low as possible, but is preferably 0.001 to 0.00001 g / m 2 ⁇ 24 h, for example, 0.0001 to 0.00001 g / m 2 ⁇ 24 h. More preferably.
  • the method for measuring the water vapor transmission rate is not particularly limited, but in the present invention, the water vapor transmission rate measurement method was measured by the Ca method described in the examples described later.
  • the method for producing the gas barrier film of the present invention is not particularly limited. For example, by applying a coating liquid containing polysilazane to obtain a coating layer, and applying a modification treatment by irradiating the coating layer with active energy rays to obtain a gas barrier layer, It can be manufactured by a method including forming a gas barrier layer.
  • at least one of the coating layers is at least one element selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table (however, silicon and (Except carbon).
  • the gas barrier layer may be formed on the other surface in the same manner.
  • the modification treatment may be performed on the coating layers on both sides.
  • a first substrate and a second substrate are prepared, and a coating liquid containing polysilazane is applied to one surface to form a coating layer, and the coating layer is irradiated with active energy rays. Then, a gas barrier layer is formed by performing a modification treatment, and then the surfaces of the first base material and the second base material on which the gas barrier layer is not formed are bonded using an adhesive to obtain a gas barrier film. be able to. At this time, at least one layer of the coating layer contains an additive element. Although it does not restrict
  • the gas barrier film of the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, this invention provides the electronic device which has an electronic device main body and the gas barrier film of this invention, or the gas barrier film obtained by the manufacturing method which concerns on this invention.
  • the gas barrier film of the present invention may be sealed so that the gas barrier layer containing the additive element is on the side close to the electronic device body, and on the opposite side of the electronic device body across the substrate. It may be sealed.
  • Examples of the electronic device include electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device.
  • electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV).
  • an organic EL device such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device.
  • LCD liquid crystal display element
  • PV solar cell
  • the gas barrier film of the present invention can also be used for device film sealing. That is, it is a method of providing the gas barrier film of the present invention on the surface of the device itself as a support.
  • the device may be covered with a protective layer before providing the gas barrier film.
  • the gas barrier film of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method.
  • the solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured.
  • an adhesive agent A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.
  • Organic EL device Examples of organic EL elements using a gas barrier film are described in detail in JP-A-2007-30387.
  • the reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a ⁇ / 4 plate, and a polarizing film in order from the bottom.
  • the gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
  • the transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a ⁇ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a ⁇ / 4 plate, and a polarization It has a structure consisting of a film. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
  • the type of the liquid crystal cell is not particularly limited, but more preferably a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment), an EC type, a B type.
  • TN type Transmission Nematic
  • STN type Super Twisted Nematic
  • HAN type Hybrid Aligned Nematic
  • VA Very Alignment
  • an EC type a B type.
  • OCB type Optically Compensated Bend
  • IPS type In-Plane Switching
  • CPA type Continuous Pinwheel Alignment
  • the gas barrier film of the present invention can also be used as a sealing film for solar cell elements.
  • the solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. For example, it is a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type.
  • Amorphous silicon-based solar cell elements III-V group compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI group compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I-III- such as copper / indium / selenium (so-called CIS), copper / indium / gallium / selenium (so-called CIGS), copper / indium / gallium / selenium / sulfur (so-called CIGS), etc.
  • Group VI compound semiconductor solar cell element dye-sensitized solar cell element, organic solar cell element, etc. And the like.
  • the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur.
  • CIS system copper / indium / selenium system
  • CIGS system copper / indium / gallium / selenium system
  • sulfur copper / indium / gallium / selenium / sulfur.
  • a group I-III-VI compound semiconductor solar cell element such as a system (so-called CIGSS system) is preferable.
  • the gas barrier film of the present invention can also be used as an optical member.
  • the optical member include a circularly polarizing plate.
  • a circularly polarizing plate can be produced by laminating a ⁇ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the ⁇ / 4 plate and the absorption axis of the polarizing plate is 45 °.
  • a polarizing plate one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used.
  • MD longitudinal direction
  • those described in JP-A-2002-86554 can be suitably used. .
  • the polysilazane-containing coating solution prepared above is 250 nm thick on one side of the base material (A side: in this example, the side on which the organic EL element is arranged) with a spin coater.
  • the film was applied to form a film, allowed to stand for 2 minutes, then subjected to additional heat treatment for 1 minute on a hot plate at 80 ° C. to form a coating layer.
  • vacuum ultraviolet irradiation treatment was performed by the following apparatus and method to produce a gas barrier film (sample No. 1).
  • Vacuum Ultraviolet Irradiator Excimer Irradiator MODEL MECL-M-1-200 Wavelength 172nm, stage temperature 100 ° C, Integrated light quantity 6500 mJ / cm 2 , oxygen concentration 0.1 volume%.
  • reference numeral 11 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber.
  • the oxygen concentration can be maintained at a predetermined concentration.
  • Reference numeral 12 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm
  • reference numeral 13 denotes an excimer lamp holder that also serves as an external electrode.
  • Reference numeral 14 denotes a sample stage. The sample stage 14 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 11 by a moving means (not shown).
  • the sample stage 14 can be maintained at a predetermined temperature by a heating means (not shown).
  • Reference numeral 15 denotes a sample on which a polysilazane coating layer is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 3 mm.
  • Reference numeral 16 denotes a light shielding plate, which prevents the vacuum ultraviolet light from being applied to the coating layer of the sample during the aging of the Xe excimer lamp 12.
  • the energy applied to the surface of the sample coating layer in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using a UV integrating photometer: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics.
  • the sensor head is installed in the center of the sample stage 14 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 11 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the process, and the sample stage 14 was moved at a speed of 0.5 m / min for measurement.
  • an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.
  • the moving speed of the sample stage was adjusted to adjust the irradiation energy to 6500 mJ / cm 2 .
  • the vacuum ultraviolet irradiation was performed after aging for 10 minutes as in the case of irradiation energy measurement.
  • the same polysilazane-containing coating as described above is formed on the surface of the substrate opposite to the surface on which the gas barrier layer is formed (B surface: the surface opposite to the side on which the organic EL element is arranged in this embodiment).
  • the solution was formed into a film with a spin coater to 250 nm and allowed to stand for 2 minutes, and then subjected to additional heat treatment for 1 minute on a hot plate at 80 ° C. to form a coating layer.
  • Example 1 An aluminum-containing coating solution was prepared by the following method.
  • a gas barrier film (Sample No. 1) was prepared in the same manner as in Comparative Example 2 except that the aluminum-containing coating solution obtained above formed a coating layer serving as the first gas barrier layer on the A surface of the substrate. 3) was produced.
  • Example 2 A gas barrier film (sample No. 4) was produced in the same manner as in Comparative Example 2 except that the coating layer serving as a gas barrier layer was formed on the B surface of the base material with the aluminum-containing coating solution obtained above. did.
  • Example 3 With the aluminum-containing coating solution obtained above, except that the coating layer serving as the first gas barrier layer was formed on the A side of the substrate, and further, the coating layer was also formed on the B side of the substrate. In the same manner as in Comparative Example 2, a gas barrier film (Sample No. 5) was produced.
  • Comparative Example 3 A gas barrier film (sample) was prepared in the same manner as in Comparative Example 2 except that when the coating layer serving as a gas barrier layer was formed on the B surface of the substrate, the spin coating rotation speed was changed to 150 nm. No. 6) was produced.
  • Example 4 A gas barrier film (sample) was formed in the same manner as in Example 1 except that when the coating layer serving as the gas barrier layer was formed on the B surface of the substrate, the spin coating rotation speed was changed to 150 nm. No. 7) was produced.
  • Example 5 A gas barrier film (sample) was formed in the same manner as in Example 2 except that when the coating layer serving as a gas barrier layer was formed on the B surface of the substrate, the spin coating rotation speed was changed to a film thickness of 150 nm. No. 8) was produced.
  • Example 6 A gas barrier film (sample) was formed in the same manner as in Example 3 except that when the coating layer serving as the gas barrier layer was formed on the B surface of the substrate, the spin coating rotation speed was changed to a film thickness of 150 nm. No. 9) was produced.
  • Example 4 When forming a coating film layer serving as a gas barrier layer on the B-side of the substrate, the total amount of light at the time of vacuum ultraviolet irradiation after the coating film layer is formed by changing the spin coating rotation speed to a film thickness of 50 nm A gas barrier film (Sample No. 10) was produced in the same manner as in Comparative Example 2 except that was set to 3000 mJ / cm 2 .
  • Example 7 When forming a coating film layer serving as a gas barrier layer on the B-side of the substrate, the total amount of light at the time of vacuum ultraviolet irradiation after the coating film layer is formed by changing the spin coating rotation speed to a film thickness of 50 nm A gas barrier film (Sample No. 11) was produced in the same manner as in Example 2 except that the pressure was 3000 mJ / cm 2 .
  • Base material polyethylene terephthalate (PET) film with clear hard coat layer (CHC) manufactured by Kimoto Co., Ltd., hard coat layer is composed of UV curable resin mainly composed of acrylic resin, PET thickness 125 ⁇ m, CHC thickness 6 ⁇ m
  • a gas barrier layer 100 nm
  • SiOC silicon oxycarbide
  • Comparative Example 6 A gas barrier film (Sample No. 13) was produced in the same manner as in Comparative Example 5 except that the same gas barrier layer as that of Sample 6 was provided on the B surface of the substrate.
  • Example 8 A gas barrier film (sample No. 14) similar to that of sample 13 was prepared except that the second layer of sample 13 was changed to the first layer of sample 3.
  • Example 9 The third layer of sample 13 was formed into a film having a thickness of 40 nm by changing the film thickness of the aluminum-containing coating solution of the first layer of sample 3 to form a polysilazane coating layer. Thereafter, vacuum ultraviolet irradiation was performed by the above apparatus and method (however, the integrated light amount was 3000 mJ / cm 2 ), and a gas barrier layer serving as a third layer was formed. In this way, a gas barrier film (sample No. 15 was produced.
  • Example 10 A gas barrier film (sample No. 16) similar to that of sample 14 was prepared except that the third layer of sample 14 was changed to the third layer of sample 15.
  • Example 11 A gas barrier film (sample No. 17) similar to that of sample 13 was prepared except that the B surface of sample 13 was changed to the B surface of sample 8.
  • Example 12 A gas barrier film (sample No. 18) similar to that of sample 16 was prepared except that the B surface of sample 16 was changed to the B surface of sample 17.
  • Example 13 A gas barrier film (sample No. 20) similar to that of sample 19 was prepared except that the second layer on the A side of sample 19 was changed to the second layer on the A side of sample 14.
  • Example 14 A gas barrier film (sample No. 21) similar to that of sample 19 was prepared except that the third layer on the A surface of sample 19 was changed to the third layer on the A surface of sample 15.
  • Example 15 A gas barrier film (sample No. 22) similar to that of sample 20 was produced except that the third layer on the A side of sample 20 was changed to the third layer on the A side of sample 15.
  • Example 16 A gas barrier film (sample No. 23) similar to that of sample 19 was prepared except that the second layer on the B surface of sample 19 was changed to the first layer on the B surface of sample 17.
  • Example 17 A gas barrier film (sample No. 24) similar to that of sample 21 was prepared except that the second layer on the B surface of sample 21 was changed to the first layer on the B surface of sample 17.
  • Example 18 A gas barrier film (sample No. 25) similar to the sample 24 was produced except that the second layer on the A side of the sample 24 was changed to the second layer on the A side of the sample 20.
  • Example 8 A gas barrier film (sample No. 26) similar to that of sample 19 was prepared except that the thickness of the base material of sample 19 was 25 ⁇ m.
  • Example 19 A gas barrier film (sample No. 27) similar to that of sample 20 was prepared except that the thickness of the base material of sample 20 was 25 ⁇ m.
  • Example 20 A gas barrier film (sample No. 28) similar to that of sample 21 was prepared except that the thickness of the base material of sample 21 was 25 ⁇ m.
  • Example 21 A gas barrier film (sample No. 29) similar to that of sample 23 was produced except that the thickness of the base material of sample 23 was 25 ⁇ m.
  • Example 22 In the aluminum-containing coating solution used for preparing the second layer, the third layer on the A side, and the second layer on the B side of the sample 25, ALCH is the same amount of gallium (III) isopropoxide (Wako Pure Chemical Industries, Ltd.).
  • a gas barrier film (Sample No. 30) was produced in the same manner as Sample 25 except that the thickness was the same as that manufactured by the company.
  • Example 23 In the aluminum-containing coating solution used for preparing the second layer, the third layer on the A side, and the second layer on the B side of the sample 25, ALCH was added in the same amount of indium (III) isopropoxide (Wako Pure Chemical Industries, Ltd.).
  • a gas barrier film (Sample No. 31) was produced in the same manner as Sample 25 except that the thickness was the same as that manufactured by the company.
  • Example 24 In the aluminum-containing coating solution used when preparing the second layer, the third layer on the A side of the sample 25, and the second layer on the B side, ALCH is the same amount of magnesium ethoxide (manufactured by Wako Pure Chemical Industries, Ltd.). A gas barrier film (Sample No. 32) was produced in the same manner as Sample 25 except that the thickness was the same.
  • Example 25 In the aluminum-containing coating solution used to prepare the second layer, the third layer, and the second layer on the B surface of the sample 25, ALCH is the same amount of calcium isopropoxide (manufactured by SIGMA-ALDRICH), A gas barrier film (Sample No. 33) was produced in the same manner as Sample 25 except that the thickness was the same.
  • Example 26 In the aluminum-containing coating solution used for preparing the second layer, the third layer on the A side, and the second layer on the B side of the sample 25, the same amount of ALCH triisopropyl borate (manufactured by Wako Pure Chemical Industries, Ltd.) A gas barrier film (Sample No. 34) was produced in the same manner as Sample 25 except that the thickness was the same.
  • Evaluation of the water vapor barrier property was performed by depositing metal calcium having a thickness of 80 nm on a gas barrier film, and evaluating the time when the formed calcium was 50% area as 50% area time (see below). ). 50% area time before and after exposure to high temperature and high humidity for 500 hours was evaluated, and 50% area time after exposure / 50% area time before exposure was calculated as retention rate (%), and shown in Tables 2-4 It was. As an index of retention rate, 70% or more was considered acceptable, and less than 70% was judged as nonconforming.
  • Vapor deposition device JEOL Ltd., vacuum vapor deposition device JEE-400 Constant temperature and humidity oven: Yamato Humidic Chamber IG47M (raw materials) Metal that reacts with water and corrodes: Calcium (granular) Water vapor impermeable metal: Aluminum ( ⁇ 3-5mm, granular) (Preparation of water vapor barrier property evaluation sample)
  • a vacuum vapor deposition apparatus manufactured by JEOL Ltd., vacuum vapor deposition apparatus JEE-400
  • metallic calcium was vapor-deposited in a size of 12 mm ⁇ 12 mm through a mask on the outermost gas barrier layer surface of the produced gas barrier film. At this time, the deposited film thickness was set to 80 nm.
  • the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet and temporarily sealed.
  • the vacuum state is released, and it is immediately transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum vapor-deposited surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX Corporation).
  • the water vapor barrier property evaluation sample was produced by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.
  • the obtained sample was stored under high temperature and high humidity of 85 ° C. and 95% RH, and the state in which metallic calcium was corroded with respect to the storage time was observed.
  • the observation was obtained by linearly interpolating the time at which the area where metal calcium was corroded with respect to the metal calcium vapor deposition area of 12 mm ⁇ 12 mm to 50% from the observation results.
  • a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample was stored under the same high temperature and high humidity conditions of 85 ° C. and 95% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.
  • Each gas barrier film was repeatedly bent 500 times at an angle of 180 ° so as to have a radius of curvature of 2 mm so that the A surface was on top. Thereafter, bending was repeated 500 times at an angle of 180 ° so that the radius was 2 mm so that the B surface was on top. Thereafter, the water vapor transmission rate (water vapor barrier property) was measured in the same manner as described above, the deterioration resistance was calculated according to the following formula from the change in the water vapor transmission rate before and after bending, and the bending resistance was evaluated according to the following criteria. .
  • Deterioration resistance (water vapor transmission rate after bending test / water vapor transmission rate before bending test) ⁇ 100 (%) 5: Deterioration resistance is 95% or more, 4: Deterioration resistance is 85% or more and less than 95%. 3: Deterioration resistance is 50% or more and less than 85%. 2: Deterioration resistance is 10% or more and less than 50%. 1: Deterioration resistance is less than 10%.
  • This test is a sample before being exposed to a high temperature and high humidity of 85 ° C. and 95% RH for 500 hours, and a sample after being exposed to a high temperature and high humidity of 85 ° C. and 95% RH for 500 hours (after 500 hours of DH). Went on both.
  • an organic EL element (after hot water treatment) was produced using a gas barrier film obtained by performing the following hot water treatment on the A surface of the gas barrier film produced above.
  • Hot water treatment The gas barrier film produced above was immersed in hot water at 90 ° C. for 15 minutes, and after natural drying, the surface was dried, and then an organic EL device was produced.
  • the hole transport layer forming coating liquid shown below is applied by an extrusion coater and then dried to form a hole transport layer. did.
  • the coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.
  • the gas barrier film was subjected to cleaning surface modification using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm 2 and a distance of 10 mm.
  • the charge removal treatment was performed using a static eliminator with weak X-rays.
  • PEDOT / PSS polystyrene sulfonate
  • Baytron P AI 4083 manufactured by Bayer
  • ⁇ Drying and heat treatment conditions After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment.
  • the back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.
  • the following coating solution for forming a white light-emitting layer was applied by an extrusion coater and then dried to form a light-emitting layer.
  • the white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.
  • the host material HA is 1.0 g
  • the dopant material DA is 100 mg
  • the dopant material DB is 0.2 mg
  • the dopant material DC is 0.2 mg
  • 100 g of toluene was prepared as a white light emitting layer forming coating solution.
  • the coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.
  • the coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.
  • the electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.
  • an electron injection layer was formed on the formed electron transport layer.
  • the substrate was put into a decompression chamber and decompressed to 5 ⁇ 10 ⁇ 4 Pa.
  • cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.
  • Second electrode Except for the portion that becomes the extraction electrode on the first electrode, aluminum is used as the second electrode forming material on the formed electron injection layer under a vacuum of 5 ⁇ 10 ⁇ 4 Pa so as to have the extraction electrode. Then, a mask pattern was formed by vapor deposition so that the light emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.
  • Each gas barrier film formed up to the second electrode was moved again to a nitrogen atmosphere and cut to a prescribed size using an ultraviolet laser to produce an organic EL device.
  • Crimping conditions Crimping was performed at a temperature of 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.
  • a sealing member was bonded to the organic EL element to which the electrode lead (flexible printed circuit board) was connected using a commercially available roll laminating apparatus to produce an organic EL element.
  • PET polyethylene terephthalate
  • PET polyethylene terephthalate
  • dry lamination adhesive two-component reaction type urethane adhesive
  • thermosetting adhesive was uniformly applied to the aluminum surface with a thickness of 20 ⁇ m along the adhesive surface (glossy surface) of the aluminum foil.
  • thermosetting adhesive The following epoxy adhesive was used as the thermosetting adhesive.
  • the sealing substrate is closely attached and arranged so as to cover the joint portion of the take-out electrode and the electrode lead, and pressure bonding conditions using the pressure roll: pressure roll temperature 120 ° C., pressure 0.5 MPa, apparatus speed 0. Adherent sealing was performed at 3 m / min.
  • Element deterioration tolerance rate (area of black spots generated in elements not subjected to accelerated deterioration processing / area of black spots generated in elements subjected to accelerated deterioration processing) ⁇ 100 (%)
  • the element deterioration resistance rate is 20% or more and less than 60%.
  • X The element deterioration resistance rate is less than 20%.
  • This evaluation was performed on both the sample that was not subjected to hot water treatment (immediately) and the sample that was subjected to hot water treatment (after hot water treatment).
  • Tables 2 to 4 below show the structures and evaluation results of the gas barrier films of each Example and each Comparative Example.
  • the gas barrier films of the present invention produced according to the examples have higher gas barrier properties than those of the prior art, and are very stable even after being stored under high temperature and high humidity conditions. High, maintaining high gas barrier properties and excellent bending resistance. Moreover, since the gas barrier property is maintained even under severe wet heat environment, it has an effect of reducing the occurrence of dark spots by using it as a sealing film for organic EL elements.
  • the gas barrier film of Comparative Example 1 having a gas barrier layer only on one side of the substrate or the gas barrier films of Comparative Examples 2 to 4 having no gas barrier layer containing an additive element are used in a high-temperature and high-humidity environment.
  • the film exhibits a high retention rate of 70% or higher. Furthermore, even after being exposed to a high temperature and high humidity environment, high bending resistance was exhibited.
  • Example 1 the gas barrier film of Example 3 having the gas barrier layer containing the additive element on both sides of the substrate was Example 1 in which the gas barrier layer containing the additive element was provided only on one side. Compared with 2, the retention rate was improved.
  • Examples 8 to 26 by providing the vapor deposition gas barrier layer adjacent to the gas barrier layer prepared using polysilazane, more excellent gas barrier properties, bending resistance, and stability in a high temperature and high humidity environment.
  • the gas barrier film which has this is obtained, and the performance outstanding as a sealing film of an organic EL element is shown.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Chemical Vapour Deposition (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention porte sur un film de barrière contre des gaz avec des propriétés de barrière contre des gaz élevées, et une excellente stabilité dans des environnements à température élevée et humidité élevée. A cet effet, l'invention porte sur un film de barrière contre des gaz, lequel film a au moins une couche de barrière contre des gaz, chacune sur les deux côtés d'un substrat, la couche de barrière contre des gaz étant obtenue par l'application d'un revêtement liquide contenant un polysilazane de façon à obtenir une couche de film de revêtement, puis la réalisation d'un processus de modification par irradiation de la couche de film de revêtement avec un faisceau d'énergie active, au moins l'une des couches de barrière contre des gaz contenant au moins un élément sélectionné parmi le groupe comprenant les éléments du groupe 2, du groupe 13 et du groupe 14 de la table périodique de forme longue (à l'exclusion du silicium et du carbone).
PCT/JP2015/058684 2014-03-24 2015-03-23 Film de barrière contre des gaz, procédé pour sa fabrication, et dispositif électronique l'utilisant WO2015146886A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017071093A (ja) * 2015-10-06 2017-04-13 コニカミノルタ株式会社 ガスバリアーフィルム、ガスバリアーフィルムの製造方法及び電子デバイス
JP2018154012A (ja) * 2017-03-17 2018-10-04 コニカミノルタ株式会社 機能性フィルム、及び、電子デバイスの製造方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10279362A (ja) * 1997-03-31 1998-10-20 Tonen Corp ＳｉＯ２系セラミックス膜の形成方法
JP2012056101A (ja) * 2010-09-06 2012-03-22 Konica Minolta Holdings Inc ガスバリアフィルムおよびそれを用いた電子機器デバイス
JP2012148416A (ja) * 2011-01-17 2012-08-09 Mitsui Chemicals Inc 積層体およびその製造方法
JP2013188942A (ja) * 2012-03-14 2013-09-26 Konica Minolta Inc 水蒸気バリアーフィルムの製造方法、水蒸気バリアーフィルム及び電子機器
WO2013161894A1 (fr) * 2012-04-25 2013-10-31 コニカミノルタ株式会社 Film barrière au gaz, substrat pour dispositif électronique, et dispositif électronique
JP2013226673A (ja) * 2012-04-24 2013-11-07 Konica Minolta Inc ガスバリア性フィルムおよびその製造方法、並びに前記ガスバリア性フィルムを含む電子デバイス
JP2013226732A (ja) * 2012-04-26 2013-11-07 Konica Minolta Inc ガスバリアフィルムの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10279362A (ja) * 1997-03-31 1998-10-20 Tonen Corp ＳｉＯ２系セラミックス膜の形成方法
JP2012056101A (ja) * 2010-09-06 2012-03-22 Konica Minolta Holdings Inc ガスバリアフィルムおよびそれを用いた電子機器デバイス
JP2012148416A (ja) * 2011-01-17 2012-08-09 Mitsui Chemicals Inc 積層体およびその製造方法
JP2013188942A (ja) * 2012-03-14 2013-09-26 Konica Minolta Inc 水蒸気バリアーフィルムの製造方法、水蒸気バリアーフィルム及び電子機器
JP2013226673A (ja) * 2012-04-24 2013-11-07 Konica Minolta Inc ガスバリア性フィルムおよびその製造方法、並びに前記ガスバリア性フィルムを含む電子デバイス
WO2013161894A1 (fr) * 2012-04-25 2013-10-31 コニカミノルタ株式会社 Film barrière au gaz, substrat pour dispositif électronique, et dispositif électronique
JP2013226732A (ja) * 2012-04-26 2013-11-07 Konica Minolta Inc ガスバリアフィルムの製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017071093A (ja) * 2015-10-06 2017-04-13 コニカミノルタ株式会社 ガスバリアーフィルム、ガスバリアーフィルムの製造方法及び電子デバイス
JP2018154012A (ja) * 2017-03-17 2018-10-04 コニカミノルタ株式会社 機能性フィルム、及び、電子デバイスの製造方法

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