JP2011194766A - Gas barrier film and organic electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film having very high barrier performance excellent UV-cutting capability and adhesion and an organic electronic device using the film, e.g. an organic photoelectric conversion element or an organic EL element.SOLUTION: In the gas barrier film and the organic electronic device, each of gas barrier layers, as a gas barrier film, on both sides of a resin substrate consists of a UV-cutting layer and at least one of a silicon oxide layer and a silicon oxide nitride layer, formed in this order.

Description

  The present invention mainly relates to a gas barrier property used for a display material such as a package of an electronic device or the like, or a plastic substrate such as an organic photoelectric conversion element (organic solar cell), an organic electroluminescence element (hereinafter also referred to as an organic EL element), or a liquid crystal. The present invention relates to a film (hereinafter also referred to as a gas barrier film) and organic electronic devices such as an organic photoelectric conversion element and an organic EL element having the gas barrier film.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging of goods and foods that require blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent alteration of products such as industrial products and pharmaceuticals.

  In addition to packaging applications, they are used in liquid crystal display elements, photoelectric conversion elements (solar cells), organic electroluminescence (organic EL) substrates, and the like.

  Aluminum foil is widely used as a packaging material in such fields, but disposal after use has become a problem, and it is basically opaque and the contents can be confirmed from the outside. In addition, the solar cell material requires transparency and cannot be applied.

  In particular, transparent substrates that have been applied to liquid crystal display elements, organic EL elements, photoelectric conversion elements, etc. can be produced in roll-to-roll in addition to the demands for weight reduction and size increase in recent years. In addition to high demands such as long-term reliability, high degree of freedom of shape, and ability to display curved surfaces, film substrates such as transparent plastics are used instead of glass substrates that are heavy, fragile and difficult to increase in area. Has begun to be adopted.

  However, a film substrate such as a transparent plastic has a problem that gas barrier properties are inferior to glass. For example, when used as a material for an organic photoelectric conversion element, if a substrate having inferior gas barrier properties is used, water vapor or air penetrates and the organic film deteriorates, which becomes a factor that impairs photoelectric conversion efficiency or durability.

  In addition, when a polymer substrate is used as a substrate for an electronic device, oxygen and water molecules permeate the polymer substrate and penetrate and diffuse into the electronic device, thereby degrading the device. Cause the problem that the degree of vacuum required in can not be maintained.

In order to solve such problems, it is known to form a metal oxide thin film on a film substrate to form a gas barrier film substrate. Recently, as a barrier film made of an organic substance that is weak against moisture, such as an organic EL element, barrier performance is required such that the water vapor transmission rate is less than 1 × 10 ⁻³ g / m ² · day.

  In order to solve such a problem, a technique of applying a polysilazane to a resin substrate and laminating a gas barrier film by ultraviolet irradiation (for example, refer to Patent Document 1), is used by laminating a barrier layer. Silicon dioxide that cannot be absorbed cannot absorb ultraviolet rays, and ultraviolet rays that degrade organic substances cause deterioration of the film substrate. In addition, ultraviolet rays that have passed through the film substrate cause deterioration of the liquid crystal display element, organic EL element, and photoelectric conversion element, which is a serious problem.

A technique of an optical film in which an ultraviolet absorbing layer and a hard coat layer are sequentially provided on a film substrate is disclosed (for example, see Patent Document 2). According to this method, ultraviolet rays can be cut, but because of the hard coat layer, the water vapor transmission rate is 5 to 150 g / m ² · day, and it cannot be said to be a barrier film of organic matter that is weak against moisture such as recent organic EL elements. .

Moreover, the technique which laminates | stacks an ultraviolet absorption layer and a gas barrier layer on a film substrate is disclosed (for example, refer patent document 3). According to this method, ultraviolet rays are cut and gas barrier properties are provided, but since the gas barrier layer is on one side, it cannot be said to be a barrier film of organic matter that is weak to moisture such as 5 ml / m ² · day and recent organic EL devices. .

JP 2009-255040 A JP 2008-233882 A JP 2005-153167 A

  An object of the present invention is to provide a barrier film excellent in extremely high barrier performance, UV cut property and adhesion, and to provide an organic electronic device such as an organic photoelectric conversion element and an organic EL element using the same. It is in.

  The above object of the present invention can be achieved by the following configuration.

  1. As a gas barrier film, a gas barrier layer is provided on both surfaces of a resin substrate, each including an ultraviolet cut layer and at least one layer selected from a silicon oxide layer and a silicon oxynitride layer in this order. Gas barrier film.

  2. 2. The silicon oxide layer or the silicon oxynitride layer is produced by applying a solution of a silicon compound having a polysilazane skeleton, and then irradiating with vacuum ultraviolet light having a wavelength of 200 nm or less. Gas barrier film.

  3. 3. The gas barrier film as described in 2 above, wherein the irradiation with vacuum ultraviolet light is front and back double-sided irradiation.

  4). 4. The gas barrier film as described in any one of 1 to 3 above, wherein the ultraviolet cut layer contains a particulate metal oxide as an ultraviolet absorber.

  5. 5. An organic electronic device using the gas barrier film according to any one of 1 to 4 above.

  According to the present invention, it is possible to provide a barrier film excellent in extremely high barrier performance, UV cut property and adhesion, and to provide an organic electronic device such as an organic photoelectric conversion element and an organic EL element using the same. Is possible.

It is a schematic sectional drawing of the example of the organic electronic device of this invention.

  The present invention is a film configuration in which an ultraviolet cut layer and a gas barrier layer are provided in this order on both surfaces of a resin substrate. By having the barrier layers on both sides, the water vapor transmission rate can be lowered. When ultraviolet light irradiation is applied to both sides in forming the barrier layer, the substrate resin is deteriorated by the ultraviolet light, which causes a problem.In the present invention, the problem is solved by sandwiching the ultraviolet cut layer between the substrate resin and the barrier layer. Settled. Surprisingly, when ultraviolet rays were irradiated only from the front side of the barrier layer, the lower part of the barrier layer was difficult to be modified, and there was a problem in adhesion to the lower layer. When the barrier layer was irradiated with ultraviolet rays, the inside of the barrier layer was uniformly modified, and the adhesion and water vapor transmission rate were greatly improved.

  Hereinafter, the present invention, its components, and embodiments for carrying out the present invention will be described in detail.

<Gas-barrier a-film>
The gas barrier film of the present invention can be obtained by forming a gas barrier layer on both surfaces by applying a liquid containing an ultraviolet absorber on both surfaces of a resin substrate and a liquid containing a silicon compound on the liquid substrate.

As the gas barrier property of the gas barrier film of the present invention, the water vapor transmission rate (water vapor transmission rate: 25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured according to the JIS K 7129B method is 10 ⁻³ g. / (M ² · 24h) or less, more preferably 10 ⁻⁴ g / (m ² · 24 h) or less, and particularly preferably 10 ⁻⁵ g / (m ² · 24 h) or less.

The oxygen permeability (oxygen permeability) measured by a method according to JIS K 7126-1987 is preferably 0.01 ml / (m ² · 0.1 MPa / day) or less, more preferably 0.8. 001 ml / (m ² · 0.1 MPa / day) or less.

(Layer structure of gas barrier film)
The present invention has a film configuration in which an ultraviolet cut layer and a gas barrier layer are provided in this order on both surfaces of a resin substrate. The gas barrier layer may be a single layer, or two or three layers. A stress relaxation layer may be sandwiched between the gas barrier layers.

  In the case of a single layer or stacked layers, the thickness of one gas barrier layer is preferably 30 nm to 1000 nm, more preferably 30 nm to 500 nm, particularly 90 nm to 500 nm. When it is 30 nm or more, the film thickness uniformity is good and the gas barrier performance is excellent. When the thickness is 1000 nm or less, cracks due to bending rapidly become extremely small, the internal stress during film formation only increases, and the generation of defects can be prevented.

<UV cut layer>
The ultraviolet cut layer used in the present invention prevents deterioration due to ultraviolet rays by adding a substance that absorbs light in the region of 200 to 340 nm. The transmittance in the visible light region is preferably high.

  The ultraviolet absorber used in the present invention is composed of a metal oxide and an organic ultraviolet absorbing compound from the viewpoint of adhesion between the ultraviolet cut layer and the resin substrate having an alicyclic structure and adhesion between the ultraviolet cut layer and the gas barrier layer. preferable. Particularly preferred is a metal oxide. As the binder for the ultraviolet cut layer, a resin binder is preferable.

(Production method of UV cut layer)
The ultraviolet cut layer is formed by preparing a coating solution in which an ultraviolet absorber is dissolved or dispersed in a resin binder. When the resin binder is not a solution, the coating solution is prepared by dissolving the resin binder in a solution obtained by dissolving or dispersing the ultraviolet absorber in a solvent. The coating liquid is preferably formed by applying a heat treatment after coating the resin base material. The coating method is not particularly limited, and examples thereof include a bar coater method, a curtain coating method, a dipping method, an air knife method, a slide coating method, a hopper coating method, a reverse roll coating method, a gravure coating method, and an extrusion coating method. A known method can be used. Of these, the slide coating method and the extrusion coating method are more preferable. These coating methods have been described for single-sided coating of a resin base material, but the same applies to double-sided coating.

  In the present invention, the thickness of the coating film is preferably selected according to the purpose, but it is preferably 0.01 μm or more and 1000 μm or less, more preferably 0.03 μm or more and 100 μm or less in terms of the film thickness after drying. preferable.

  In addition, content of the said solvent can be adjusted with conditions changes, such as temperature conditions in the drying process after an application | coating process. The content of the solvent can be measured by gas chromatography under conditions suitable for detecting the contained solvent.

  The ultraviolet cut layer can be fixed by applying to a resin base material and drying, and the effect of the present invention can be confirmed, but as a method of fixing to the resin base material as necessary, an ultraviolet ray and electron beam curing method and A thermosetting method is used. If necessary, add a photopolymerization initiator and a thermal polymerization initiator to the UV-cutting layer coating solution, apply it on the resin substrate, and then fix it to the resin substrate by irradiating it with heat, ultraviolet rays, and an electron beam. What is necessary is just to make it.

  Examples of the photopolymerization initiator used here include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine. Carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) Photoradical initiation of 2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. Etc. The. On the other hand, when fixing to a resin base material with the thermosetting method, thermal polymerization initiators, such as a thermal radical generator, may be added to the said ultraviolet cut layer coating liquid as needed. Examples of the thermal polymerization initiator used here include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile), organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis (t-butylperoxy) cyclohexane, etc. It is done.

  Even in the absence of an initiator, it can be fixed by activating the polymer surface by a corona discharge treatment, a plasma discharge treatment or the like on the resin base material to which the ultraviolet cut layer coating solution is applied.

(Fine particle metal oxide)
The ultraviolet absorber used in the present invention is preferably a particulate metal oxide. The fine particle metal oxide refers to those having an average primary particle diameter in the range of 1 to 100 nm and having an ultraviolet protection effect, and examples thereof include fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and fine particle iron oxide. One or more, preferably two or more of these particulate metal oxides may be combined. Further, the shape of the fine particle metal oxide is not particularly limited such as spherical, needle-like, rod-like, spindle-like, indefinite shape, or plate shape, and the crystal form is not particularly limited such as amorphous, rutile type, or anatase type.

  Furthermore, these fine particle metal oxides are conventionally known surface treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, N-acylation. It is preferably surface-treated in advance by lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, etc., particularly silicone, silane, fluorine compound, amino acid compound, It is preferable that the water-repellent treatment is performed with one or more surface treatment agents selected from metal soaps.

  Examples of silicone treatment include coating and heat treatment of methyl hydrogen polysiloxane, examples of silane include alkylsilane treatment, and examples of fluorine compounds include perfluoroalkyl phosphate ester, perfluoropolyether, perfluoroalkyl silicone, perfluoro Alkyl / polyether co-modified silicones, perfluoroalkylsilanes, and the like are mentioned. Examples of amino acid compounds include N-lauroyl-L-lysine, and examples of metal soaps include aluminum stearate.

  As a commercial product of fine particle oxide, for example, as fine particle zinc oxide, “FINEX-25”, “FINEX-50”, “FINEX-75” {above, Sakai Chemical Industry Co., Ltd.}; “MZ500” series, “MZ700” series {above, Teika Co., Ltd.} “ZnO-350” {above, Sumitomo Osaka Cement Co., Ltd.}, “TYN” series {above, Toyo Ink Co., Ltd.} and the like.

  Fine titanium oxide includes “TTO-55, 51, S, M, D” series {above, Ishihara Sangyo Co., Ltd.}; “JR” series, “JA” series {above, Teika Co., Ltd.}, “TYN” "Series {above, Toyo Ink Co., Ltd.}" and the like. The fine cerium oxide includes high-purity cerium oxide sold by Nikki Co., Ltd. or Seimi Chemical Co., Ltd. Of these, titanium oxide and zinc oxide are particularly preferable.

  The average primary particle diameter or average primary short axis particle diameter of titanium oxide used in the present invention is preferably 1 to 45 nm, more preferably 3 to 40 nm, still more preferably 5 to 30 nm. Here, the “average primary particle diameter” is an average value of sphere equivalent diameters when the primary particle shape is spherical or almost spherical, and the “average primary short axis particle diameter” is a columnar primary particle shape. Or it is the average value of the short axis particle diameter in the case of a spindle shape. In the case of spindle-shaped or cylindrical (preferably spindle-shaped) particles, the major axis diameter is preferably 3 to 200 nm, more preferably 5 to 150 nm, and still more preferably 10 to 100 nm. Further, the long axis diameter / short axis diameter ratio (hereinafter referred to as aspect ratio) is preferably 2 to 10, more preferably 2.5 to 8, and further preferably 3 to 6.

Although the coating amount of the ultraviolet absorber of the present invention can be selected according to the purpose, it is preferably used so as to be 0.01 to 20 g / m ² . When the amount used is large, the absorption of ultraviolet rays increases, and when the amount is not more than the upper limit value, the decrease in transparency can be suppressed. A more preferable amount is 0.02 to 10 g / m ² , and further preferably 0.05 to ² g / m ² .

(Organic UV protection compound)
In the present invention, an organic ultraviolet ray preventing compound may be used as the ultraviolet absorber. As the organic ultraviolet ray preventing compound, a benzotriazole type, a triazine type or the like can be used. Examples of the benzotriazole type include 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) phenol]], 2- (2H- Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- ( tert-butyl) phenol and the like. Examples of the triazine type include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.

  Commercially available products include Ciba Japan's TINUVIN series and ADEKA's Adekastab series.

  Further, a HALS agent having a function of preventing deterioration equivalent to that of the ultraviolet light inhibitor may be used as the ultraviolet light absorber, and a hindered amine or the like can be used as the HALS agent. Examples of hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5. -Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] Dibutylamine, 1,3,5-triazine, N, N-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine, N- (2,2,6, 6-tetramethyl-4-piperidyl) butylamine polycondensate, etc. Examples of the metal deactivator include 2,3-bis [[3- [3,5-di-tert-butyl-4. -Hydroxyphenyl] Pioniru]] can be mentioned propionohydrazide like.

  Commercially available products include Ciba Japan's TINUVIN series and ADEKA's Adekastab series.

  Since the organic ultraviolet protection compound itself is an organic substance, it is deteriorated by ultraviolet rays. For this reason, an inorganic particulate metal oxide is more preferable as an ultraviolet absorber.

(Resin binder)
Examples of the resin binder used in the ultraviolet cut layer used in the present invention include a polymerization type thermoplastic resin or a condensation type thermoplastic resin.

  Examples of the polymerization type thermoplastic resin include (meth) acrylic resin, styrene resin, polyalkylene resin and the like.

  Condensation type thermoplastic resins include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, aromatic carboxylic acids such as 4,4-diphenyldicarboxylic acid, or esters thereof with ethylene glycol, propylene glycol, 1,4- Examples thereof include conventionally known polyester resins that can be obtained by condensation polymerization with an aliphatic glycol such as butanediol, diethylene glycol, 1,4-cyclohexanedimethanol and the like.

  Typical examples include polyester resins such as polyethylene terephthalate and polybutylene terephthalate.

(Method of mixing UV absorber and resin binder)
The ultraviolet absorber used in the present invention is mixed with a resin binder by a known technique. Usually, a resin binder is used as a solution, and the ultraviolet absorber is mixed while stirring the solution using a stirrer. The dispersant and other additives that may be added at the time of stirring are added and stirred before or after the introduction of the ultraviolet absorber as necessary. When the viscosity of the resin binder is high or solid, a solvent may be added as appropriate.

  If dispersion is not easy, an ultraviolet absorber, a resin binder, and a solvent are added, and they are mixed uniformly using a high shear mixer such as a Henschel mixer or a super mixer.

  The solvent is not particularly limited, and ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate and butyl acetate, aromatic compounds such as toluene and xylene, diethyl ether, tetrahydrofuran and the like And ethers such as methanol, ethanol, isopropanol and the like. Dissolve resin binders such as aromatic solvents such as toluene and xylene, chlorinated solvents such as dichloromethane and carbon tetrachloride, hydrocarbon solvents such as n-hexane and cyclohexane, and ketone solvents such as cyclohexanone and methyl isobutyl ketone. Use a solvent that swells.

  The concentration of the UV absorber in the UV cut layer coating solution varies depending on the film thickness of the target UV cut layer and the pot life of the coating solution, but is about 0.2 to 50% by mass of the resin binder. Preferably, it is 5-50 mass%.

(Method for producing gas barrier layer)
In the method for producing a gas barrier film of the present invention, a coating liquid containing a polysilazane compound is coated and dried on an ultraviolet cut layer, and then oxidized by ultraviolet irradiation in a nitrogen atmosphere containing oxygen and water vapor to produce a gas barrier layer. To do.

  Any appropriate method can be adopted as a method for applying the polysilazane compound. 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. By these methods, both sides may be applied simultaneously, or one side may be applied.

The “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, and is composed of Si—N, Si—H, N—H, etc., SiO ₂ , Si ₃ N ₄ and both intermediate solid solutions SiO _x N _y. Such as a ceramic precursor inorganic polymer.

  In order not to damage the film base material, it is preferable to use ceramics modified at a relatively low temperature and modified to silica as described in JP-A-8-112879, which is represented by the following general formula (1). What can be preferably used.

In the formula, R ¹ , R ² and R ^{3 each} represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. In perhydropolysilazane, all of R ¹ , R ² , and R ³ are hydrogen atoms, and in organopolysilazane, any of R ¹ , R ² , and R ³ is an alkyl group, alkenyl group, cycloalkyl group, aryl group, An alkylsilyl group, an alkylamino group or an alkoxy group; In the present invention, perhydropolysilazane in which all of R ¹ , R ² , and R ³ are hydrogen atoms is particularly preferred because of the denseness of the barrier film obtained.

  On the other hand, organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base substrate is improved and the ceramic made of polysilazane which is hard and brittle The film can be toughened, and there is an advantage that generation of cracks can be suppressed even when the (average) film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As another example of polysilazane which is ceramicized at a low temperature, silicon alkoxide-added polysilazane obtained by reacting silicon alkoxide with polysilazane of the above chemical formula 1 (Japanese Patent Laid-Open No. 5-238827), glycidol addition obtained by reacting glycidol Polysilazane (JP-A-6-122852), alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), metal carboxylate-added polysilazane obtained by reacting a metal carboxylate 6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (specialty) Kaihei 7-19 986 JP), and the like.

  As an organic solvent for preparing a liquid containing polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane. Specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of solvents may be mixed.

  The polysilazane concentration in the polysilazane-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the target silica film thickness and the pot life of the coating solution.

  The organic polysilazane may be a derivative in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like. Adhesion with the base substrate is improved by having an alkyl group, particularly the methyl group with the lowest molecular weight, and it is possible to impart toughness to a hard and brittle silica film, and even when the film thickness is increased, cracks are generated. Is suppressed.

  In order to promote the conversion to a silicon oxide compound, an amine or metal catalyst may be added. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. Among these, it is most preferable to use NN120 and NN110 made of perhydropolysilazane containing no catalyst in order to form a denser barrier layer having a higher barrier property.

  The coated film is preferably annealed to obtain a uniform dry film from which the solvent has been removed. The annealing temperature is preferably 60 ° C to 200 ° C, more preferably 70 ° C to 160 ° C. The annealing time is preferably about 5 seconds to 24 hours, more preferably about 10 seconds to 2 hours.

  As described above, by performing annealing in the above-described range before the conversion process following the next step, a uniform coating film can be stably obtained.

  The annealing may be performed at a constant temperature, the temperature may be changed stepwise, or the temperature may be continuously changed (temperature increase and / or temperature decrease). During annealing, it is preferable to adjust the humidity in order to stabilize the reaction, and is usually 30% RH to 90% RH, more preferably 40% RH to 80% RH.

<Reforming treatment>
As the oxidation treatment of polysilazane, steam oxidation and / or heat treatment (including drying treatment), treatment by ultraviolet irradiation, and the like are known.

  An ultraviolet irradiation treatment is preferably used in the present invention. By irradiating ultraviolet light in the presence of oxygen, active oxygen and ozone are generated, and the oxidation reaction can be further advanced.

  This active oxygen and ozone are very reactive.For example, when polysilazane is selected as the silicon compound, the polysilazane coating film that is a precursor of silicon oxide is directly oxidized without passing through silanol. A silicon oxide film with higher density and fewer defects is formed.

  Further, ozone may be generated from oxygen by a known method such as a discharge method at a portion different from the light irradiation portion for the shortage of reactive ozone, and introduced into the ultraviolet irradiation portion.

  The wavelength of the ultraviolet light irradiated at this time is not particularly limited, but the wavelength of the ultraviolet light is preferably 100 nm to 450 nm, and more preferably irradiated with ultraviolet light of about 150 nm to 300 nm.

As the light source, a low-pressure mercury lamp, a deuterium lamp, a Xe excimer lamp, a metal halide lamp, an excimer laser, or the like can be used. As the output of the lamp 400W～30kW, more preferably preferably ^{10mJ / cm 2 ~5000mJ / cm 2} , 100mJ / cm 2 ~2000mJ / cm 2 as ^{100mW / cm 2 ~100kW / cm 2} , irradiation energy as illuminance . Moreover, the illuminance at the time of ultraviolet irradiation is preferably 1 mW / cm ^{2 to} 10 W / cm ² . By irradiating the polysilazane coating film with ultraviolet rays in an oxidizing gas atmosphere, the polysilazane is converted into a high-density silicon oxide film, that is, a high-density silica film. Control is possible by irradiation time and wavelength (energy density of light), and it is possible to select appropriately such as properly using different types of lamps in order to obtain a desired film structure. In addition to continuous irradiation, multiple irradiations may be performed, and multiple irradiations may be so-called pulse irradiation in a short time.

  In addition, heating the coating film simultaneously with ultraviolet irradiation is also preferably used to promote a reaction (also referred to as an oxidation reaction or a conversion treatment). The heating method is such that the substrate is brought into contact with a heating element such as a heat block, the coating film is heated by heat conduction, the atmosphere is heated by an external heater such as a resistance wire, and infrared light such as an IR heater is applied. Although the method used etc. are mentioned, it does not specifically limit. You may select suitably the method which can maintain the smoothness of a coating film.

  As temperature to heat, the range of 50 to 200 degreeC is preferable, More preferably, it is the range of 80 to 150 degreeC, As a heating time, the range of 1 second-10 hours is preferable, More preferably, it is 10 seconds-1 Heating for a range of time.

  Among these, it is preferable to perform the treatment by irradiation with vacuum ultraviolet rays having a wavelength component of 200 nm or less having a higher photon energy. This is because if the energy is small, the effect of polysilazane is insufficient and the barrier property is lowered.

<Treatment by irradiation with vacuum ultraviolet rays having a wavelength component of 200 nm or less>
In the present invention, a preferable method includes a modification treatment by irradiation with vacuum ultraviolet rays. The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, which is larger than the interatomic bonding force in the compound, and the oxidation reaction by active oxygen or ozone while directly cleaving the bonds of atoms by the action of only photons called photon processes. Is a method of forming a film at a relatively low temperature.

  In particular, in the treatment of a polysilazane film, which is a preferred method of the present invention, when a single layer is applied and then an excimer irradiation treatment is performed while keeping the atmosphere constant, two layers having different compositions in the thickness direction of the polysilazane layer are modified. A film is formed. Although the mechanism is not clear, the fact that the density of the modified layer near the surface is high, and the film thickness of the modified layer near the surface changes depending on the processing time. The direct cleavage of the silazane compound and the surface oxidation reaction with active oxygen and ozone generated in the gas phase proceed simultaneously, resulting in a difference in the reforming rate between the surface side and the inside of the reforming process. It is estimated that a quality layer is formed.

  As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

1. Excimer light emission is called an inert gas because atoms of rare gases such as Xe, Kr, Ar, and Ne do not form a molecule by chemically bonding. However, a rare gas atom (excited atom) that has gained energy by discharge or the like can combine with other atoms to form a molecule. When the rare gas is xenon, e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. In addition, since the luminous efficiency is higher than that of other rare gases and a lamp for irradiating a large area can be made of quartz glass, a Xe excimer lamp can be preferably used.

  From the standpoint of energy alone, Ar excimer light (wavelength 126 nm) is the highest, and a high polysilazane layer reforming effect is expected. However, since Ar excimer light becomes so large that absorption by quartz glass cannot be ignored, it is necessary to use calcium carbonate glass instead of silicon dioxide glass. However, the fact is that calcium carbonate glass is very fragile and difficult to manufacture as a lamp that irradiates a large area.

  The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane film can be modified in a short time. Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

  According to the study by the present inventors, the oxygen concentration is preferably 0.001 to 5% as the environment during the excimer irradiation treatment. Furthermore, if it is 0.01 to 3%, performance is stable and preferable. When the oxygen concentration exceeds 5%, energy is used to generate active oxygen rather than bond breakage, and even if it is lowered to 0.001% or less, the excimer light irradiation efficiency hardly changes, and modification Since the efficiency and the composition controllability of the film do not change, an extra atmosphere replacement time is required, so that it is difficult to improve productivity. As for the stage temperature, it is preferable to apply heat to advance the reaction. In this case, the temperature is preferably 50 ° C. or higher and the substrate Tg + 80 ° C. or lower, and the substrate Tg + 30 ° C. or lower is more preferable because the reactivity is improved without damaging the substrate.

  In addition, when excimer irradiation is used, it is possible to simultaneously manufacture a three-layer structure of one unit. As described above, it is possible to modify only near the surface by excimer irradiation, and by adjusting the reaction time in a low oxygen concentration atmosphere (preferably in a nitrogen atmosphere) by utilizing the property, N It is possible to increase the content rate. Furthermore, after processing under low oxygen conditions, it is possible to form a layer with a high oxygen ratio on the surface portion by introducing oxygen within the above-mentioned range in continuous processing and adjusting the processing time. The inventors have found.

  In principle, it is possible to form four or more layers with different compositions in a coating film formed by one application by controlling the atmosphere and time while irradiating the film applied to a relatively thick film while excimer irradiation. Although it is possible, a thick film exceeding the above-mentioned range is liable to generate defects, so that the gas barrier function is difficult to develop. Further, even if each layer is formed at 5 nm, for example, to form a laminated structure of 6 layers or more, each layer Since the film thickness is too thin, the intended function of each layer does not work effectively. From such a viewpoint, the thickness of the barrier layer is preferably in the range of 5 nm to 100 nm, more preferably about 10 nm to 60 nm.

  The film thickness of each layer is measured from this image because each layer can be detected as a difference in image density by cross-sectional observation with a transmission electron microscope. The ratio of oxygen atoms and nitrogen atoms in each layer is calculated from the composition ratio profile data in the depth direction by X-ray photoelectron spectroscopy (XPS) while cutting the gas barrier film from the film surface to the depth direction by Ar sputtering. Is possible.

<High irradiation intensity treatment and maximum irradiation intensity>
If the irradiation intensity is high, the probability that the photons and chemical bonds in the polysilazane collide increases, and the modification reaction can be shortened. Further, since the number of photons penetrating to the inside increases, the modified film thickness can be increased and / or the film quality can be improved (densification). However, if the irradiation time is too long, the flatness may be deteriorated and other materials of the barrier film may be damaged. In general, the progress of the reaction is considered by the integrated light quantity expressed by the product of irradiation intensity and irradiation time. The absolute value of intensity may be important.

Therefore, in this invention, it is preferable to perform the modification process which gives the maximum irradiation intensity of 100 to 200 mW / cm ² at least once in the vacuum ultraviolet irradiation process. By setting it to 100 mW / cm ² or more, the processing time can be shortened without causing rapid deterioration of the reforming efficiency, and by setting it to 200 mW / cm ² or less, gas barrier performance can be efficiently provided. (Even when irradiation exceeds 200 mW / cm ² , the increase in gas barrier properties slows down), and not only damage to the substrate but also damage to the lamp and other members of the lamp unit, and the life of the lamp itself Can be extended.

<Vacuum ultraviolet irradiation time>
Although the irradiation time can be arbitrarily set, the irradiation time in the high illuminance process is preferably 0.1 second to 3 minutes from the viewpoint of substrate damage and film defect generation and from the viewpoint of reducing variation in gas barrier performance. More preferably, it is 0.5 second to 1 minute.

<Oxygen concentration during vacuum ultraviolet light irradiation>
In the present invention, the oxygen concentration at the time of irradiation with vacuum ultraviolet light is preferably 10 ppm to 50000 ppm (5%). More preferably, it is 1000 ppm to 30000 ppm (3%). If the oxygen concentration is higher than the above concentration range, a gas barrier film containing excessive oxygen is formed, and the gas barrier property is deteriorated. If the oxygen concentration is lower than the above range, the replacement time with the atmosphere will be longer and the productivity will be reduced.At the same time, if continuous production such as roll-to-roll is performed, the web will be transported into the vacuum ultraviolet irradiation chamber. The amount of air to be entrained (including oxygen) increases, and the oxygen concentration cannot be adjusted unless a large flow rate of gas is passed.

  According to the inventors' investigation, in the polysilazane-containing coating film, oxygen and a small amount of water are mixed at the time of application, and there are also adsorbed oxygen and adsorbed water on the support other than the coating film, and dare in the irradiation chamber. It has been found that there are enough oxygen sources to supply oxygen required for the reforming reaction without introducing oxygen. Rather, when irradiation with vacuum ultraviolet light is performed in an atmosphere containing a large amount of oxygen gas (5 to 10% level), the gas barrier film after the modification has an excessive oxygen structure, and the gas barrier properties deteriorate. Further, as described above, the 172 nm vacuum ultraviolet light is absorbed by oxygen and the amount of light at 172 nm reaching the film surface is reduced, thereby reducing the efficiency of the light treatment. That is, at the time of vacuum ultraviolet light irradiation, it is preferable to perform the modification treatment in a state where the vacuum ultraviolet light efficiently reaches the coating film in a state where the oxygen concentration is as low as possible.

  A gas other than oxygen at the time of irradiation with vacuum ultraviolet light is preferably a dry inert gas, and particularly dry nitrogen gas is preferred from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

<Irradiation method on both sides>
The gas barrier layer applied to both surfaces of the resin base material may be modified simultaneously on both sides according to the ultraviolet irradiation conditions, or may be modified on each side.

(Resin substrate)
The resin substrate is not particularly limited as long as it is formed of an organic material that can hold the barrier layer and the ultraviolet cut layer.

  For example, acrylic ester, methacrylate 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, polyether imide, triacetyl cellulose (TAC), diacetyl cellulose (DAC), cellose acetate propio Heat-resistant transparent film (product name Sila-DE) based on each resin substrate such as nate (CAP), or fluororesin, or silsesquioxane having an organic-inorganic hybrid structure , Manufactured by Chisso Corporation), and further can be mentioned a resin substrate or the like formed by laminating the plastic two or more layers. In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), and the like are preferably used. Also, optical transparency, heat resistance, inorganic layer and In terms of adhesion, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used. The thickness of the substrate is preferably about 5 to 500 μm, more preferably 25 to 250 μm. In view of the case where the barrier film of the present invention is used as a light emitting device, the glass transition temperature (Tg) is preferably 100 ° C. or higher. Moreover, it is preferable that a heat shrinkage rate is also low.

  Furthermore, the resin substrate according to the present invention is preferably transparent. Since the substrate is transparent and the layer formed on the substrate is also transparent, it becomes possible to make a transparent barrier film, so that it becomes possible to make a transparent substrate such as a solar cell or an organic EL element. It is.

  Further, the resin substrate using the above-described plastics may be an unstretched film or a stretched film.

  The resin substrate used in the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a plastic material using an extruder, extruding it with an annular die or a T-die, and rapidly cooling it. Further, an unstretched substrate is uniaxially stretched, a tenter-type sequential biaxial stretch, a tenter-type simultaneous biaxial stretch, a tubular-type simultaneous biaxial stretch, or the like, by a known method such as a substrate flow (vertical axis) direction or a substrate A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  Further, the resin substrate according to the present invention may be subjected to corona treatment.

(Stress relaxation layer)
In the present invention, a stress relaxation layer may be provided between the barrier layers for the purpose of relaxing the stress against bending of the barrier film. Such a stress relaxation layer is preferably formed by, for example, coating and drying a composition containing a photosensitive resin, followed by curing.

  The basic skeleton of the components constituting the stress relaxation layer is composed of carbon, hydrogen, oxygen, nitrogen, sulfur, etc., and when inorganic atoms such as silicon, titanium, aluminum, and zirconium are used as the basic skeleton, It is difficult to obtain the effect.

  Examples of the photosensitive resin for the stress relaxation layer include a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, and urethane acrylate. And a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  The composition of the photosensitive resin contains a photopolymerization initiator. As photopolymerization initiators, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino-acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin methyl Ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene ) Cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- ( o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, mihi -Ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride, Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide, Examples include a combination of a photoreducible dye such as eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more.

  The method for forming the stress relaxation layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method.

  In addition, regardless of the position of the stress relaxation layer, an appropriate resin or additive may be used in any stress relaxation layer in order to improve the film forming property and prevent the generation of pinholes in the film.

  As a solvent used when forming a stress relaxation layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, Terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dip Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, diethylene glycol Dialkyl ether, dipropylene glyco Le dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smoothness of the stress relaxation layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 30 nm or less. If it is larger than this range, it may be difficult to smooth the irregularities after applying the inorganic compound.

  The thickness of the stress relaxation layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the smoothness as a film having a stress relaxation layer sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of optical properties of the film.

  In addition, multiple layers of stress relaxation layers and gas barrier layers may be laminated alternately, and a material configuration or a layer configuration that does not cause cracks or local adhesion failure at the layer interface over time due to heat, humidity, and time. It is preferable to select.

<Use of gas barrier film>
The gas barrier film of the present invention can be used as various sealing materials and films.

  The gas barrier film of the present invention can be particularly useful for photoelectric conversion elements and EL elements. Since the gas barrier film of the present invention is transparent, when this gas barrier film is used as a support for a photoelectric conversion element, it can be configured to receive sunlight from this side, and when used for an EL element, Light emission efficiency is not deteriorated because light emission from the light source is not hindered.

(Organic electronic device configuration)
An example of the basic configuration of the organic electronic device of the present invention is shown in FIG.

  The organic electronic device 1 has a second electrode 5 on a substrate 6, an organic functional layer 4 on the second electrode 5, a first electrode 3 on the organic functional layer 4, The gas barrier film 2 of the present invention is provided on one electrode 3.

  Examples of the organic functional layer 4 include an organic light emitting layer, an organic photoelectric conversion layer, a liquid crystal polymer layer, and the like without any particular limitation. The present invention includes an organic light emitting layer in which the functional layer is a thin film and is a current-driven device, This is particularly effective when the layer includes an organic photoelectric conversion layer.

  That is, the barrier film of the present invention is preferably applied to an organic EL element or an organic photoelectric conversion element that requires the most barrier property among electronic devices.

(Sealing)
The case where the barrier film of the present invention is applied as an organic electronic device will be described.

  First, for example, in the case of an organic EL element, functional layers made of various organic compounds such as an anode layer / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode layer are prepared.

  The whole or upper part of the obtained organic EL element is sealed.

Examples of the sealing member include the barrier film of the present invention, polyethylene terephthalate, polycarbonate, polystyrene, nylon, polyvinyl chloride, fluororesin and other plastics, and composites thereof, glass, and the like. In particular, in the case of a resin film, a layer in which a gas barrier layer such as aluminum, aluminum oxide, silicon oxide, or silicon nitride is laminated can be used as in the case of a resin substrate. The gas barrier layer can be formed by sputtering, vapor deposition or the like on both surfaces or one surface of the sealing member before molding the sealing member, or may be formed on both surfaces or one surface of the sealing member after sealing by a similar method. . Also about this, oxygen permeability is 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) (1 atm is 1.01325 × 10 ⁵ Pa) or less, water vapor permeability (25 ± 0.5 ° C. , Relative humidity (90 ± 2)% RH) is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less.

<Packaging form>
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. In particular, when used as a sealing material for organic thin-film devices, it often causes defects due to dust (particles) adhering to the surface, and a protective sheet is stuck in a clean place to prevent the adhesion of dust. Is very effective. In addition, it is effective in preventing scratches on the gas barrier layer surface that enters during winding.

  Although it does not specifically limit as a protective sheet, The general "protective sheet" and the "release sheet" of the structure which provided the weak adhesive layer on the resin substrate about 100 micrometers or less in thickness can be used. .

  The measurement methods used above and the measurement methods used in the examples described below are described below.

<Measurement method>
<Thickness of each layer>
The film thickness of each layer was measured from the intensity of the image and the degree of electron beam damage by cross-sectional observation with a transmission electron microscope (TEM).

(TEM image of cross section in film thickness direction)
Cross-sectional TEM observation After observing the specimen with the following FIB processing apparatus, TEM observation is performed. At this time, if the sample is continuously irradiated with the electron beam, a contrast difference appears between the portion that is damaged by the electron beam and the portion that is not so, and can be calculated by measuring the region. The high density region on the modification treatment side is not easily damaged by electron beam, but the other part is damaged by electron beam damage and alteration is confirmed.

(FIB processing)
Device: SII SMI2050
Processed ions: (Ga 30 kV)
Sample thickness: 100 nm to 200 nm
(TEM observation)
Apparatus: JEOL JEM2000FX (acceleration voltage: 200 kV)
Electron beam irradiation time: 5 to 60 seconds <Measurement of water vapor transmission rate (WVTR)>
Various methods have been proposed for measuring the water vapor transmission rate according to the above-mentioned JIS K 7129B method. For example, the cup method, the wet and dry sensor method (Lassy method), and the infrared sensor method (mocon method) can be cited as representatives, but as the gas barrier properties improve, these methods may reach the measurement limit. The following method has also been proposed. The method for measuring the water vapor transmission rate is not particularly limited, but in the present invention, evaluation by the Ca method was performed.

(Water vapor permeability measurement method other than the above)
Ca method A method in which metal Ca is vapor-deposited on a gas barrier film and the phenomenon in which metal Ca is corroded by moisture that has permeated through the film. The water vapor transmission rate is calculated from the corrosion area and the time to reach the corrosion area.

Method proposed by MORESCO (December 8, 2009, NewsRelease)
A method of passing water vapor through a cold trap between a sample space under atmospheric pressure and a mass spectrometer in an ultra-high vacuum.

HTO method (US General Atomics)
A method of calculating water vapor transmission rate using tritium.

Method proposed by A-Star (Singapore) (WO05 / 95924)
A method of calculating a water vapor transmission rate from a change in electric resistance and a 1 / f fluctuation component inherent therein using a material (for example, Ca, Mg) whose electric resistance is changed by water vapor or oxygen as a sensor.

<Ca method used for evaluation of the present invention>
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
Production of cell for evaluating water vapor barrier property A part (12 mm) of a barrier film sample to be vapor-deposited before applying a transparent conductive film on a gas barrier layer surface of the barrier film sample using a vacuum vapor deposition apparatus (vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.) Other than 9 x 12 mm masks, metal calcium was vapor-deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays. In addition, in order to confirm the change in the gas barrier property before and after bending, a water vapor barrier property evaluation cell was similarly prepared for the barrier film which was not subjected to the bending treatment.

  The obtained sample with both sides sealed is stored at 60 ° C. and 90% RH under high temperature and high humidity for 100 hours. Based on the method described in Japanese Patent Application Laid-Open No. 2005-283561, the corrosion amount of metallic calcium is introduced into the cell. The amount of moisture permeated was calculated.

  In addition, in order to confirm that there is no permeation of water vapor other than from the barrier film surface, instead of the barrier film sample as a comparative sample, a sample in which metallic calcium was vapor-deposited using a quartz glass plate having a thickness of 0.2 mm, The same 60 ° C., 90% RH high temperature and high humidity storage was performed, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

(Measurement of light transmittance of film)
The total transmitted light amount with respect to the incident light amount of visible light was measured according to a spectrophotometer ASTM D-1003. The measurement results at 550 nm, 380 nm, and 360 nm are shown in Table 1 below.

<Retention rate of tensile strength and elongation>
Using a variable temperature tensile tester (“Shimadzu Autograph AGS-100D” manufactured by Shimadzu Corporation), a barrier film specimen cut to a width of 10 mm was subjected to conditions of 23 ° C., a distance between chucks of 50 mm, and a tensile speed of 200 mm / min. The tensile strength and elongation rate until pulling to break were determined. As a result of similarly obtaining the tensile strength and the elongation rate of the uncoated PET film, it was confirmed that there was no difference in the tensile strength (3 GPa) and the elongation rate (150%).

<Adhesion>
The cross-cut adhesion is evaluated according to the description of JIS K 5600 5.6 (2004 edition), 100 pieces of 1 mm square reaching the substrate through the ultraviolet absorption cut layer with a cutter knife from one side of the laminate. A grid-cut cut of 1mm is attached using a cutter guide with a 1mm interval, cellophane adhesive tape ("CT405AP-18" manufactured by Nichiban Co., Ltd .; 18mm width) is applied to the cut surface, and scraped from above with an eraser to completely rub the tape After making it adhere, it peeled off to the orthogonal | vertical direction and performed visually confirming how much an ultraviolet-ray absorption layer remained on the base-material surface.

  The number of peels in 100 pieces was examined and evaluated according to the following criteria.

○: The number of peels in the cross cut test is 10 or less Δ: The number of peels in the cross cut test is 11 to 20 ×: The number of peels in the cross cut test is 21 or more <Bending treatment>
A bending process in which the gas barrier film thus produced is bent once to make the gas barrier layer bend once so that the surface of one side of the gas barrier layer is on the inside, and once on the outside so that the curvature is 50 mmφ, and is repeated 100 times. Was given.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.

Example 1: Comparison with gas barrier film <Production of Sample 1-1>
(Resin substrate)
As the resin substrate, a 50 μm thick polyester film (A4300, manufactured by Toyobo Co., Ltd.) that was easily bonded on both sides was used.

(Formation of UV cut layer)
After applying a UV curable hard coating agent Rioduras TYT65-01 (TiO ₂ ) manufactured by Toyo Ink Co., Ltd. on one side of the resin substrate and applying with a wire bar so that the (average) film thickness after drying is 4 μm. After drying at 80 ° C. for 1 minute, using a high-pressure mercury lamp, curing conditions: 200 mJ / cm ² curing was performed to form a UV cut layer.

  The maximum cross-sectional height Rt (p) at this time was 16 nm.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured with an AFM (Atomic Force Microscope) and a detector having a stylus with a minimum tip radius, and the measurement direction is 30 μm with a stylus with a minimum tip radius. This is the average roughness for the amplitude of fine irregularities, measured many times in the section.

(Formation of barrier layer)
Using a UV ozone cleaner Model UV-1 manufactured by SAMCO, the atmosphere at the time of irradiation was replaced with nitrogen, the ozone concentration was adjusted to 300 ppm, and surface treatment was performed at 80 ° C. for 5 minutes.

  Spin coating (5000 rpm, 60 seconds) using a 10% by mass dibutyl ether solution of perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica NN120-10, non-catalytic type) as a silicon compound-containing liquid on the resin substrate surface. ) And then dried at 80 ° C. for 10 minutes to form a film containing a silicon compound.

  Thereafter, using a stage movable type xenon excimer irradiation device MODEL: MECL-M-1-200 manufactured by MD Excimer, the stage is moved while controlling the atmosphere in the irradiation chamber using nitrogen and oxygen as follows. The sample was reciprocated at a speed of 5 mm / second and irradiated a total of 5 reciprocations, and then the sample was taken out and used as Sample 1-1. This apparatus is equipped with one Xe excimer lamp with an effective irradiation width of 10 mm, and corresponds to 1 second processing / pass when transported at a stage transport speed of 10 mm / sec. The film thickness of the barrier layer after the modification treatment was 150 nm.

(conditions)
Excimer light intensity: 60 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 100 ° C
(Atmosphere conditions for sample 1-1)
1-3 round trip: oxygen concentration 0.05%
4-5 round trip: oxygen concentration 1.5%
<Preparation of Sample 1-2>
Sample 1-2 (barrier layer film thickness is 150 nm) in which a barrier layer was formed directly on both surfaces of the resin base material by the same method as Sample 1-1, except for the UV cut layer during the preparation of Sample 1-1. Produced.

<Preparation of Sample 1-3>
Sample 1-3 (barrier layer film thickness) in which only the barrier layer (no UV cut layer) was formed directly on the resin substrate on the surface opposite to the barrier layer forming surface of Sample 1-1 by the same method as Sample 1-1 150 nm).

<Preparation of Sample 1-4>
A sample 1-4 (barrier layer thickness 150 nm) was prepared by forming a UV cut layer and a barrier layer on the surface of the sample 1-1 opposite to the barrier layer forming surface in the same manner as the sample 1-1.

<Preparation of Sample 1-5>
UV curing type hard coating agent using UV cut layer of Sample 1-4 Sample 1 was prepared in the same manner as Sample 1-4, except that Rio Dura TYT65-01 (TiO ₂ ) was replaced with Rio Dura TYN64-01 (ZnO). 5 (barrier layer film thickness is 150 nm).

<Preparation of Sample 1-6>
UV curing type hard coating agent using UV cut layer of Sample 1-4 Adeka Stub LA-32 (ultraviolet absorber) manufactured by ADEKA Corporation instead of Rio Duras TYT65-01 (TiO ₂ ) . Sample 1-6 (barrier layer film thickness is 150 nm) was prepared in the same manner as Sample 1-4, except that a solution dissolved in 349 (acrylic resin binder) at 20% by mass was used.

<Preparation of Sample 1-7>
UV curing type hard coating agent using UV cut layer of Sample 1-4 TINUVIN-123 (HALS agent) manufactured by Ciba Japan Co., Ltd. instead of Rio Duras TYT65-01 (TiO ₂ ) . Sample 1-7 (with a barrier layer thickness of 150 nm) was prepared in the same manner as Sample 1-4, except that a solution dissolved in 349 so as to be 20% by mass was used.

<Preparation of Samples 1-8 to 1-14>
Samples 1-8 to 1-14 were prepared by adjusting the concentration of the coating solution so that the film thicknesses of the UV cut layer and the barrier layer of Sample 1-4 were as shown in Table 1.

<Preparation of Sample 1-15>
Sample 1-15 (the second barrier layer film thickness is 150 nm) was prepared by laminating a barrier layer on the one-side barrier layer of Sample 1-4 by the same method as Sample 1-1.

<Preparation of Sample 1-16>
Sample 1-16 (the barrier layer film thickness of the second layer is 150 nm) in which a barrier layer was laminated on the barrier layers on both sides of Sample 1-4 by the same method as Sample 1-1 was produced.

<Preparation of Sample 1-17>
After applying UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 made by JSR Corporation on the barrier layers on both sides of Sample 1-4, and applying with a wire bar so that the film thickness after drying becomes 4 μm, After drying at 80 ° C. for 3 minutes, the resin was cured at 500 mJ / cm ² in an air atmosphere using a high-pressure mercury lamp to form a stress relaxation layer. Furthermore, Sample 1-17 (the second barrier layer film thickness is 150 nm) in which a barrier layer was stacked on the stress relaxation layers on both sides by the same method as Sample 1-1 was produced.

<Preparation of Sample 1-18>
When preparing Sample 1-1, except for the UV-cut layer, the first barrier layer only forms a film containing a silicon compound, does not irradiate excimer, and is the surface opposite to the surface on which the barrier layer film is formed. A barrier layer film was directly formed on the resin substrate (no UV cut layer). After forming the barrier layer film on both surfaces, excimer irradiation was performed only from the first barrier layer side in the same manner as in Sample 1-1 to prepare Sample 1-18 (the barrier layer thickness was 150 nm each).

(Evaluation)
With the measurement method as described above, the water vapor transmission rate, the light transmittance of the film, the tensile strength and the elongation rate, and the adhesion were evaluated.

  The evaluation results of Samples 1-1 to 1-18 are shown in Table 1.

  As is clear from Table 1, the gas barrier film with a UV cut layer on both sides of the present invention has a high gas barrier property and adhesion, a high UV light cut rate, and a tensile strength and elongation rate that are not deteriorated by ultraviolet rays. .

  Moreover, it turns out that adhesiveness is very deteriorated by the ultraviolet irradiation from one side compared with double-sided irradiation.

Example 2: Evaluation of organic thin film device Each of the gas barrier films of Samples 1-1 to 1-18 prepared in Example 1 was prepared, and an organic photoelectric conversion element and an organic EL element were prepared. The degree of deterioration was evaluated.

<Method for producing organic thin film device>
<Method for producing organic photoelectric conversion element>
A gas barrier film having an indium tin oxide (ITO) transparent conductive film deposited to a thickness of 150 nm (sheet resistance 10 Ω / □) is patterned to a width of 2 mm using a normal photolithography technique and wet etching to form a first film An electrode was produced.

  The patterned first electrode was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

  On this transparent substrate, Baytron P4083 (manufactured by Starck Vitec), which is a conductive polymer, was applied and dried to a film thickness of 30 nm, and then heat treated at 150 ° C. for 30 minutes to form a hole transport layer. .

  Thereafter, the substrate was brought into a nitrogen chamber and manufactured in a nitrogen atmosphere.

First, the substrate was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere. Next, P3HT in chlorobenzene (plectrovirus Toro Nix Co., Ltd. regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Corporation: 6,6-phenyl _{-C 61} - butyric acid methyl ester) and 3.0 wt% Then, a liquid mixed at 1: 0.8 was prepared so that the film thickness was 100 nm while being filtered through a filter, and the film was allowed to stand at room temperature and dried. Subsequently, a heat treatment was performed at 150 ° C. for 15 minutes to form a photoelectric conversion layer.

Next, the substrate on which the series of functional layers is formed is moved into a vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then fluorinated at a deposition rate of 0.01 nm / second. Laminate 0.6 nm of lithium, and then continue to deposit 100 nm of Al metal at a deposition rate of 0.2 nm / sec through a shadow mask with a width of 2 mm (vaporization is performed so that the light receiving part is 2 × 2 mm). A second electrode was formed.

  Each of the obtained organic photoelectric conversion elements was moved to a nitrogen chamber and sealed with a sealing cap and a UV curable resin to produce an organic photoelectric conversion element having a light receiving portion of 2 × 2 mm size.

(Preparation of gas barrier film sample for sealing and sealing of organic photoelectric conversion element)
In an environment purged with nitrogen gas (inert gas), two gas barrier films were used, and an epoxy photocurable adhesive was applied as a sealing material to the surface provided with the gas barrier layer. It was produced as a film.

  Next, the organic photoelectric conversion element is sandwiched and adhered between the adhesive-coated surfaces of the two gas barrier film samples coated with the adhesive, and then cured by irradiating UV light from one side of the substrate. The organic photoelectric conversion element was subjected to sealing treatment to prepare organic photoelectric conversion elements 1-1 to 1-18.

<Evaluation>
In the evaluation, each element was ranked according to the following criteria. The practical range is more than ○.

A solar simulator (AM1.5G filter) is irradiated with light of 100 mW / cm ² , a mask with an effective area of 4.0 mm ² is superimposed on the light receiving part, and IV characteristics are evaluated, whereby the short circuit current density Jsc ( mA / cm ² ), open-circuit voltage Voc (V), and fill factor FF (%) were measured for each of four light receiving portions formed on the element, and energy conversion efficiency PCE (%) determined according to the following formula 1 The four-point average value was estimated.
(Formula 1) PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency maintenance rate when a film with a bending process was used was calculated against the absence of the gas barrier film bending process, and was ranked as follows.

Conversion efficiency maintenance ratio = conversion efficiency of element using a film subjected to bending treatment / conversion efficiency of element using a film without bending treatment × 100 (%)
A: 90% or more B: 60% or more, less than 90% Δ: 20% or more, less than 60% ×: less than 20% Table 2 shows the evaluation results of the organic photoelectric conversion elements.

<Method for producing organic EL element>
On the inorganic layer of the gas barrier film, ITO (indium tin oxide) having a thickness of 150 nm was formed by sputtering, and patterned by photolithography to form a first electrode layer. The pattern was such that the light emission area was 50 mm square.

<Formation of hole transport layer>
On the 1st electrode layer of the barrier film in which the 1st electrode layer was formed, after apply | coating the coating liquid for hole transport layer formation shown below with an extrusion coater, it dried and formed the hole transport layer. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

Before coating the hole transport layer forming coating solution, cleaning surface modification treatment of the barrier film was carried out 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.

(Application conditions)
The coating process was performed in the atmosphere at 25 ° C. and a relative humidity of 50%.

(Preparation of coating solution for hole transport layer formation)
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with pure water at 65% and methanol at 5% was prepared as a coating solution for forming a hole transport layer.

(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 forming 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.

<Formation of light emitting layer>
Subsequently, on the hole transport layer of the barrier film 1 formed up to the hole transport layer, the following white light emitting layer forming coating solution 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.

(Coating liquid for white light emitting layer formation)
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, and dissolved in 100 g of toluene to form a white light emitting layer. It was prepared as a coating solution.

(Application conditions)
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.

(Drying and heat treatment conditions)
After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., followed by a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.

<Formation of electron transport layer>
Subsequently, after forming the light emitting layer, the following coating liquid for forming an electron transport layer was applied by an extrusion coater and then dried to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

(Application conditions)
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.

(Coating liquid for electron transport layer formation)
The electron transport layer was prepared by dissolving 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.

(Drying and heat treatment conditions)
After applying the coating solution for forming the electron transport layer, the solvent is removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
Subsequently, an electron injection layer was formed on the formed electron transport layer. First, the substrate was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. In advance, 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.

(Formation of second electrode)
Subsequently, the second electrode forming material is formed on the formed electron injection layer under a vacuum of 5 × 10 ⁻⁴ Pa except for the portion that becomes the take-out electrode on the first electrode on the formed electron injection layer. A mask pattern was formed by vapor deposition so that a light emitting area was 50 mm square by using aluminum as an extraction electrode, and a second electrode having a thickness of 100 nm was laminated.

(Cutting)
The barrier film 1 formed up to the second electrode was moved again to a nitrogen atmosphere and cut into a prescribed size to produce an organic EL device.

(Cutting method)
The cutting method is not particularly limited, but is preferably performed by ablation processing using a high energy laser such as an ultraviolet laser (for example, wavelength 266 nm), an infrared laser, a carbon dioxide gas laser or the like. Since the gas barrier film has an inorganic thin film that is easily broken, cracks may occur in detail when cut with a normal cutter. The same applies to not only cutting of the element but also cutting of the gas barrier film alone. Furthermore, the cracking at the time of cutting can also be suppressed by installing a protective layer containing an organic component on the surface of the inorganic layer.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced organic EL element, and a flexible printed board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm, Surface treatment NiAu plating) was connected.

  Pressure bonding conditions: Pressure bonding 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.

(Sealing)
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, and the organic EL element 101 was manufactured.

  In addition, as a sealing member, a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.), a polyethylene terephthalate (PET) film (12 μm thick) with an adhesive for dry lamination (two-component reaction type urethane adhesive). The laminate used (adhesive layer thickness 1.5 μm) was used.

  A thermosetting adhesive was uniformly applied to the aluminum surface with a thickness of 20 μm along the adhesive surface (shiny surface) of the aluminum foil using a dispenser.

  The following epoxy adhesives were used as the thermosetting adhesive.

Bisphenol A diglycidyl ether (DGEBA)
Dicyandiamide (DICY)
Epoxy adduct-based curing accelerator After that, 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. The organic EL elements 1-1 to 1-18 were fabricated by closely sealing at 5 MPa and an apparatus speed of 0.3 m / min.

<Evaluation>
In the evaluation, each element was ranked according to the following criteria. The practical range is more than ○.

(Evaluation of sunspots)
A current of 1 mA / cm ² was applied to the sample to emit light continuously for 300 hours, and then a part of the panel was magnified with a 100 × microscope (MORITEX MS-804, lens MP-ZE25-200) and photographed. Went. The photographed image is cut out in a 2mm square, visually observed, the situation of black spots is examined, the performance maintenance ratio when using a film with bending is calculated against the absence of bending of the gas barrier film, and the following ranking is calculated. Went.

300-hour life maintenance ratio = area of black spots generated in an element using a film subjected to bending treatment / area of black spots generated in an element using a film without bending treatment × 100 (%)
◎: 90% or more ○: 60% or more, less than 90% △: 20% or more, less than 60% ×: less than 20% Table 2 shows the evaluation results of black points.

  As is apparent from Table 2, the conversion efficiency maintenance ratio of the organic photoelectric conversion element using the gas barrier film of the present invention is high, and the black spot of the organic EL element hardly changes. That is, it can be seen that both high gas barrier properties and high flexibility are achieved.

DESCRIPTION OF SYMBOLS 1 Organic electronic device 2 Gas barrier film 3 First electrode 4 Organic functional layer 5 Second electrode 6 Base material

Claims (5)

  As a gas barrier film, a gas barrier layer is provided on both surfaces of a resin substrate, each including an ultraviolet cut layer and at least one layer selected from a silicon oxide layer and a silicon oxynitride layer in this order. Gas barrier film.   The silicon oxide layer or the silicon oxynitride layer is formed by applying a solution of a silicon compound having a polysilazane skeleton and then irradiating with vacuum ultraviolet light having a wavelength of 200 nm or less. The gas barrier film according to the description.   The gas barrier film according to claim 2, wherein the irradiation of the vacuum ultraviolet light is front and back double-sided irradiation.   The gas barrier film according to any one of claims 1 to 3, wherein the ultraviolet cut layer contains a particulate metal oxide as an ultraviolet absorber.   An organic electronic device using the gas barrier film according to any one of claims 1 to 4.

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