JP2012076386A - Ultraviolet-shieldable film and organic electronic device obtained by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-shieldable film excellent in ultraviolet ray cuttability and flaw resistance (hereinafter also called hard coat properties) and a barrier film which has extremely-high gas barrier performance and is excellent in ultraviolet ray cuttability and flaw resistance (hereinafter also called hard coat properties) and to provide organic electronic devices such as an organic photoelectric conversion element and an organic EL element which are obtained by using the ultraviolet-shieldable film and the barrier film.SOLUTION: The ultraviolet-shieldable film is obtained by layering a weather-resistant layer 1 comprising an organic compound-based ultraviolet absorbent and a resin binder on at least one surface of a resin substrate and layering another weather-resistant layer 2 comprising metal oxide fine particles and the resin binder on the weather-resistant layer 1.

Description

  The present invention is mainly used for packages such as electronic devices, organic electroluminescence elements (hereinafter also referred to as organic EL elements), display materials such as plastic substrates such as liquid crystals, or organic photoelectric conversion elements (organic solar cells). Further, the present invention relates to a gas barrier film having an ultraviolet shielding function, a gas barrier film having gas barrier properties, and a production method thereof, and also relates to an organic electronic device such as an organic photoelectric conversion element or an organic EL element having the 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 the alteration of industrial products and pharmaceuticals.

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

  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 cannot be confirmed from the outside. Furthermore, the solar cell material is required to be transparent 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 the ability to display curved surfaces, films such as transparent plastic are used in place of glass substrates that are heavy, easy to break, and difficult to increase in area. Substrates are beginning 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 with inferior gas barrier properties is used, water vapor or air permeates 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 of not being able to maintain the required vacuum.

In order to solve such problems, it is known to form a gas barrier film substrate by forming a metal oxide thin film on a film substrate. Recently, as a gas barrier film used for organic electronic devices that are sensitive to moisture such as organic solar cells and organic EL elements, gas barrier performance is required such that the water vapor transmission rate is lower than 1 × 10 ⁻³ g / (m ² · 24 h). ing.

  In particular, when used as a material for solar cells, it is used outdoors, so it prevents UV light from being deteriorated by ultraviolet rays of sunlight. What has the flaw resistance for carrying out is required.

  In order to solve such problems, a weather resistant resin film is proposed in which a light resistant layer containing metal oxide particles is provided in the first layer and a weather resistant layer containing an organic ultraviolet absorber is provided in the second layer. (For example, patent document 1), there is no description of a gas barrier layer, the metal oxide particle is using only a limited amount, and the ultraviolet cut effect is not enough. Further, the water vapor that has permeated water vapor and passed through the film substrate also causes deterioration of the photoelectric conversion element, which causes a problem. There is also a problem with scratch resistance when exposed to wind and rain outdoors.

In addition, there is one in which an inorganic vapor deposition film is formed as a first layer on a transparent plastic substrate, and a barrier layer is formed thereon to improve the gas barrier property (for example, Patent Document 2). The side is an ultraviolet cut layer made of only metal oxide particles, and cannot block ultraviolet rays around 380 nm for protecting the photoelectric conversion element (solar cell) inside the gas barrier layer. Moreover, the gas barrier performance which water vapor permeability is less than 1 * 10 < ^-3 > g / m < ² > * day calculated ^| required as a gas barrier film for organic photoelectric conversion elements, organic EL elements, etc. is not acquired.

Similarly, there is one in which a barrier layer is formed as a first layer on a transparent plastic substrate and an ultraviolet curable polymer layer is formed thereon to improve gas barrier properties (for example, Patent Document 3). The water vapor transmission rate is such that the gas barrier performance is less than 1 × 10 ⁻³ g / m ² · day, but the opposite side of the barrier layer is only an organic ultraviolet absorber and is exposed to ultraviolet rays for a long time. As a result, the organic ultraviolet absorber is decomposed and the ultraviolet ray blocking function is lost. Furthermore, when exposed to wind and rain outdoors, there is a problem with scratch resistance.

  There is no weather-resistant film having a functional layer with sufficient UV-cut function and scratch resistance as described above, and further, a gas barrier film or weather resistance having both a UV-cut function and a gas barrier property and having a scratch-resistant functional layer. There is no film.

JP 2006-326971 A JP 2004-338201 A JP 2006-297737 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an ultraviolet shielding film excellent in ultraviolet cut-off property and excellent in scratch resistance (hereinafter also referred to as hard coat property). Furthermore, providing a barrier film excellent in extremely high gas barrier performance, ultraviolet cut-off property and scratch resistance (hereinafter also referred to as hard coat property), and an organic photoelectric conversion element using these films, An object of the present invention is to provide an organic electronic device such as an organic EL element.

  The above object of the present invention is achieved by the following means.

  1. It has a weathering layer 1 containing an organic compound ultraviolet absorber and a resin binder on at least one surface of a resin substrate, and has a weathering layer 2 containing metal oxide fine particles and a resin binder on the weathering layer 1. A characteristic ultraviolet shielding film.

  2. 2. The ultraviolet shielding film as described in 1 above, wherein the resin binder contains an actinic ray curable resin.

  3. The weather-resistant layer contains a light stabilizer (HALS agent) in an amount of 1% by mass to 20% by mass based on the total mass of the organic compound ultraviolet absorber or the metal oxide fine particles and the resin binder. 3. The ultraviolet shielding film as described in 1 or 2 above.

  4). Having a weathering layer 1 containing an organic compound ultraviolet absorber and a resin binder on at least one surface of the resin substrate, and having a weathering layer 2 containing metal oxide fine particles and a resin binder on the weathering layer 1; An ultraviolet shielding film, wherein a gas barrier layer is provided on the surface of the resin substrate opposite to the surface on which the weathering layers 1 and 2 are provided.

  5. 5. The ultraviolet shielding film as described in 4 above, wherein the resin binder contains an actinic ray curable resin.

  6). The weather-resistant layer contains a light stabilizer (HALS agent) in an amount of 1% by mass to 20% by mass based on the total mass of the organic compound ultraviolet absorber or the metal oxide fine particles and the resin binder. 6. The ultraviolet shielding film as described in 4 or 5 above.

  7). The ultraviolet shielding according to any one of 4 to 6 above, wherein the gas barrier layer is obtained by applying a solution of a silicon compound having a polysilazane skeleton and irradiating vacuum ultraviolet light having a wavelength of 200 nm or less. Sex film.

  8). 8. An organic electronic device using the ultraviolet shielding film according to any one of 4 to 7.

  According to the present invention, an ultraviolet shielding film excellent in ultraviolet cutability and scratch resistance, an extremely high gas barrier performance, an ultraviolet shielding gas barrier film excellent in ultraviolet cutability and scratch resistance, and an organic photoelectric conversion element and an organic EL element using the same. Such an organic electronic device could be provided.

It is an example of the basic composition of an organic electronic device.

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

  The present invention relates to an ultraviolet shielding film having scratch resistance (hard coat property) having a configuration in which two ultraviolet cut layers are provided on at least one side of a resin substrate, and two ultraviolet cut layers on at least one side of a resin substrate. It is related with the ultraviolet-shielding gas barrier film which has a film structure which was equipped and was equipped with the gas barrier layer in the opposite side surface, and also has scratch resistance (hard-coat property).

  Usually, metal oxide UV absorbers, such as zinc oxide and titanium oxide, have lower UV-cutting efficiency compared to organic systems (many of them block UV rays of 350 nm or less), but they are not suitable for long-term UV irradiation. Little deterioration even when exposed.

  In contrast, organic compound-based UV absorbers have good UV-cutting efficiency (shielding UV rays of 400 nm or less), but when they are exposed to UV rays for a long time, they decompose themselves and lose their UV-cutting function. End up.

  Therefore, an organic compound-based UV absorber layer is formed in the first layer, and a metal oxide-based UV absorber layer is formed in the second layer (upper layer). The decomposition of the organic compound UV absorber in the first layer (lower layer) was reduced, and long-term UV cut was made possible. Further, the vacuum ultraviolet light of 200 nm or less used for curing the barrier layer on the side opposite to the substrate of the weather resistant layers 1 and 2 passes through the transparent plastic substrate, and the organic compound system of the weather resistant layer 1 on the opposite side Will reach even the UV absorber. At that time, the organic compound-based ultraviolet absorber absorbs the vacuum ultraviolet light and converts the light energy into heat energy, thereby causing a thermosetting action in addition to the ultraviolet curing. Therefore, the adhesiveness of the first weathering layer containing a transparent plastic substrate and an organic compound UV absorber was improved. Surprisingly, the first and second layers of the weather-resistant layer were further cured, so that it was possible to impart stronger scratch resistance (hard coat properties) to the weather-resistant layers 1 and 2.

  By providing an ultraviolet-shielding weathering layer on the opposite side of the gas barrier layer, it is possible to reduce the transmission of ultraviolet rays to the barrier layer and to prolong the lifetime of the barrier layer.

<What is UV shielding (hereinafter also referred to as UV blocking)>
Ultraviolet rays are electromagnetic waves of invisible light having a wavelength of 10 to 400 nm, that is, shorter than visible light and longer than soft X-rays. As a classification method according to wavelength, near ultraviolet light (wavelength 380 to 200 nm), deep ultraviolet light (wavelength 200 to 10 nm) or vacuum ultraviolet light (far UV (FUV) or vacuum UV (VUV)), extreme ultraviolet light (wavelength 1 to 10 nm) or It is divided into extreme ultraviolet (extreme UV, EUVorXUV). Moreover, from a viewpoint of influence on human health and the environment, it may be divided into UVA (400 to 315 nm), UVB (315 to 280 nm), and UVC (less than 280 nm). The term “ultraviolet shielding” as used in the present invention means that light having the wavelengths of UVA, UVB, and UVC is not transmitted.

<Ultraviolet shielding gas barrier film>
The ultraviolet shielding gas barrier film of the present invention includes a weather barrier layer 1 comprising a gas barrier layer on at least one surface of a resin substrate, and an organic compound ultraviolet absorber and a resin binder on the surface opposite to the surface provided with the gas barrier layer. And having a weathering layer 2 containing metal oxide fine particles and a resin binder on the weathering layer 1.

As the gas barrier performance of the ultraviolet shielding 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 ⁻ It is preferably 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. is there.

(Layer structure of UV shielding gas barrier film)
In the present invention, the gas barrier layer formed on the surface opposite to the weather-resistant layer on the resin substrate may be one layer or two or three layers. A stress relaxation layer may be sandwiched between the gas barrier layers.

  Whether it is a single layer or a stacked layer, the thickness of one gas barrier layer is preferably 5 nm to 1000 nm, more preferably 10 nm to 500 nm, and particularly 30 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 are extremely less likely to occur, and generation of defects can be prevented.

<Weather-resistant layer>
The organic thin film electronic device such as a solar cell used outdoors is a functional layer for preventing deterioration (scratch resistance) due to exposure to ultraviolet rays or wind and rain in sunlight. There are two functions required for the weather-resistant layer, which can be divided into an ultraviolet cut function for cutting ultraviolet rays in sunlight, and a scratch resistance function for preventing scratches on the outermost surface of the film due to wind and rain, particularly sand and dust. When an actual exposure test that is exposed to ultraviolet rays from sunlight or wind and rain is performed, it is impossible to evaluate the deterioration by actual exposure in the case of a solar cell that requires a durability of 10 to 20 years. Therefore, as an ultraviolet ray cut evaluation for an accelerated evaluation test of actual exposure, for example, an ultraviolet irradiation test is performed using an iSuper UV tester manufactured by Iwasaki Electric Co., Ltd. to evaluate deterioration.

  The UV-cutting function required for the weather resistant layer of the present invention is a layer having a performance that hardly deteriorates the base resin in the UV irradiation test (metal halide forced deterioration test) using the eye super UV tester.

  As the scratch resistance evaluation, a steel wool test (hereinafter also referred to as SW test) is generally used. The SW test is a layer that is not damaged by a speed variation of 500 mm / s, a distance of 50 mm, and 10 reciprocations using a load variation friction and wear test system HHS2000 manufactured by Haydon.

  The layer having both UV-cutting ability and scratch resistance is used as the weather resistant layer of the present invention.

  The weather-resistant layer 1 has an organic compound-based ultraviolet absorber and a resin binder for fixing it, and may further contain a light stabilizer (hereinafter also referred to as a HALS agent).

  The higher the organic compound ultraviolet absorber content, the better the ultraviolet shielding properties. In the present invention, the weather resistant layer 1 contains an organic compound ultraviolet absorber in an amount of 1% by mass to 30% by mass based on the (total) mass of the organic compound ultraviolet absorber and the resin binder. Preferably, they are 2 mass% or more and 20 mass% or less. If it is contained in an amount of more than 30% by mass, bleeding out occurs, and if it is less than 1%, the ultraviolet shielding property is inferior.

  The weather resistant layer 2 has metal oxide fine particles and a resin binder that fixes the metal oxide fine particles, and may further contain a light stabilizer (hereinafter also referred to as a HALS agent). As the content of the metal oxide fine particles is larger, the ultraviolet shielding property is improved. In the present invention, the weather resistant layer 2 contains metal oxide fine particles in an amount of 30% by mass to 80% by mass based on the (total) mass of the metal oxide fine particles and the resin binder. If it is contained in an amount of more than 80% by mass, it becomes cloudy and is not preferable.

(Method for producing weather-resistant layer)
The weathering layer is formed by preparing a coating solution in which an organic compound-based ultraviolet absorber or metal oxide fine particles are dispersed in a resin binder, for example, an actinic ray curable resin. A coating solution is prepared by dissolving a resin binder in a solution obtained by dissolving the UV absorber in a solvent or by dispersing metal oxide fine particles in a solvent, and applying the coating solution to a resin substrate. A film is formed by irradiating the curable resin with actinic rays. 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.

  Each weathering layer may be formed as a single layer or a laminate, and the film thickness of one weathering layer is preferably selected in accordance with the purpose, but the film thickness after drying is 0.1 μm or more and 100 μm or less. More preferably, it is preferably 0.5 μm or more and 50 μm or less.

  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 weathering layer may be a resin cured by a thermosetting method, or may be cured by actinic rays. However, if actinic rays are blocked, unnecessary curing does not occur, and actinic rays are particularly preferable. It is preferably cured and fixed by ultraviolet rays or electron beams. If necessary, a photopolymerization initiator and a thermal polymerization initiator are added to the UV-cutting layer (weather resistant layer) coating solution, and after coating on the resin substrate, the resin base material is irradiated with UV or electron beam. What is necessary is just to fix to.

  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, tri Phenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4- Photoradical initiation such as isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one Etc. The. On the other hand, when fixing to a resin base material by the thermosetting method, thermal polymerization initiators, such as a thermal radical generator, should just be added to the said weathering 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.

  When the weathering layer is cured by irradiating an electron beam, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.

  In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excessive electron beam.

  The irradiation dose is preferably such that the crosslinking density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy, preferably 10 to 100 kGy, and further 30 to 70 kGy.

  The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.

  When curing the weather resistant layer by irradiating ultraviolet rays, the wavelength of the ultraviolet rays is not particularly limited, but the wavelength of the ultraviolet light is preferably 100 nm to 450 nm, and more preferably irradiating with ultraviolet light of about 100 nm to 300 nm. .

As the light source, a low-pressure mercury lamp, deuterium lamp, Xe excimer lamp, metal halide lamp, 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 .

  It is more preferable to perform the treatment by vacuum ultraviolet irradiation having a wavelength component of 200 nm or less having a higher photon energy among the ultraviolet irradiation. This is because the deterioration of the substrate can be minimized.

(Organic compound UV absorber)
The weathering layer 1 used in the present invention further prevents deterioration due to ultraviolet rays than the weathering layer 2 containing only metal oxide fine particles by containing an organic compound-based ultraviolet absorber that absorbs light in the region of 200 to 400 nm. Can do. The organic compound-based ultraviolet absorber preferably has a high transmittance in the visible light region.

  Examples of the organic compound-based ultraviolet absorber that can be preferably contained in the weathering layer 1 of the present invention include benzotriazole-based and triazine-based compounds. 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 can be selected from TINUVIN series manufactured by Ciba Japan, Adeka Stub series manufactured by Asahi Denka Kogyo Co., Ltd. and the like.

  The content of the organic compound ultraviolet absorber in the weather resistant layer 1 is preferably 1% by mass or more and 30% by mass or less based on the mass of the organic compound ultraviolet absorber and the resin binder.

(Metal oxide fine particles)
The weather resistant layer 2 used in the present invention contains metal oxide fine particles. The metal oxide fine particles refer to those having a number average primary particle diameter in the range of 1 to 100 nm and also 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 metal oxide fine particles may be combined. Further, the shape of the metal oxide fine particles is not particularly limited such as spherical, needle-like, rod-like, spindle-like, indefinite shape, plate-like, and the crystal form is not particularly limited such as amorphous, rutile type, anatase type.

  The number average primary particle size of the metal oxide fine particles is a photographic image (excluding aggregated particles) obtained by taking an enlarged photograph of 10,000 times with a scanning electron microscope (manufactured by JEOL Ltd.) and randomly capturing 300 particles with a scanner. A) automatic image processing analyzer LUZEX AP (Nireco Corp.) software version Ver. The number average primary particle size was calculated using 1.32.

  Further, these metal oxide fine particles are treated with 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, and 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.

  Examples of commercially available metal oxide fine particles include, 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", "Sumifine" series {above, Sumitomo Osaka Cement Co., Ltd.}; "TYN" series {above, Toyo Ink Co., Ltd.} Can be mentioned. Fine titanium oxide includes “TTO-55, 51, S, M, D” series {above, Ishihara Sangyo Co., Ltd.}; “JR” series, “JA” series {above, Teika Co., Ltd.}; “TYT” "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 metal oxide fine particles in the weather resistant layer 2 are preferably 30% by mass or more and 80% by mass or less based on the (total) mass of the metal oxide fine particles and the resin binder.

(Light stabilizer)
Light stabilizers can also be used in the weathering layer. The HALS agent prevents the surrounding resin from deteriorating by capturing radicals that are deteriorated by ultraviolet rays or heat. As a HALS agent, a hindered amine system etc. can be used. Examples of the hindered amine HALS agent include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-hydroxyph Sulfonyl] propionyl]] propionohydrazide, and the like.

  Commercially available products can be selected from TINUVIN series manufactured by Ciba Japan, Adeka Stub series manufactured by Asahi Denka Kogyo Co., Ltd. and the like.

  The content of the light stabilizer (HALS agent) in the weather resistant layer is preferably 1% by mass or more and 20% by mass or less based on the mass of the organic compound ultraviolet absorber or metal oxide fine particles and the resin binder. .

(Resin binder)
The resin binder of the present invention is preferably an actinic ray curable resin that is cured by irradiation with actinic rays such as ultraviolet rays and electron beams. As the actinic ray curable resin, for example, the types of resins listed below can be preferably used.

(1.1) Silicone Resin A silicone resin having a siloxane bond with Si—O—Si as the main chain can be used. As the silicone resin, a silicone resin made of a predetermined amount of polyorganosiloxane resin can be used (for example, see JP-A-6-9937).

  The polyorganosiloxane resin is usually used after being dissolved in a hydrocarbon solvent such as toluene, xylene or petroleum solvent, or a mixture of these with a polar solvent. Moreover, you may mix | blend and use what differs in a composition in the range which mutually melt | dissolves.

  The method for producing the polyorganosiloxane resin is not particularly limited, and any known method can be used. For example, it can be obtained by hydrolysis or alcoholysis of one or a mixture of two or more organohalogenosilanes, and polyorganosiloxane resins generally contain hydrolyzable groups such as silanol groups or alkoxy groups. A group is contained in an amount of 1 to 10% by mass in terms of a silanol group.

  These reactions are generally performed in the presence of a solvent capable of melting the organohalogenosilane. It can also be obtained by a method of synthesizing a block copolymer by cohydrolyzing a linear polyorganosiloxane having a hydroxyl group, an alkoxy group or a halogen atom at the molecular chain terminal with an organotrichlorosilane. The polyorganosiloxane resin thus obtained generally contains the remaining HCl, but in the composition of the present embodiment, the storage stability is good, so that the one having 10 ppm or less, preferably 1 ppm or less is used. Is good.

(1.2) Epoxy resin An alicyclic epoxy resin such as 3,4-epoxycyclohexylmethyl 3'-4'-cyclohexylcarboxylate (see International Publication No. 2004/031257 pamphlet) can be used. An epoxy resin containing a spiro ring or a chain aliphatic epoxy resin can also be used.

(1.3) Resin containing allyl ester compound Bromine-containing (meth) allyl ester not containing an aromatic ring (see JP-A-2003-66201), allyl (meth) acrylate (see JP-A-5-286896) , Allyl ester resins (see JP-A-5-286896 and JP-A-2003-66201), copolymer compounds of acrylate esters and epoxy group-containing unsaturated compounds (see JP-A-2003-128725), acrylate compounds (Refer to Unexamined-Japanese-Patent No. 2003-147072), an acrylic ester compound (refer to Unexamined-Japanese-Patent No. 2005-2064), etc. can be used preferably.

(1.4) Acrylate resin As the acrylate resin used in the present invention, for example, a resin having an unsaturated double bond is methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, styrene. And the like.

  In addition, as resins having two or more unsaturated double bonds, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, trimethylolpropane triacrylate And pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and isobonyl acrylate.

  Commercially available UV curable resins include Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by ADEKA Corporation); Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8 MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10, DP-20 DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, Daiichi Seika Kogyo Co., Ltd.) ); KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, manufactured by Daicel UC Corporation); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC -5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (above, manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (above, manufactured by Sanyo Chemical Industries, Ltd.) SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.); RCC-15C (above, Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Toagosei) NK Hard B-420, B-500 (above, Shin-Nakamura Chemical Co., Ltd.), UV1700B, UV7600B (above, Nippon Synthetic Chemical Industry Co., Ltd.), etc. can be appropriately selected and used.

  Moreover, it is although it does not specifically limit as a hardening | curing agent of an epoxy resin, An acid anhydride hardening agent, a phenol hardening agent, etc. can be illustrated.

  Specific examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride. Examples thereof include an acid, a mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride and the like.

  The polymerization initiator is a polymerization of an acrylic monomer, and is preferably an initiator that generates radicals. An azo initiator or a peroxide initiator can be used.

  Oil-soluble peroxide-based or azo-based initiators are preferred. For example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, benzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl Peroxide initiators such as peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 2,2'-azobisisobutyronitrile, 2,2 '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,3-dimethylbutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2' Azobis (2,3,3-trimethyl Butyronitrile), 2,2'-azobis (2-isopropylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvalero) Nitrile), 2- (carbamoylazo) isobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobisisobutyrate and the like.

  In particular, organic peroxides such as tertiary isobutyl hydroperoxide, cumene hydroperoxide, paramentane hydroperoxide, and hydrogen peroxide are preferable.

  These polymerization initiators are preferably used in an amount of 0.01 to 20% by mass, particularly 0.1 to 10% by mass, based on the polymerizable monomer.

  Moreover, a hardening accelerator is contained as needed. The curing accelerator is not particularly limited as long as it has good curability and is not colored. For example, imidazole such as 2-ethyl-4-methylimidazole (2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd.) is used. Bicyclic amidines such as tertiary amines, quaternary ammonium salts, diazabicycloundecene and derivatives thereof, phosphines, phosphonium salts, etc., which can be used alone or in combination of two or more. May be used.

  In addition, in the resin binder of this invention, other resin binders other than actinic-light curable resin may be contained in the range which does not impair the effect of this invention.

(Mixing method of organic compound UV absorber or metal oxide fine particles and resin binder)
The organic compound-based UV absorber or metal oxide fine particles used in the present invention are mixed with a resin binder by a known technique. Usually, a resin binder is used as a solution, and an organic compound-based ultraviolet absorber or metal oxide fine particles are 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 addition of the organic compound-based ultraviolet absorber or metal oxide fine particles as necessary. When the resin binder has a high viscosity or is solid, a solvent may be appropriately added. If dispersion is not easy, an organic compound-based ultraviolet absorber or metal oxide fine particles, a resin binder, and a solvent are added and 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.

(Method for producing gas barrier layer)
The method for producing an ultraviolet shielding gas barrier film of the present invention comprises applying a coating solution containing a polysilazane compound on the side of the weathering layer opposite to the resin substrate, drying and then oxidizing by ultraviolet irradiation in a nitrogen atmosphere containing oxygen and water vapor. Process to produce a gas barrier layer.

  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.

“Polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond represented by the general formula (1), and includes SiO ₂ , Si ₃ N _4, and both of Si—N, Si—H, N—H, and the like. A ceramic precursor polymer such as an intermediate solid solution of SiO _x N _y .

In the formula, each of R ₁ , R ₂ , and R ₃ independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group, or the like.

In the present invention, perhydropolysilazane in which all of R ₁ , R _2, and R ₃ are hydrogen atoms is particularly preferable from the viewpoint of the denseness as a gas barrier film to be 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, a silicon alkoxide-added polysilazane obtained by reacting a polysilazane of the above general formula 1 with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827), a glycidol obtained by reacting glycidol Addition polysilazane (JP-A-6-122852), alcohol-added polysilazane obtained by reacting alcohol (JP-A-6-240208), metal carboxylate-added polysilazane obtained by reacting metal carboxylate (special Kaihei 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 ( JP-A-7- JP), etc. 96986 can be mentioned.

  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 terpene, 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. Among these, it is most preferable to use NN120 and NN110 made of perhydropolysilazane not containing a catalyst in order to form a gas barrier layer having a higher density and 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>
The modification treatment means that a coating film containing a polysilazane compound, which is a ceramic precursor inorganic polymer, is irradiated with ultraviolet rays, steam oxidation or heat treatment (including drying treatment), etc., to form a silicon oxide or oxide such as silicon dioxide. This refers to a process of conversion to a silicon oxynitride compound such as silicon nitride.

  The modification treatment preferably used in the present invention is an ultraviolet irradiation treatment. Irradiation with ultraviolet light in the presence of oxygen generates active oxygen and ozone, and the conversion reaction can be further advanced.

  This active oxygen and ozone are very reactive. In the case of polysilazane, the polysilazane coating film, which is the precursor of silicon oxide, is directly oxidized without passing through silanol, resulting in higher density and fewer defects. A silicon oxide film 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 about 100 nm to 300 nm.

As the light source, a low-pressure mercury lamp, deuterium lamp, Xe excimer lamp, metal halide lamp, 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.

  It is more preferable to perform the treatment by vacuum ultraviolet irradiation having a wavelength component of 200 nm or less having a higher photon energy among the ultraviolet irradiation. This is because if the energy is small, the effect of modifying the polysilazane is insufficient and the barrier property is lowered.

<Vacuum ultraviolet irradiation 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. Among these, excimer light is particularly preferable.

  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 has not been clarified, the present inventors use light energy because the density of the modified layer close to the surface is high and the film thickness of the modified layer close to 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, resulting in two layers of reforming as a result. It is assumed that a layer is formed.

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

Since noble gas atoms such as Xe, Kr, Ar, Ne and the like are chemically bonded and do not form molecules, they are called inert gases. 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.

  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. In addition, the ratio of oxygen atoms and nitrogen atoms in each layer was determined from the composition ratio profile data in the depth direction by X-ray photoelectron spectroscopy (XPS) while scraping the gas barrier film from the film surface to the depth direction by Ar sputtering. Calculation 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 the irradiation intensity and the irradiation time. However, in the case of a material that has the same composition as silicon oxide but has various structural forms, the irradiation intensity The absolute value of 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 treatment time can be shortened in a short time without suddenly deteriorating the reforming efficiency, and by setting it to 200 mW / cm ² or less, gas barrier performance can be efficiently provided ( Even if it exceeds 200 mW / cm ² , the increase in gas barrier properties will slow down), and not only damage to the substrate, but also damage to the lamp and other components 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 irradiation with vacuum ultraviolet light>
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.

(Resin substrate)
The resin substrate is not particularly limited as long as it is formed of an organic material that can hold the gas barrier layer and the weathering 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, a transparent barrier film can be obtained. Therefore, a transparent substrate such as a photoelectric conversion element (solar cell) or an organic EL element is used. It is also possible.

  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.

<Usage of UV shielding gas barrier film>
The ultraviolet shielding gas barrier film of the present invention can be used as various sealing materials and support films.

  The ultraviolet-shielding gas barrier film of the present invention can be particularly useful as a photoelectric conversion element and an organic EL element as an organic electronic device. When the ultraviolet shielding gas barrier film of the present invention is transparent, when this 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 organic EL element, Light emission efficiency is not deteriorated because light emission from the element 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 ultraviolet shielding 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 organic electronic devices.

(Sealing)
The case where the barrier film of the present invention is applied to 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, it is preferable that water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 10 ⁻³ g / (m ² · 24 h) or less.

<Package presentation>
The ultraviolet shielding 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.

"Measuring 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 A thin piece is prepared with the following FIB processing apparatus, and then the 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 in accordance with 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)
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)
Preparation of cell for evaluating water vapor barrier property A part (12 mm) of a gas barrier film sample before applying a transparent conductive film on a gas barrier layer surface of the gas barrier film sample using a vacuum deposition apparatus (vacuum 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 sealing with aluminum, the vacuum state is released, and in a dry nitrogen gas atmosphere, the silica sealing side (through Nagase Chemtex Co., Ltd.) is sealed on quartz glass having a thickness of 0.2 mm via a sealing UV curable resin An evaluation cell was produced by facing and irradiating with ultraviolet rays. In addition, in order to confirm the change in gas barrier properties before and after bending, a water vapor barrier property evaluation cell was similarly prepared for the gas barrier film that was not subjected to the bending treatment.

  The obtained sample with both sides sealed is stored for 3000 hours under high temperature and high humidity of 60 ° C. and 90% RH. 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 gas barrier film surface, instead of the gas barrier film sample as a comparative sample, a sample in which metallic calcium was deposited using a quartz glass plate having a thickness of 0.2 mm, The same high temperature and high humidity storage at 60 ° C. and 90% RH was carried out, and it was confirmed that no metallic calcium corrosion occurred even after 3000 hours.

<Measurement of film transmittance>
A spectrophotometer UV-2500PC: manufactured by Shimadzu Corporation was used to measure the total transmitted light amount with respect to the incident light amount of visible light. The measurement results at 550 nm, 380 nm, and 360 nm are shown in Table 1 below.

<Evaluation of weather resistance>
(Elongation at break)
The ultraviolet shielding property was evaluated by conducting the following deterioration test and measuring the elongation at break.

Using an I-Super UV tester (SUV-W151) manufactured by Iwasaki Electric Co., Ltd. as an evaluation of ultraviolet shielding properties, a metal halide forced deterioration test (temperature: 63 ° C., humidity: 50%, irradiation intensity: 100 mW /) of each gas barrier film test piece cm ² , continuously 200 hours). Irradiation was performed from the weathering layer side.

  Using each test piece after the metal halide forced deterioration test and each test piece before the test, the elongation at break was measured as follows.

  Using a variable temperature type tensile tester (“Shimadzu Autograph AGS-100D”; manufactured by Shimadzu Corporation), a gas 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 50 mm / min. The elongation until the breakage was determined by the following formula.

Elongation rate (%) = [(length at break-original length) / original length] × 100
(Evaluation of yellowing)
The yellow discoloration was evaluated using a gas barrier film test piece, a metal halide forced deterioration test (temperature: 63 ° C., humidity: 50%, irradiation intensity: 100 mW / cm) using an I-super UV tester (SUV-W151) manufactured by Iwasaki Electric Co., Ltd. ² and continuously 200 hours), the deterioration due to ultraviolet rays was visually confirmed.

  Evaluation was made according to the following criteria.

◎: Equivalent transparency before deterioration ○: Almost transparent △: Slightly yellowish ×: Yellow <Evaluation of scratch resistance>
A steel wool test (hereinafter also referred to as SW test) is used. In the SW test, a load variation type frictional wear test system HHS2000 manufactured by Haydon Co., Ltd. was used to set the load to 500 g, and the speed was 500 mm / ms, the distance was 50 mm, and 10 reciprocations were performed. did. Steel wool # 0000 was used.

  Evaluation was made according to the following criteria.

◎: No scratches ○: Slightly scratches △: Scratches are clearly visible on black paper ×: Scratches are immediately known.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless there is particular notice, it represents "mass part" or "mass%".

<Example 1: Comparison with gas barrier film>
<Preparation 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 weathering layer 1)
Ciba Japan Co., Ltd. Tinuvin 477 (organic UV absorber) is mixed with China Paint Co., Ltd. Forse Seed 461C (acrylic resin) so that the content rate is 10% by mass, and the (average) film thickness after drying is After coating with a wire bar so as to be 4 μm, drying conditions: 80 ° C., drying at 1 minute, then using a high-pressure mercury lamp in an air atmosphere, curing conditions: curing at 400 mJ / cm ² , the first weathering layer A layer was formed.

(Formation of weathering layer 2)
After the weathering layer 1 of the resin substrate is formed, a UV curable hard coat agent manufactured by Toyo Ink Co., Ltd., Rio Duras TYT65-01 (including TiO ₂ and acrylic resin) is applied, and the (average) film thickness after drying is after coating with a wire bar so as to 4 [mu] m, drying conditions; form perform curing at 400 mJ / cm ^2, the weathering layer 2; 80 ° C., dried in 1 minute, under an air atmosphere, a high-pressure mercury lamp used, the curing conditions did.

(Formation of gas barrier layer 1)
Using the UV ozone cleaner Model UV-1 manufactured by SAMCO on the opposite side of the resin substrate on which the weathering layers 1 and 2 are formed, the atmosphere during irradiation is replaced with nitrogen, and the ozone concentration is adjusted to 300 ppm. Then, surface treatment was performed at 80 ° C. for 5 minutes.

  Using a 10% by mass dibutyl ether solution of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NN-120-10, non-catalytic type) as a silicon compound-containing liquid on the opposite side of the weathering layer of the resin substrate, spin After coating with a coat (5000 rpm, 60 seconds), the film was 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 / sec 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 gas barrier layer 1 after the modification treatment was 60 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 Samples 1-2 to 1-26>
In the same manner as Sample 1-1, however, when preparing the coating solution for the weathering layer of Sample 1-1, the particle type, content, and organic compound-based ultraviolet absorber (hereinafter also referred to as UVA) listed in Table 1 , UVA content rate, HALS agent type, HALS agent content rate adjusted to dry (average) after coating with a wire bar so that the film thickness is 4 μm, then drying conditions; After drying, curing was performed in an air atmosphere using a high-pressure mercury lamp, curing conditions: 400 mJ / cm ² to form a weather resistant layer.

  Sample No. In 1-17 and 1-19, the following gas barrier layer 2 was formed instead of the gas barrier layer 1.

(Formation of gas barrier layer 2)
A mixture of silicon, silicon dioxide and magnesium fluoride (mixing ratio: 46 mol%: 46 mol%: 8 mol%) was applied to the surface of the substrate opposite to the weathering layer using an electron beam heating type continuous winding vacuum deposition machine. ) Was used as a raw material for heating and vacuum deposition to obtain a transparent deposition layer. (The thickness of the transparent vapor deposition layer is about 10nm)
(Evaluation)
With the measurement method described above, water vapor transmission rate, light transmittance of the film, elongation at break, yellowing, and steel wool resistance were evaluated.

  Tables 1 and 2 show the evaluation results of Samples 1-1 to 1-26.

Forse Seed 461C: China Paint Co., Ltd. (UV curable resin)
Forse Seed 460: China Paint Co., Ltd. (UV curable resin)
EXP100419: DIC Corporation (thermosetting resin)
Tinuvin 477: Ciba Japan Co., Ltd. (Organic compound UV absorber)
Tinuvin 292: Ciba Japan Co., Ltd. (HALS agent)
TYT65-01: Toyo Ink Manufacturing Co., Ltd. Rio Duras TYT65-01 (TiO ₂ , acrylic resin binder included)
As is apparent from Table 1, the gas barrier film of the present invention has good gas barrier properties and a high UV cut rate, and at the same time, the breaking elongation (water resistance, UV cut property) after the deterioration test, and the results of yellowing. It can be seen that there is little deterioration due to ultraviolet rays.

<Example 2: Evaluation of organic thin film device>
The gas barrier films of Samples 1-1 to 1-26 created in Example 1 were prepared, organic photoelectric conversion elements were prepared, and the performance deterioration of the organic thin film elements was evaluated.

<Method for creating organic photoelectric conversion element>
A gas barrier film on which a transparent conductive film of indium tin oxide (ITO) is deposited to a thickness of 150 nm (sheet resistance 10 Ω / □) is patterned to a width of 2 mm by using a normal photolithography technique and wet etching. An electrode was created.

  The patterned first electrode was cleaned 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 prepared in a nitrogen atmosphere.

First, the substrate was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere. Next, 3.0 masses of P3HT (manufactured by Prectronics: regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon: [6,6] -phenyl C ₆₁ -butyric acid methyl ester) on chlorobenzene. A liquid mixed at 1: 0.8 so as to be% was prepared, applied to a film thickness of 100 nm while being filtered through a filter, and allowed to dry at room temperature. Subsequently, 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. By laminating 0.6 nm of lithium, and subsequently passing through a shadow mask with a width of 2 mm (depositing so that the light receiving part is orthogonal to be 2 × 2 mm), laminating 100 nm of Al metal at a deposition rate of 0.2 nm / sec. A second electrode was formed.

  It moved to each obtained organic photoelectric conversion element nitrogen chamber, and it sealed using the cap for sealing and UV curable resin, and produced the organic photoelectric conversion element whose light-receiving part is 2x2 mm size.

(Creation of gas barrier film sample for sealing and sealing of organic photoelectric conversion element)
A sealing film in which two gas barrier films are used in an environment purged with nitrogen gas (inert gas) and an epoxy photocurable adhesive is applied as a sealing material to the surface provided with the gas barrier layer Created as.

  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 sealed.

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

<Rank of organic photoelectric conversion element>
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 same 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
Conduct a metal halide forced deterioration test (temperature: 63 ° C., humidity: 50%, irradiation intensity: 100 mW / cm ² , continuous 200 hours input) using an I-super UV tester (SUV-W151) manufactured by Iwasaki Electric Co., Ltd. The conversion efficiency maintenance ratio after deterioration with respect to was calculated and ranked as follows.

Conversion efficiency maintenance ratio = Conversion efficiency of element using film subjected to metal halide forced deterioration test / Conversion efficiency of element using film without deterioration × 100 (%)
A: 90% or more B: 60% or more, less than 90% Δ: 20% or more, less than 60% ×: less than 20% The conversion efficiency maintenance rate of the organic photoelectric conversion element prepared in Example 2 was evaluated. The results are shown in Table 2.

  Although all the organic photoelectric conversion elements corresponding to the gas barrier films 1-1 to 1-19 and 1-26 of the present invention were 60% or more, the organic photoelectric conversion corresponding to the gas barrier films 1-21 to 1-25 of the comparative examples. All conversion elements were less than 20%. In the element using the gas barrier film of the present invention, the performance of the organic thin film device hardly changes. That is, it can be seen that both high gas barrier properties and ultraviolet shielding properties are achieved.

1 Organic Electronic Device 2 Gas Barrier Film 3 First Electrode 4 Organic Functional Layer 5 Second Electrode 6 Base Material

Claims (8)

  It has a weathering layer 1 containing an organic compound ultraviolet absorber and a resin binder on at least one surface of a resin substrate, and has a weathering layer 2 containing metal oxide fine particles and a resin binder on the weathering layer 1. A characteristic ultraviolet shielding film.   The ultraviolet light shielding film according to claim 1, wherein the resin binder contains an actinic ray curable resin.   The weather-resistant layer contains a light stabilizer (HALS agent) in an amount of 1% by mass to 20% by mass based on the total mass of the organic compound ultraviolet absorber or the metal oxide fine particles and the resin binder. The ultraviolet shielding film according to claim 1 or 2, characterized in that   Having a weathering layer 1 containing an organic compound ultraviolet absorber and a resin binder on at least one surface of the resin substrate, and having a weathering layer 2 containing metal oxide fine particles and a resin binder on the weathering layer 1; An ultraviolet shielding film, wherein a gas barrier layer is provided on the surface of the resin substrate opposite to the surface on which the weathering layers 1 and 2 are provided.   The ultraviolet shielding film according to claim 4, wherein the resin binder contains an actinic ray curable resin.   The weather-resistant layer contains a light stabilizer (HALS agent) in an amount of 1% by mass to 20% by mass based on the total mass of the organic compound ultraviolet absorber or the metal oxide fine particles and the resin binder. The ultraviolet shielding film according to claim 4 or 5, characterized in that   The ultraviolet ray according to any one of claims 4 to 6, wherein the gas barrier layer is obtained by applying a solution of a silicon compound having a polysilazane skeleton and irradiating with vacuum ultraviolet light having a wavelength of 200 nm or less. Shielding film.   An organic electronic device using the ultraviolet shielding film according to any one of claims 4 to 7.

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