JP2011156752A - Gas barrier film, method of manufacturing the same, and organic electron device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier film having remarkably high barrier performance while keeping smoothness and excellent bending resistance (flexibility) and an organic electronic device such as an organic photoelectronic conversion element and an organic EL element using the same. <P>SOLUTION: The gas barrier film has a gas barrier unit comprising a gas barrier layer A, a gas barrier layer B and a gas barrier layer C which comprise silicon oxide and/or silicon oxynitride respectively on at least one surface of a resin substrate. The gas barrier unit has the layer A, the layer B and the layer C positioned from a substrate side in this order, wherein the ratio of the number of nitrogen atoms to the number of oxygen atoms (the number of N atom/the number of O atoms) in the silicon oxide and/or the silicon oxynitride in each layer is (that of layer A)<(that of layer B)>(that of layer C). <P>COPYRIGHT: (C)2011,JPO&INPIT

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), a method for producing 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.

  Under such circumstances, a technique using silicon oxynitride that is denser and denser than silicon dioxide is known. A technique for laminating a silicon nitride oxide layer 1 (a film richer in nitrogen than the silicon nitride oxide layer 2) and a silicon nitride oxide layer 2 in this order on a resin substrate is disclosed (for example, Patent Document 1: Japanese Patent No. 3859518). See) However, the gas barrier property is still insufficient, and further, there is a problem in smoothness due to a manufacturing method in which projections due to particles are easily formed in the manufacturing method, such as an atomic deposition method using a vacuum process. Moreover, since silicon oxynitride is harder and more brittle as the nitrogen component increases, cracks are likely to occur due to bending, and it is difficult to maintain high gas barrier properties in a flexible state. Furthermore, since thin films having different densities, refractive indexes, and hardnesses are laminated, there is a problem that the transmittance is lowered due to peeling at each interface between layers and reflection at the interface.

  In order to solve such a problem, when the silicon nitride oxide layer 1 (a film richer in nitrogen than the silicon nitride oxide layer 2) and the silicon nitride oxide layer 2 are stacked in this order on the resin substrate, a layer is formed between the layers 1 and 2. A technique is disclosed in which an intermediate layer 3 that continuously changes from an oxygen-nitrogen component ratio of 1 to an oxygen-nitrogen component ratio of the layer 2 is inserted (for example, Japanese Patent Application Laid-Open No. 2009-196155). According to this method, since an apparent interface does not exist apparently, the problems of delamination and a decrease in transmittance are reduced. However, since it is necessary to change the composition continuously by atomic deposition, there are disadvantages that the film formation conditions are complicated, the number of layers to be stacked is increased, and the size of the apparatus is increased, and the surface is smoothed by particles. The sex problem is not solved.

  On the other hand, as a method capable of forming a film by a simple coating process rather than a vapor deposition method that requires a vacuum process, the film was converted by applying a conversion treatment to a film coated with a silicon compound coating solution such as polysilazane on the substrate. Several methods for forming a gas barrier layer made of a silica film are also known (see, for example, Patent Document 3: Japanese Patent Laid-Open No. 10-279362 and Patent Document 4: Japanese Patent Laid-Open No. 2008-159824). Patent Document 4 discloses a process of converting a polysilazane coating film into a silica film by oxygen plasma discharge treatment under atmospheric pressure, and a gas barrier layer can be formed without requiring a vacuum process.

It is known that film formation by these coating methods can form a film with extremely high surface smoothness, and it is possible to avoid deterioration of smoothness due to particles, which is a fundamental problem of the vacuum atomic deposition method. However, the water vapor transmission rate of the obtained film is 0.35 g / (m ² · 24 h), which cannot be said to be a gas barrier layer applicable to the device as described above.

  On the other hand, as a method for converting polysilazane to form a dense silica film, a method of irradiating a polysilazane coating film with ultraviolet rays has been disclosed (for example, Patent Document 5: JP 2009-255040 A). According to this method, since the reaction is considered to proceed by direct oxidation without going through dehydration condensation, silica conversion at a lower temperature is possible, and a very effective method for forming a barrier layer on a resin film. It can be said.

  However, in the method described in this patent document, although a single film of silicon dioxide is formed, it is necessary to increase the film thickness of the gas barrier layer in order to realize the gas barrier property that has been required recently. When the barrier film is formed by the modification treatment of the coating film, it is accompanied by a very large film shrinkage. Therefore, if the coating film thickness is too thick, cracks are generated during the modification to the barrier film. Therefore, a desired gas barrier property is achieved by laminating thin films that do not cause cracks. However, each layer is made of silicon dioxide, and at least three layers, preferably five layers or more are required to realize the above-described gas barrier properties.

Japanese Patent No. 3859518 JP 2009-196155 A Japanese Patent Laid-Open No. 10-279362 JP 2008-159824 A JP 2009-255040 A

  An object of the present invention is to provide a barrier film excellent in extremely high barrier performance and bending resistance (flexibility) while maintaining smoothness, and like an organic photoelectric conversion element and an organic EL element using the same. Is to provide a simple organic electronic device.

  The object of the present invention has been achieved by the following constitution.

  1. A gas barrier unit comprising a gas barrier layer A, a gas barrier layer B, and a gas barrier layer C each made of silicon oxide and / or silicon oxynitride is provided on at least one surface of the resin substrate. , Layer B, and layer C in this order, and the ratio of the number of nitrogen atoms to the number of oxygen atoms (number of N atoms / number of O atoms) in the silicon oxide and / or silicon oxynitride of each layer is layer A <layer B> A gas barrier film which is layer C.

  2. 2. The gas barrier film as described in 1 above, wherein the total thickness of the layer A, the layer B and the layer C is from 30 nm to 500 nm.

  3. 3. The gas barrier film as described in 1 or 2 above, wherein two or more units of the gas barrier unit are provided on at least one surface of the resin substrate.

  4). The ratio of the number of nitrogen atoms to the number of oxygen atoms (number of N atoms / number of O atoms) of the gas barrier layer B of the gas barrier unit closest to the substrate is the smallest among the layers B of all the gas barrier units. 4. The gas barrier film as described in 3 above, which is characterized in that

  5. At least three or more gas barrier units are laminated, and the layer B in each unit adjacent from the second unit counting from the resin substrate side is closer to the resin substrate than the layer B in the unit adjacent to the side far from the resin substrate. The ratio of the number of nitrogen atoms to the number of oxygen atoms (N atom number / O atom number) is larger in the closer layer B, and this relationship is established in any of the adjacent units after the second unit. 5. The gas barrier film as described in 4 above.

  6). A method for producing a gas barrier film as described in 1 above, wherein a solution of a silicon compound having a polysilazane skeleton is applied, and vacuum ultraviolet light having a wavelength of 200 nm or less is applied to oxygen in the atmosphere at the time of irradiation. A method for producing a gas barrier film, comprising a step of irradiating and modifying while controlling a ratio of nitrogen.

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

  8). 8. The organic electronic device as described in 7 above, wherein the organic electronic device is an organic photoelectric conversion element.

  9. 8. The organic electronic device as described in 7 above, wherein the organic electronic device is an organic electroluminescence element.

  According to the present invention, it is possible to provide a barrier film excellent in extremely high barrier performance and bending resistance (flexibility) while maintaining smoothness, and a highly flexible organic photoelectric conversion element using the same And an organic electronic device such as an organic EL element can be provided.

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

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

<Gas-barrier a-film (hereinafter also referred to as gas-barrier film)>
The gas barrier film of the present invention has at least one gas barrier layer (also referred to as one unit in the present invention) by applying a liquid containing a silicon compound on the surface of a substrate or film (resin substrate) containing an organic resin component. Can be obtained by forming

As the gas barrier property of the gas barrier film of the present invention, the water vapor permeability measured according to the JIS K 7129B method (water vapor permeability: 25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 10 ⁻³ g / preferably ^(m 2 · 24h) or less, still more preferably ^{10 -4 g / (m 2 ·} 24h) or less, particularly preferably ^{10 -5 g / (m 2 ·} 24h) 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 is a gas barrier film including one or more gas barrier units having a layer configuration in which a gas barrier layer A, a gas barrier layer B, and a bus barrier layer C are laminated in this order on at least one surface on a resin substrate, Each of the C layers is a layer made of silicon oxide and / or silicon oxynitride, and is characterized in that the ratio of oxygen element to nitrogen element (number of N atoms / number of O atoms) contained in each layer satisfies the following formula 1.

N / O ratio of layer A <N / O ratio of layer B> N / O ratio of layer C (Equation 1)
The order of the layers needs to be in the order of layer A, layer B, and layer C from the substrate side. Silicon oxynitride has a higher density and hardness and a higher gas barrier property as the nitrogen atom ratio is higher. However, as described above, it becomes a fragile layer and is susceptible to defects such as cracks.

  The reason is not clear, but by adopting the configuration of the present invention, it is laminated from the top and bottom with a relatively low density (soft) layer, and defects such as cracks occur in the layer B that exhibits the most gas barrier performance. I think we can prevent this. That is, a layer having a high nitrogen component ratio and a high gas barrier property can be maintained in a state in which there are very few defects even under an external force such as a bend, so that both a high gas barrier property and a high flexibility can be achieved.

  In the present invention, “layer A, layer B, layer C” is one unit and two or more units are laminated, so that it is possible to achieve both higher barrier properties and flexibility.

  When stacking gas barrier units according to the present invention (hereinafter also simply referred to as units), the N / O ratio of the layer B of the gas barrier unit closest to the substrate is greater than the N / O ratio of the layer B of the other gas barrier unit. Thus, by setting the lowest value, the barrier property and bending resistance are improved. The bus barrier unit closest to the substrate is subjected to the deformation of the substrate and the greatest force generated by the deformation (because the substrate film thickness is overwhelmingly thick in the configuration). By providing the function of making the external force difficult to propagate to brittle physical properties of silicon oxynitride, it is possible to achieve both higher levels of gas barrier properties and flexibility. Further, the unit according to the present invention contains oxygen atoms at the interface portion of the adjacent layer, and it becomes possible to introduce a functional group containing oxygen by known surface treatment such as corona discharge, oxygen plasma, UV ozone, Since the interlayer adhesion between the units can be improved, the effect of stacking can be sufficiently obtained. For example, when layer B of the present invention forms an interface with an adjacent unit, it is difficult for silicon nitride to introduce a functional group by the surface treatment, and even when laminated, gas barrier properties are significantly deteriorated by delamination. I understood.

  In addition, since the second unit and subsequent layers B satisfy the following formula 2, the layer B having the highest N / O ratio that is most likely to break is positioned near the center line of the bending deformation, and the influence of external force due to the deformation is reduced. The generation of cracks can be suppressed by making it difficult to receive.

Unit 2-layer BN / O ratio> Unit 3-layer BN / O ratio>...> Unit n-layer BN / O ratio (Equation 2)
(Lamination of multiple units)
When laminating a plurality of units as described above, the following embodiments are preferable.

  In the case where an inorganic film is produced by applying a modification treatment after applying a silicon compound such as polysilazane, which is a preferred embodiment within the present invention as described later, a silicon compound coating and modification treatment (with a three-layer structure) It is preferable to fabricate one unit), and then to fabricate one unit, and then apply a second unit silicon compound and perform a modification treatment to produce a two-unit laminated unit. When the number of units is further increased, the silicon compound is applied to the surface of the second unit, the modification process is performed to produce the third unit, and the process of coating and modification processes as one set is repeated a plurality of times. Thus, it is possible to produce a laminated gas barrier film having an arbitrary number of units.

  In addition, in order to improve the coating property of the silicon compound when laminating the units, it is preferable to apply the silicon compound after treating the substrate surface or the outermost surface of the already produced unit by a known surface treatment method.

(Inorganic layer)
In the present invention, the layer A and the layer C contain at least silicon oxide or silicon oxynitride. From the viewpoint of adhesion, when the N / O ratio satisfies the formula 1 and the layer A <layer C has one unit, the N / O ratio is layer A <layer in all units. In the case where the composition of layer A> layer C is 1 unit, the N / O ratio is preferably layer A> layer C in all units.

  The N / O ratio of the layer A and the layer C is 0 to 0.5, and more preferably 0 to 0.3. If it does not exceed 0.5, the layer A or the layer B itself is hardly cracked, and the effect of suppressing the occurrence of cracks in the layer B is increased. Moreover, this N / O ratio of the layer B is 0.3-5, Preferably it is 0.4-2. When it is 0.3 or more, the denseness of the layer is increased, and a high gas barrier property can be exhibited. When it is not more than 5, moderate flexibility can be maintained.

  The thickness of one unit 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 per unit 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. Furthermore, when the units are stacked, cracks can be prevented by setting the film thickness of the first unit ≧ the film thickness of the second unit ≧ the film thickness of the third unit ≧ ··· ≧≧ the film thickness of the nth unit. ,preferable.

  As a method for forming the inorganic layer, an atomic deposition method using a vacuum system such as a physical vapor deposition method (PVD) such as an evaporation method, a sputtering method or an ion plating method, or a chemical vapor deposition method (CVD). A sol-gel method or the like can be used, but a coating method is preferred from the viewpoint of productivity and smoothness.

  As a coating method, general coating methods such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a spin coating method, a gravure coating method, and a slide coating method can be used. is there.

  Among these, the machine layer is preferably prepared by applying a coating solution containing at least one polysilazane compound. Moreover, it is preferable that the inorganic layer is oxidized from the viewpoint of barrier properties.

  In particular, the inorganic layer of the present invention is preferably obtained by coating. When a dry process is used, a large vacuum device is required, so that productivity is deteriorated. In addition, an ordinary interface forms a clear interface between layers, and delamination tends to occur. In particular, when a hard layer such as silicon oxynitride is formed, the stress generated at the time of deformation increases, and therefore delamination is more likely to occur. Furthermore, when a laminated structure is produced by a dry process, the surface smoothness tends to deteriorate.

(Coating film of polysilazane-containing liquid)
The inorganic layer according to the present invention is preferably obtained by applying a polysilazane compound and modifying it. With the single unit structure of layer A, layer B, and layer C, one unit having the above three-layer structure can be formed by one application by controlling the energy applied for controlling the atmosphere and modifying.

  Specifically, first, in order to form a layer A having a low N / O ratio for the total film thickness of layer A + layer B + layer C, a reforming process is performed with an oxygen ratio in the atmosphere of 1 to 5%. Thereafter, in order to achieve a high N / O layer of layer B, the atmosphere is changed to an oxygen concentration of 1% or less, preferably 0.1% or less, and a reforming process is performed. When changing the atmosphere, it is preferable not to expose to the atmosphere as much as possible. Further, after that, in order to form the layer C having a low N / O, the atmosphere is 1 to 5%, and the film is formed at an oxygen concentration equal to or lower than that of the layer A. The film thickness of each layer can be controlled by the processing time, and can be increased by increasing the processing time and decreased by decreasing the processing time. Further, when the layer A is formed, there are many oxygen sources such as moisture and oxygen adsorbed on the substrate surface and moisture and oxygen mixed in the silicon compound coating solution. The modification process is started from the conditions for producing the layer B, and the treatment time is adjusted, so that the layer A and the layer B can be produced once. When a process for removing the oxygen source of the substrate and the silicon compound coating solution is separately provided, the film forming conditions for the layer A cannot be omitted.

  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.

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 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 preferred from the viewpoint of the denseness as the 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, 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 going 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 layer A, the layer B, and the layer C in one unit is preferably in the range of 5 nm to 100 nm, and 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 (1%). 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 barrier 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, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide and other resin substrates, silsesquioxane having an organic-inorganic hybrid structure And a heat-resistant transparent film (product name: Sila-DEC, manufactured by Chisso Corporation), and a resin substrate formed by laminating two or more layers of the plastic. 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.

(Organic layer)
In the present invention, in addition to the purpose of relieving the stress for bending the barrier film, the rough surface of the transparent resin substrate where protrusions and the like are present is flattened, or generated in the transparent inorganic compound layer by the protrusions existing on the transparent resin substrate. An organic layer may be provided at least between the resin substrate and the inorganic compound layer in order to fill the unevenness and pinholes and planarize. Such an organic 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 organic layer is composed of carbon, hydrogen, oxygen, nitrogen, sulfur, etc., and the effects described above when inorganic atoms such as silicon, titanium, aluminum, and zirconium are used as the basic skeleton. Is difficult to obtain.

  As the photosensitive resin of the organic layer, for example, 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, urethane acrylate, Examples thereof include 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 organic layer is not particularly limited, but it 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 the formation of the organic layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. Further, in any organic layer, an appropriate resin or additive may be used for improving the film forming property and preventing the generation of pinholes in the film regardless of the position of the organic layer.

  Solvents used when forming an organic layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, α -Or terpenes such as β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Group hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropiate Glycol ethers such as lenglycol 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 glycol Alkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smoothness of the organic 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 organic layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. When the thickness is 1 μm or more, the smoothness of the film having an organic layer can be easily improved, and when the thickness is 10 μm or less, the balance of optical properties of the film can be easily adjusted.

(Organic layer as stress relaxation layer)
In the present invention, the organic layer may be provided between the substrate and the gas barrier layer as a layer for relaxing stress applied to the gas barrier film. In particular, when the above-described coating type barrier layer of the present invention is formed on a resin substrate or the like, the coating film such as polysilazane which is a precursor such as an inorganic oxide is converted into a silicon dioxide film and a silicon oxynitride film. At this time, since the density is increased and the film is contracted, there is a case where the stress is concentrated to cause a problem that a crack is generated in the barrier layer.

  Therefore, for example, it is considered that providing a stress relaxation layer having physical properties such as hardness, density, or elastic modulus located between the resin substrate and the gas barrier layer has an effect of suppressing the occurrence of cracks.

  Specifically, it is possible to form the stress relaxation layer from the materials mentioned as the silicon compound for forming the gas barrier layer of the present invention described later. For example, when designing the stress relaxation layer so that the density is lower than that of the upper gas barrier layer, even if the same material as the gas barrier layer is used, the degree of conversion reaction is selected or the gas barrier layer to be provided is selected or provided. It is possible to control the film thickness by appropriately selecting the film thickness. It is also possible to control the obtained film density itself by selecting the material used for the stress relaxation layer.

  As a specific material, for example, organopolysilazane, perhydropolysilazane, alkoxysilane, or a mixture thereof is preferably used.

  In particular, when a mixture of an organopolysilazane such as methylhydropolysilazane and perhydropolysilazane is used as the stress relaxation layer and perhydropolysilazane is used for the gas barrier layer, the physical property values such as hardness, density or elastic modulus should be given a gradient. It is very preferable in that it can have a function of relieving stress against bending of the barrier film and can improve the adhesion between the stress relaxation layer and the gas barrier layer.

  The mixing ratio of the organopolysilazane and perhydropolysilazane may be appropriately selected for the purpose of controlling the desired physical property value, and is not particularly limited. For example, when the ratio of organopolysilazane is high, the density can be set low, and when the ratio of perhydropolysilazane is high, the density can be set high.

  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.

(Additive to organic layer)
One preferred embodiment includes reactive silica particles (hereinafter also simply referred to as “reactive silica particles”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the photosensitive resin.

  Here, examples of the photopolymerizable photosensitive group include polymerizable unsaturated groups represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be.

  Moreover, as a photosensitive resin, what adjusted solid content by mixing a general purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.

  Here, the average particle size of the reactive silica particles is preferably 0.001 μm to 0.1 μm. By setting the average particle size in such a range, the antiglare property and the resolution, which are the effects of the present invention, can be obtained by using in combination with a matting agent composed of inorganic particles having an average particle size of 1 μm to 10 μm, which will be described later. It becomes easy to form a smooth layer having both optical properties satisfying a good balance and hard coat properties.

  In addition, from the viewpoint of making it easier to obtain such an effect, it is more preferable to use an average particle diameter of 0.001 μm to 0.01 μm.

  Improves adhesion of organic layer to gas barrier layer, prevents generation of cracks when the substrate is bent or heat-treated, and improves optical properties such as transparency and refractive index of gas barrier film From the viewpoint of maintaining the thickness, the smooth layer preferably contains the inorganic particles as described above in a mass ratio of 20% to 60%.

  In the present invention, a polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to a silica particle by generating a silyloxy group by a hydrolysis reaction of a hydrolyzable silyl group. Can be used as reactive silica particles.

  Examples of the hydrolyzable silyl group include a carboxylylated silyl group such as an alkoxysilyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oximesilyl group, and a hydridosilyl group.

  Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

  As the thickness of the smooth layer used in the present invention, the smoothness of the substrate is improved, the balance of the optical characteristics of the substrate can be easily adjusted, and the smoothness in the case where the smooth layer is provided only on one surface of the substrate. From the viewpoint of preventing curling of the film, a range of 1 μm to 10 μm is preferable, and a range of 2 μm to 7 μm is more preferable.

(Bleed-out prevention layer)
The bleed-out prevention layer is a smooth layer for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the film substrate to the surface when the film having the smooth layer is heated and contaminates the contact surface. Is provided on the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  Examples of the unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer include a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or in the molecule And monounsaturated organic compounds having one polymerizable unsaturated group.

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 μm to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 100 parts by mass of the solid content of the bleed-out prevention layer. It is desirable that they are mixed in a proportion of 18 parts by mass or less, more preferably 16 parts by mass or less.

  The bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator and the like as other components of the hard coat agent and the mat agent.

  The bleed-out prevention layer as described above is formulated as a coating solution with a hard coating agent, a matting agent, and other components as necessary, and appropriately prepared as a dilution solvent to support the coating solution. It can form by apply | coating to a body film surface by a conventionally well-known coating method, and then irradiating with ionizing radiation and making it harden | cure.

  In addition, as a method of irradiating with ionizing radiation, ultraviolet rays in a wavelength region of 100 nm to 400 nm, preferably 200 nm to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, etc. are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer improves the heat resistance of the substrate, makes it easier to adjust the balance of the optical characteristics of the substrate, and the bleed-out prevention layer of the substrate when the bleed-out prevention layer is provided only on one side of the substrate. From the viewpoint of preventing curling, a range of 1 μm to 10 μm is preferable, and a range of 2 μm to 7 μm is more preferable.

<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, from the element The light emission efficiency is not deteriorated because the light emission 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. 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, and the like, and composites thereof, glass, and the like. In this case, as in the case of the resin substrate, a laminate of gas barrier layers such as aluminum, aluminum oxide, silicon oxide, and silicon nitride can be used. 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) or less, water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 1 X10 ⁻³ g / (m ² · 24 h) or less is preferable.

<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. .

<Definition of 1 unit and multiple units>
In the present invention, a unit where a layer A layer BC having a different ratio N / O of nitrogen atom to oxygen atom is continuously present in the order and gradient of the present invention is determined as one unit. The lamination of a plurality of units refers to the existence of a plurality of the 1 unit regions on the substrate. A plurality of units may be stacked continuously or a plurality of units may be discontinuous. In addition, a configuration in which one unit is arranged on each side of the substrate is also considered as two units, and various combinations such as a three-unit configuration with one unit on one side and two units on the opposite side can be considered as a plurality of units in the present invention. it can.

  The unit is determined from observation of a tomographic plane with a transmission electron microscope (TEM) as described below and element distribution in the thickness direction by X-ray photoelectron spectroscopy.

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 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 <ratio N / O of the number of nitrogen atoms and the number of oxygen atoms in each layer>
The composition distribution in the film thickness direction can be known by X-ray photoelectron spectroscopy (XPS) while scraping in the depth direction from the film surface by sputtering with Ar. This data was compared with the film thickness calculated from the above-mentioned tomographic TEM image, and the ratio of the number of nitrogen atoms and the number of oxygen atoms was calculated from the XPS data.

  In addition, since 1 unit forms a precursor layer by one application | coating, it changes without showing a clear interface, having a composition gradient in a composition change part. In such a case, N / O was calculated every 1 nm in each of the layers A, B, and C, and the average of all was taken as the N / O ratio of the layer.

(Sputtering conditions)
Ion species: Ar ion Acceleration voltage: 1 kV
(X-ray photoelectron spectroscopy measurement conditions)
Apparatus: ESCALAB-200R manufactured by VG Scientific Fix
X-ray anode material: Mg
Output: 600W (acceleration voltage 15kV, emission current 40mA)
<Bending treatment>
A bending process in which the gas barrier film thus prepared is bent once to make the gas barrier layer bend once so that the curvature is 50 mmφ, and once to be outside, and is bent 100 times. gave.

<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 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 with a thickness of 0.2 mm via a sealing UV curable resin (manufactured by Nagase ChemteX). An evaluation cell was produced by facing and 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 was stored under high temperature and high humidity of 60 ° C. and 90% RH, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water 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 metallic calcium corrosion occurred even after 1000 hours.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.
<Example 1: Comparison with one unit>
<Preparation of Sample 1-1>
(Resin substrate)
As a resin substrate, a substrate of a 125 μm-thick polyester film (Tetron O3, manufactured by Teijin DuPont Films, Ltd.) that was easily bonded on both sides was annealed at 170 ° C. for 30 minutes.

(Formation of organic layer)
On the resin substrate, a UV curable organic / inorganic hybrid hard coating material OPSTAR Z7501 manufactured by JSR Corporation was applied, applied with a wire bar so that the (average) film thickness after drying was 4 μm, and then drying conditions; 80 After drying at 3 ° C. for 3 minutes, using a high-pressure mercury lamp in an air atmosphere, curing conditions: 1.0 J / cm ² curing was performed to form a smooth 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 inorganic 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.

  Using a 10% by mass dibutyl ether solution of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NN120-10, non-catalytic type) as a silicon compound-containing liquid on the surface of the substrate on which the organic layer surface has been surface-treated, 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 / 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. In addition, the film thickness of the inorganic layer (ABC total thickness) 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 was produced in the same manner as Sample 1-1 except that the thickness of the perhydropolysilazane solution coating film was adjusted so that the total film thickness after modification was 20 nm.

<Preparation of Sample 1-3>
Sample 1-3 was prepared in the same manner as Sample 1-1 except that the thickness of the perhydropolysilazane solution coating film was adjusted so that the total film thickness after modification was 40 nm.

<Preparation of Sample 1-4>
Sample 1-4 was produced in the same manner as Sample 1-1, except that the thickness of the perhydropolysilazane solution coating film was adjusted so that the total film thickness after modification was 550 nm.

<Preparation of Sample 1-5>
Sample 1-5 was produced in the same manner as Sample 1-1 except that the atmospheric condition was kept constant at an oxygen concentration of 1.5%.

<Preparation of Sample 1-6>
Sample 1-6 was produced in the same manner as Sample 1-1 except that the atmospheric condition was constant at an oxygen concentration of 0.01% and the number of reciprocating transfers was ten.

<Preparation of Sample 1-7>
Sample 1-7 was produced in the same manner as Sample 1-1, except that the atmospheric condition was constant at 1% oxygen concentration and the number of reciprocating transfers was three.

<Preparation of Sample 1-8>
Sample 1-8 was produced in the same manner as Sample 1-1 except that the atmospheric conditions were changed as follows.

(Sample 1-8 atmospheric conditions)
1-2 round trip: oxygen concentration 0.5%
3-5 round trip: Oxygen concentration 0.01%
<Preparation of Sample 1-9>
Films were formed in a total film thickness of 150 nm so that the N / O ratio would be the ratio described in Table 1 by the same method as in Example 1 described in JP-A-2009-196155. In addition, the component inclination layer described in the said cited publication patent document was installed with the film thickness of 5 nm each between the layer A and the layer B, and between the layer B and the layer C.

(Evaluation)
Before and after performing the bending process as described above, the water vapor transmission rate was measured by the measurement method described above, and the barrier performance and bending resistance were evaluated.

  Table 1 shows the evaluation results of Samples 1-1 to 1-9.

  As is apparent from the table, it can be seen that the gas barrier film of the present invention has a high gas barrier property, and its performance hardly changes before and after the bending treatment. Moreover, as a result of observing smoothness visually about the materials 1-1 to 1-4, smoothness was favorable.

<Example 2: Comparison with 3 units>
The method for producing one unit of Example 1 was repeated three times to produce a 3-unit gas barrier film. In addition, about the sample 2-2, different atmosphere control is performed for every unit so that it may mention later.

<Preparation of Sample 2-1>
Three units of Sample 1-1 were stacked.

<Preparation of Sample 2-2>
Three units were stacked by changing the conditions of the atmosphere for each unit as follows.

(Atmosphere conditions for the first unit)
1-3 round trip: Oxygen concentration 0.01%
4-5 round trip: oxygen concentration 0.1%
(Atmosphere conditions for the second unit)
1-2 round trip: oxygen concentration 0.1%
3rd and 4th round trip: oxygen concentration 0.01%
5th round: oxygen concentration 2%
(Atmosphere conditions for the third unit)
1-2 round trip: oxygen concentration 0.1%
3rd and 4th rounds: oxygen concentration 0.05%
5th round: oxygen concentration 2%
<Preparation of Sample 2-3>
Three units of one unit of Sample 1-5 were stacked.

<Preparation of Sample 2-4>
Three units of one unit of Sample 1-6 were stacked.

<Preparation of Sample 2-5>
Three units of one unit of Sample 1-8 were stacked.

<Preparation of Sample 2-6>
Three units of one unit of Sample 1-9 were stacked.

  Table 2 shows the evaluation results of Samples 2-1 to 2-6.

  As is clear from the table, it can be seen that the gas barrier film of the present invention has a remarkable effect of lamination and exhibits a very high gas barrier property, and its performance hardly changes before and after the bending treatment.

<Example 3: Evaluation of organic thin film device>
Samples 2-1 to 2-5 produced in Example 2 were prepared for the presence or absence of the bending treatment of the gas barrier film, and the organic photoelectric conversion element and the organic EL element were prepared. The degree of performance degradation 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 the deposition rate is 0.01 nm / second. Laminate lithium fluoride at 0.6 nm, and then continue through a shadow mask with a width of 2 mm (deposited so that the light receiving part is 2 × 2 mm) and deposit 100 nm of Al metal at a deposition rate of 0.2 nm / sec. Thus, 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 sealed.

<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. Close sealing was performed at 5 MPa and an apparatus speed of 0.3 m / min.

<Evaluation of organic thin film element>
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 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 (%)
◎: 90% or more ○: 60% or more, less than 90% △: 20% or more, less than 60% ×: less than 20% (rank of organic EL element)
(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 (%)
A: 90% or more B: 60% or more, less than 90% Δ: 20% or more, less than 60% ×: less than 20% Table 3 shows the evaluation results of Example 3.

  As is apparent from the table, the element using the gas barrier film of the present invention has no bending treatment, and the performance of the organic thin film device 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 (9)

  A gas barrier unit comprising a gas barrier layer A, a gas barrier layer B, and a gas barrier layer C each made of silicon oxide and / or silicon oxynitride is provided on at least one surface of the resin substrate. , Layer B, and layer C in this order, and the ratio of the number of nitrogen atoms to the number of oxygen atoms (number of N atoms / number of O atoms) in the silicon oxide and / or silicon oxynitride of each layer is layer A <layer B> A gas barrier film which is layer C.   The gas barrier film according to claim 1, wherein the total thickness of the layer A, the layer B, and the layer C is 30 nm or more and 500 nm or less.   3. The gas barrier film according to claim 1, wherein two or more gas barrier units are provided on at least one surface of the resin substrate.   The ratio of the number of nitrogen atoms to the number of oxygen atoms (number of N atoms / number of O atoms) of the gas barrier layer B of the gas barrier unit closest to the substrate is the smallest among the layers B of all the gas barrier units. The gas barrier film according to claim 3, wherein the film is a gas barrier film.   At least three or more gas barrier units are laminated, and the layer B in each unit adjacent from the second unit counting from the resin substrate side is closer to the resin substrate than the layer B in the unit adjacent to the side far from the resin substrate. The ratio of the number of nitrogen atoms to the number of oxygen atoms (N atom number / O atom number) is larger in the closer layer B, and this relationship is established in any of the adjacent units after the second unit. The gas barrier film according to claim 4.   It is a manufacturing method of the gas barrier film which manufactures the gas barrier film of Claim 1, Comprising: The solution of the silicon compound which has a polysilazane frame | skeleton is apply | coated, The vacuum ultraviolet light with a wavelength of 200 nm or less is oxygen in the atmosphere at the time of irradiation A method for producing a gas barrier film, which comprises a step of irradiating and modifying while controlling a ratio of nitrogen to nitrogen.   An organic electronic device using the gas barrier film according to any one of claims 1 to 5.   The organic electronic device according to claim 7, wherein the organic electronic device is an organic photoelectric conversion element.   The organic electronic device according to claim 7, wherein the organic electronic device is an organic electroluminescence element.

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