JP2012000546A - Method for producing gas-barrier film and organic electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a gas-barrier film at low cost, the film being very high in gas-barrier performance and excellent in stability with time; and to provide an organic electronic device, which uses the gas-barrier film manufactured by the method concerned and is very high in durability, such as an organic photoelectric transducer and an organic EL element.SOLUTION: In the method for manufacturing the gas-barrier film, a layer of a silicon compound having a polysilazane skeleton is formed at least on one face of a resin base board, and then the layer of the silicon compound is irradiated at least with vacuum ultraviolet rays having a wavelength of 200 nm or below to reform the layer itself, and then a gas-barrier layer comprising silicon oxide or acid silicon nitride is formed as a film. In this case, the gas-barrier layer is formed as the film under the conditions that a specific expression 1 is satisfied.

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 method for producing a film (hereinafter also referred to as a gas barrier film) and an organic electronic device such as an organic photoelectric conversion element or an organic EL element having a gas barrier film produced using the film.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging of goods and foods that require blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent 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 gas barrier film used for an organic electronic device 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 · 24 h).

Under such circumstances, as a method capable of forming a film by a simple coating process rather than a conventional vapor deposition method that requires a vacuum process, a conversion process is performed on a film in which a coating liquid of a silicon compound such as polysilazane is coated on a substrate. There are also known some methods for forming a gas barrier layer (also referred to as a barrier layer or a barrier layer) made of a converted silica film (see, for example, Patent Documents 1 and 2). Patent Document 1 discloses a process for 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 the need for 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 permeability of the obtained film is 0.35 g / (m ² · 24 h), which cannot be said to be a gas barrier layer that can be applied to the above-described devices.

  On the other hand, as a method of forming a dense silica film by converting polysilazane, a method of irradiating the polysilazane coating film with ultraviolet light, particularly vacuum ultraviolet light (VUV) that has high photon energy and can be efficiently modified is disclosed. (For example, patent document 3). 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 the above-mentioned patent document, VUV of 10000 mJ / cm ² or more is irradiated to a polysilazane layer of 100 nm to 250 nm, and the modification of the whole layer proceeds, but the method of light irradiation from the surface is used. In terms of characteristics, the modification of the surface portion proceeds so much that it becomes hard and brittle, so that defects such as so-called microcracks are likely to be generated. In particular, when a flexible resin film is used as the substrate, defect generation becomes significant.

A technique for forming a protective layer of an electronic device by a similar method is also disclosed (for example, Patent Document 4). According to this method, a polysilazane layer having a thickness of about 500 nm is irradiated with VUV under reduced pressure or in a substantially oxygen-free atmosphere, and a protective layer having a SiON composition for preventing deterioration of a semiconductor element due to oxygen and moisture. Can be manufactured at low cost. However, the irradiation of energy of 8500 mJ / cm ² or more is performed, and the modification of the surface portion is too advanced so that cracks easily occur.

Further, among this document, it is written that it is preferable to set the irradiation integrated light quantity and ^{100mJ / cm 2 ~1000mJ / cm 2} , the irradiation of this level energy polysilazane layer of about 500 nm, the barrier layer It was found that an insufficiently reactive portion remains on the substrate side, and water and ammonia are released while changing over time, resulting in rapid deterioration of the barrier performance.

Japanese Patent Laid-Open No. 10-279362 JP 2008-159824 A JP 2009-255040 A JP 2006-261616 A

  An object of the present invention is to provide a production method for producing a barrier film having extremely high barrier performance and excellent in temporal stability at low cost, and to use a gas barrier film produced by the method. Another object of the present invention is to provide an organic electronic device such as an organic photoelectric conversion element or an organic EL element with extremely high durability.

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

  1. A gas barrier property comprising silicon oxide or silicon oxynitride by providing a silicon compound layer having a polysilazane skeleton on at least one surface of a resin substrate, and modifying the silicon compound layer by irradiating vacuum ultraviolet light having a wavelength of 200 nm or less. In the manufacturing method of the gas barrier film which forms a layer, the gas barrier film is formed on the conditions which satisfy | fill following (Formula 1), The manufacturing method of the gas barrier film characterized by the above-mentioned.

(Formula 1)
30 nm ≦ d ≦ 500 nm and 100 mJ / cm ² ≦ J ≦ 8400 mJ / cm ²
d: Modified layer thickness (nm) after the silicon compound layer is modified by irradiation with vacuum ultraviolet light
J: Integrated light quantity of vacuum ultraviolet light (mJ / cm ² )
2. 2. The method for producing a gas barrier film according to the above 1, wherein the following (Equation 2) is further satisfied.

(Formula 2)
In the case of 30 nm ≦ d ≦ 200 nm 100 mJ / cm ² ≦ J ≦ 7500 mJ / cm ²
When 200 nm ≦ d ≦ 500 nm J ≧ 3d−500 and J ≦ 3d + 6900
3. 3. The method for producing a gas barrier film as described in 1 or 2 above, wherein a plurality of the gas barrier layers are laminated.

  4). 4. The method for producing a gas barrier film according to any one of 1 to 3, wherein 0.1 to 5.0% by mass of a catalyst is added to the silicon compound layer having the polysilazane skeleton.

  5. 5. The method for producing a gas barrier film as described in any one of 1 to 4 above, wherein the temperature at the time of irradiation with vacuum ultraviolet light is 25 ° C. or more and 150 ° C. or less.

  6). 6. An organic electronic device using a gas barrier film produced by the method for producing a gas barrier film according to any one of 1 to 5 above.

  7). 7. The organic electronic device as described in 6 above, wherein the organic electronic device is an organic photoelectric conversion element.

  8). 7. The organic electronic device as described in 6 above, wherein the organic electronic device is an organic electroluminescence element.

  According to the present invention, it was possible to provide a production method for producing a barrier film having extremely high barrier performance and excellent stability over time at low cost. Furthermore, by using the gas barrier film produced by the method, an organic electronic device such as an organic photoelectric conversion element and an organic EL element with extremely high durability could be provided.

It is a figure which shows the relationship between the polysilazane film thickness of this invention, and VUV irradiation energy. It is an example of the schematic sectional drawing 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 cm ³ / (m ² · 24 h · 0.1 MPa) or less, more preferably 0. 0.001 m ³ / (m ² · 24 h · 0.1 MPa) or less.

(Gas barrier layer and gas barrier film)
In the present invention, a precursor coating composed of at least one layer of a silicon compound, particularly preferably a compound having a polysilazane skeleton, is formed on one surface of a resin substrate and irradiated with ultraviolet rays, particularly vacuum ultraviolet rays having a wavelength of 200 nm or less. The present invention also relates to a method for producing a gas barrier film in which a gas barrier layer made of silicon oxide and / or silicon oxynitride is formed by modifying a precursor coating film made of a compound having a polysilazane skeleton.

As described above, when the gas barrier layer is formed by modifying the coating film using vacuum ultraviolet light, the modification treatment is performed by applying a high integrated light amount of 8500 mJ / cm ² or more. The feature of this method is that after the precursor film is formed, light treatment is performed from the surface side, and the modification progresses essentially in the film thickness direction of the precursor film due to attenuation of irradiation light in the precursor film. A difference in degree, that is, a gradient of the degree of reforming occurs. Since the surface part is irradiated with light from the surface, the progress of the modification is fast, and the progress of the modification is slow at the lower part (substrate side) of the precursor film. When the reaction progress is slow at the following low temperature, it is expected that the reforming gradient in the film thickness direction becomes steep. Further, in order to give such a large integrated light amount, if an existing excimer lamp is used, a processing time of about 10 minutes is required. Even if the precursor is formed by a coating method with high productivity, the excimer Since the productivity is reduced by the treatment, the productivity improvement of the coating method cannot be fully utilized unless the reforming treatment can be performed in a treatment time of preferably 30 sec or less, more preferably 10 sec or less.

  When a large degree of modification gradient is formed in the film thickness direction, defects not only easily enter the part of the surface that has undergone modification, but also the deterioration of the low-modified part over time (reaction progress is considered. ) Because of this, it was found that it causes a sudden performance degradation. As a result of intensive studies by the present inventors, it is effective to reduce the low reforming part as much as possible in order to avoid such rapid performance deterioration, and gas barrier performance and stability that does not cause rapid performance deterioration. The barrier layer thickness obtained by modifying a precursor layer made of a compound having a polysilazane skeleton and the integrated light quantity of irradiation light are within the scope of the present invention shown in FIG. 1 (indicated by dotted lines and four arrows). I realized that I can achieve it. By performing the reforming treatment within the scope of the present invention, the above-mentioned gradient of the degree of modification is reduced, the most reforming made on the surface of the barrier layer progresses, and the gas barrier performance of the portion having a high gas barrier property is exhibited, In addition, it can be considered that the stability over time is also improved because the components having a large change over time can be very small under the barrier layer.

  1 which is the scope of the present invention will be described.

  It is a graph in which the horizontal axis represents the thickness of the gas barrier layer and the vertical axis represents the integrated light quantity of excimer light required for modification. As already described, in order to produce a high-performance and stable barrier layer, it is necessary to form a layer having a sufficient degree of modification and a small gradient of the degree of modification in the thickness direction.

As a result of intensive studies by the present inventors, the film thickness of the barrier layer is 30 nm or more and 500 nm or less, and when the excimer light energy applied for film formation is in the range of 100 mJ / cm ² or more and 8400 mJ / cm ² or less, the film A reforming gradient in the thickness direction is small, and a high-performance and stable barrier layer can be formed. When the thickness of the barrier layer is smaller than 30 nm, the barrier performance is hardly exhibited. When the thickness is larger than 500 nm, the modification of the portion near the substrate is difficult to proceed, and it is difficult to reduce the thickness direction gradient of the modification degree. come. For this reason, defects are likely to occur during film formation, and stability over time also deteriorates.

As for the integrated light amount, if the energy is less than 100 mJ / cm ^2, it is difficult to achieve high barrier performance due to insufficient modification, and even if energy greater than 8400 mJ / cm ² is applied, the barrier performance is saturated. Not only will it end up, it may turn into degradation. Perhaps, this is because the rate of excimer light used to destroy the barrier film increases rather than the energy used for film formation.

Furthermore, when a thin barrier film is formed, the modification energy required for the entire film is reduced. Therefore, a suitable point exists with a smaller energy than when a thick barrier film is formed. It has been found that it is necessary to give a larger energy when forming the film than when forming a thin barrier film. As a result of detailed studies by the inventors on this point, when the film thickness is 30 nm or more and 200 nm or less, it is preferable that the film thickness is 100 mJ / cm ² or more and 7500 mJ / cm ² or less. In the case of forming a film with a thickness (d) greater than 200 nm and less than or equal to 500 nm, a straight line of d = 200 (nm) and d = 500 (nm) and J (integrated energy) = 3 × It is understood that the treatment is preferably performed under conditions in a range surrounded by a straight line represented by d (barrier film thickness) −500 and a straight line represented by J (integrated energy) = 3 × d (barrier film thickness) +6900. It was.

In FIG. 1, for the linear expression J (integrated energy) = 3 × d (barrier film thickness) −500J ≧ 3d−500 indicating the lower limit of the integrated light quantity, the water vapor transmission rate is as follows at film thicknesses of 200 nm, 300 nm, 400 nm, and 500 nm. The range of the integrated light amount including a point indicating a value of 2 × 10 ⁻³ or less, which is a preferable value, respectively, and the integrated light amount that becomes a point exceeding this value when the water vapor transmission rate is 200 nm, 300 nm, 400 nm, or 500 nm. The boundary to be removed is shown by an expression. The boundary is almost a straight line with this gradient.

  For the straight line represented by the equation of J (integrated energy) = 3 × d (barrier film thickness) +6900 indicating the upper limit of the integrated light quantity, the equation has the same gradient when the allowable upper limit value is observed for each film thickness. (See Example data).

  When modifying a thick film (d = 200 nm or more) with a film thickness in the above range, the surface portion directly exposed to excimer light and the portion on the substrate side where the excimer light attenuates and reaches due to absorption of the film itself are modified. The quality speed will vary greatly. For this reason, it is expected that the reforming degree gradient in the film thickness direction increases as the reforming of the surface portion proceeds. It can be easily imagined that the magnitude of the modification degree gradient depends on the film thickness of the film before the modification. The reason is not clear, but if the relationship between the film thickness and the integrated light amount is within the above range, it is considered that a highly stable barrier layer is formed by the magnitude of the reforming gradient falling within a certain range. It is done.

  That is, within the scope of the present invention, by forming a barrier layer, it is possible to form a barrier layer having a small degree of modification gradient in the film thickness direction and excellent stability while having high barrier performance. Become.

  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.

(Substrate temperature during irradiation with vacuum ultraviolet light)
The substrate temperature at the time of irradiation with vacuum ultraviolet light is preferably warmed from room temperature to 150 ° C. or lower. More preferably, it is preferable to carry out at a temperature not higher than the Tg (glass transition temperature) of the base material, where the base material is difficult to be thermally deformed. However, the temperature can be raised to Tg or higher as long as the deformation of the substrate can be mechanically suppressed by a back roll or a tenter clip. In addition, in order to suppress as much as possible the influence of the deformation and fluctuation of the base material due to heat during the reforming treatment on the barrier layer formation, the base material is heated to the temperature at the time of processing in advance, and is in a thermal equilibrium state It is also effective to suppress the thermal fluctuation of the base material during the modification treatment.

  Although it is possible to set the temperature higher than 150 ° C., the temperature range in which a general-purpose resin substrate can be used is preferably 150 ° C. or lower.

(Addition of catalyst to the barrier layer)
In order to promote the formation reaction of the barrier layer and to reduce the low reforming portion, it is preferable to add a known catalyst such as an amine catalyst to the barrier layer precursor. However, since the catalyst itself can also be a gas barrier defect, the addition in the range of 0.1% by mass to 5% by mass with respect to the barrier layer precursor material is preferable, and more preferably 0.3% by mass to The addition amount is 3% by mass, more preferably 0.5% by mass to 1.5% by mass. If it is lower than this range, there is almost no effect of adding the catalyst. If it is added more than this range, the catalyst starts to act as a defect, and even if the reforming conditions are strengthened, the barrier performance cannot be improved.

(Lamination of gas barrier layer)
It is also preferable to stack a plurality of gas barrier layers formed by the method of the present invention in order to realize high gas barrier performance. In the method of laminating, a precursor layer having a polysilazane skeleton is further applied within the scope of the present invention to a gas barrier layer obtained by modifying a precursor layer having a polysilazane skeleton within the scope of the present invention. Arbitrary layers can be stacked by repeating the reforming process sequentially. By laminating in this way, not only can the gas barrier layer not be cracked easily while increasing the total film thickness of the barrier layer, but also the leveling effect for each layer and defects such as pinholes formed in the lower layer The effect of repairing can also be obtained. This is an effect peculiar to the coating type, and means that defects in the lower layer can be canceled while directly laminating the inorganic layer, which is difficult in the vapor deposition system film formation.

(Coating film of polysilazane-containing liquid)
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. A compound having a partial structure represented by the following general formula (I).

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 that is ceramicized at a low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with a polysilazane having a partial structure represented by the above general formula (I) (Japanese Patent Laid-Open No. 5-23827) Glycidol-added polysilazane obtained by reacting glycidol (JP-A-6-122852), alcohol-added polysilazane obtained by reacting alcohol (JP-A-6-240208), and metal carboxylate Metal carboxylate-added polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal fine particles are added Metal particles obtained Pressurized polysilazane (JP-A-7-196986) 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, usually 20% RH to 90% RH, more preferably 30% RH to 80% RH.

<Reforming treatment>
As 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 (water and adsorbed oxygen contained in the material are also considered as an oxygen source), 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.

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

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

  Among them, it is preferable to perform the treatment by irradiation with vacuum ultraviolet light 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 light 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 light. The treatment by irradiation with vacuum ultraviolet light uses light energy of 100 to 200 nm, which is larger than the interatomic bonding force in the compound, and is oxidized by active oxygen or ozone while directly cutting the bonds of the atoms by the action of only photons called photon processes. This is a method of forming a film at a relatively low temperature by advancing the reaction.

  As the vacuum ultraviolet light source, 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. .

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

Therefore, in this invention, it is preferable to perform the modification | reformation process which gives the maximum irradiation intensity | strength of 100-200 mW / cm < ² > at least once in a vacuum ultraviolet light 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.

<Oxygen concentration during irradiation with vacuum ultraviolet light>
In the present invention, the oxygen concentration at the time of irradiation with vacuum ultraviolet light is preferably 10 ppm to 50000 ppm (5%). More preferably, it is 1000 ppm to 10000 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.

  The thickness of the smooth layer used in the present invention improves the smoothness of the substrate, facilitates the adjustment of the balance of the optical characteristics of the substrate, and provides a film when the smooth layer is provided only on one side of the substrate. From the viewpoint of preventing curling, the range of 1 μm to 10 μm is preferable, and the 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. The present invention includes an organic light emitting layer in which the functional layer is a thin film and is a current-driven device, This is particularly effective when the layer includes an organic photoelectric conversion layer.

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

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

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

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

Examples of the sealing member include the barrier film of the present invention, polyethylene terephthalate, polycarbonate, polystyrene, nylon, polyvinyl chloride, 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.

<Package presentation>
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. .

<Measuring method>
(Film 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 <N / O ratio between 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)
<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.

<Ca method used for evaluation of the present invention>
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
Production of cell for evaluating water vapor barrier property A part (12 mm) of a barrier film sample to be vapor-deposited before applying a transparent conductive film on a gas barrier layer surface of the barrier film sample using a vacuum vapor deposition apparatus (vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.) Other than 9 x 12 mm masks, metal calcium was vapor-deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After 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.

<Preparation of substrate>
(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 6 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.

<Example 1: No catalyst, treatment at room temperature>
Integration of the film thickness of the gas barrier layer obtained by vacuum ultraviolet light treatment and the irradiated vacuum ultraviolet light on the base material in which an organic layer (smooth layer) is formed on the resin substrate as shown in Tables 1 and 2. Samples with different amounts of light were prepared, and the water vapor transmission rate was measured by the aforementioned Ca evaluation. Normally, the time during which Ca was corroded by 1% was measured and the water vapor transmission rate was calculated in a certain evaluation area, but the time during which Ca was corroded by 50% was also measured to see if there was a rapid deterioration. It was judged that the longer the 50% corrosion time, the more rapid deterioration of the barrier performance was suppressed.

(Formation of gas barrier layer)
SAMCO UV ozone cleaner Model UV-1 was used to adjust the ozone concentration to 300 ppm while substituting the atmosphere at the time of irradiation with nitrogen, and surface treatment at 80 ° C. for 3 minutes was performed to form an organic layer. Went to wood.

  A dibutyl ether solution (percentage of perhydropolysilazane as a silicon compound-containing liquid adjusted to a desired film thickness on the surface of the substrate on which the organic layer surface has been surface-treated (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NN120-20, none) Using a catalyst type, diluting solution: dehydrated dibuty ether), spin coating (5000 rpm, 60 seconds) was applied, followed by drying at 80 ° C. for 10 minutes to form a precursor film containing a silicon compound.

  Thereafter, using a stage movable xenon excimer irradiation device MODEL: MECL-M-1-200 manufactured by MD Excimer, the oxygen concentration of the atmosphere in the irradiation chamber is controlled to 0.1% using nitrogen and oxygen. The sample was reciprocated at a stage moving speed of 10 mm / second and irradiated with vacuum ultraviolet rays. The peak illuminance and integrated light quantity were measured using an illuminometer H95535-172 (manufactured by Hamamatsu Photonics) having sensitivity at 172 nm while transporting under the same conditions.

(conditions)
Excimer light intensity: 120 mW / cm ² (172 nm)
Distance between sample and light source: 3mm
Stage heating temperature: 25 ° C (room temperature)
The evaluation results of Example 1 are shown in Tables 1 and 2.

As is apparent from the table, the water vapor permeability [g / (m ² · 24h)] calculated from the 1% corrosion of Ca can be kept low by performing the treatment with the film thickness and the integrated light quantity within the range of the present invention. In addition to this, it can be seen that the 50% corrosion time also becomes longer, and rapid deterioration of the barrier performance is suppressed.

  Further, it can be seen that even if excimer light is irradiated beyond the scope of the present invention, the performance hardly changes or shows a tendency to deteriorate.

  Furthermore, it can be seen that when a film having a thickness greater than 200 nm is modified, the barrier performance is drastically increased within the scope of claim 2 of the present invention, and in particular, the time to 50% corrosion is extended. As explained earlier, by forming a modified layer with a certain degree of barrier performance, the strength gradient in the film thickness direction falls within an appropriate range, so that the overall strength of the film can be balanced and rapid breakdown is suppressed. It is thought that. It can be seen that the 50% corrosion time is particularly deteriorated when the integrated light quantity is further increased. This is because a harder and more fragile modified layer is formed on the surface side, while the lower part of the film thickness direction (base material side) does not advance due to light attenuation, and the degree of modification is unbalanced again This is thought to occur.

<Example 2: Addition of catalyst>
The perhydropolysilazane material used in Example 1 and the same material mixed with an amine catalyst (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NAX120-20 (amine catalyst 5% by mass)) and a dibuty ether solution of the same amine catalyst ( 10 mass%), dehydrated dibutyl ether for dilution, and coating solutions with different catalyst concentrations as shown in Tables 3 and 4 were prepared. Under the same conditions, a sample was prepared in which the catalyst concentration and the integrated amount of irradiated vacuum ultraviolet light were changed.

  The evaluation results of Example 2 are shown in Tables 3 and 4.

  As is clear from Tables 3 and 4, the gas barrier film to which the catalyst was added within the scope of the present invention had a lower integrated light amount (= short-time reforming treatment) than Example 1, and It can be seen that similar barrier performance can be obtained.

<Example 3: Temperature at the time of vacuum ultraviolet light irradiation>
In the same manner as the sample having a barrier layer thickness of 100 nm prepared in Example 1, the base material was changed to polyether sulfone (Tg = 220 ° C.), and only the temperature at the time of vacuum ultraviolet light irradiation was changed as shown in Table 5. A sample was made. In addition, the temperature at the time of vacuum ultraviolet light irradiation heated the stage which sets a sample, and made the setting temperature the temperature at the time of irradiation. That is, it is a process of irradiating vacuum ultraviolet light after the sample itself is in a thermal equilibrium state by heating the time during which the irradiation atmosphere is replaced with 0.1% oxygen concentration from the atmosphere.

  The evaluation results of Example 3 are shown in Table 5.

  As is apparent from Table 5, it can be seen that both the 1% corrosion time and the 50% corrosion time are greatly improved by applying the temperature during irradiation with vacuum ultraviolet light within the scope of the present invention. The treatment efficiency is further improved by processing at a high temperature, but the improvement width is becoming smaller at 150 ° C. or higher.

  Although not shown in the table, when polyester (PET) is used as a base material in the same manner as in Example 1, the base material is greatly deformed by the 170 ° C. treatment, and partly cracks due to the deformation. Has occurred. That is, in order to use a general-purpose and inexpensive resin base material, it is understood that treatment at 150 ° C. or lower is preferable.

<Example 4: Lamination of barrier layer>
The first barrier layer was formed under the conditions that the temperature during vacuum ultraviolet light irradiation was 80 ° C. and the film thickness after modification was 100 nm using the perhydropolysilazane solution of Example 1, and the second layer under the same conditions. A two-layer laminated sample and a three-layer laminated sample formed with the third layer were produced by changing the integrated light quantity per layer.

  The evaluation results of Example 4 are shown in Table 6.

  As apparent from Table 6, by laminating the barrier layer formed within the scope of the present invention, high barrier properties can be obtained even with a low integrated amount of light (short-time modification treatment) in which the vacuum ultraviolet light irradiated per layer is low. It can be seen that stability can be realized.

<Evaluation as a gas barrier film for organic thin film devices>
Using 1-3 (comparative example), 1-11, 1-19, 1-35, 1-53 (comparative example), 2-19, 3-3, 4-3, 4-11 as the sealing film Then, an organic photoelectric conversion element and an organic light emitting element were prepared, subjected to an accelerated deterioration treatment for 1000 hours in an environment of 60 ° C. and 90% RH, and compared with the performance before the accelerated deterioration, the gas barrier performance and its stability were evaluated.

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

(Evaluation 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 using a film with accelerated deterioration treatment was calculated against the absence of accelerated deterioration of the gas barrier film, and was ranked as follows.

Conversion efficiency maintenance ratio = Conversion efficiency of the element using the film subjected to accelerated deterioration treatment / Conversion efficiency of the element using the film without accelerated deterioration treatment × 100 (%)
◎: 90% or more ○: 60% or more, less than 90% △: 20% or more, less than 60% ×: less than 20% (Evaluation 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 2 mm square, visually observed, the situation of black spots is examined, and the performance maintenance rate when using a film with accelerated deterioration is calculated against the absence of accelerated deterioration of the gas barrier film. Ranking was done.

300-hour life maintenance ratio = area of black spots generated in the element using the film subjected to accelerated deterioration treatment / area of black spots generated in the element using the film not subjected to the accelerated deterioration treatment × 100 (%)
◎: 90% or more ○: 60% or more, less than 90% Δ: 20% or more, less than 60% ×: less than 20% <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. 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 (manufactured by Prectronics: regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Co., Ltd .: 6,6-phenyl-C61-butyric acid methyl ester) are added to 3.0% by mass of chlorobenzene. 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 according to the following procedure 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.

  The evaluation results of Example 5 are shown in Table 7.

  As is apparent from the table, the performance change of the organic thin film device is very small in the element using the gas barrier film of the present invention without accelerated deterioration treatment. That is, it can be seen that it has high gas barrier properties and stability that can be maintained for a long time.

  In particular, when used as a sealing material for organic EL elements, even if a minute defect occurs, the light emitting element is affected. Therefore, if a sealing material that is thick and easily cracks is used, stable performance can be obtained. I can't understand.

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 (8)

A gas barrier property comprising silicon oxide or silicon oxynitride by providing a silicon compound layer having a polysilazane skeleton on at least one surface of a resin substrate, and modifying the silicon compound layer by irradiating with vacuum ultraviolet light having a wavelength of 200 nm or less In the manufacturing method of the gas barrier film which forms a layer, the gas barrier film is formed on the conditions which satisfy | fill following (Formula 1), The manufacturing method of the gas barrier film characterized by the above-mentioned.
(Formula 1)
30 nm ≦ d ≦ 500 nm and 100 mJ / cm ² ≦ J ≦ 8400 mJ / cm ²
d: Modified layer thickness (nm) after the silicon compound layer is modified by irradiation with vacuum ultraviolet light
J: Integrated light quantity of vacuum ultraviolet light (mJ / cm ² ) The method for producing a gas barrier film according to claim 1, wherein the following (Equation 2) is further satisfied.
(Formula 2)
In the case of 30 nm ≦ d ≦ 200 nm 100 mJ / cm ² ≦ J ≦ 7500 mJ / cm ²
When 200 nm ≦ d ≦ 500 nm J ≧ 3d−500 and J ≦ 3d + 6900   The method for producing a gas barrier film according to claim 1, wherein a plurality of the gas barrier layers are laminated.   The method for producing a gas barrier film according to any one of claims 1 to 3, wherein 0.1 to 5.0 mass% of a catalyst is added to the silicon compound layer having the polysilazane skeleton.   5. The method for producing a gas barrier film according to claim 1, wherein the temperature at the time of irradiation with vacuum ultraviolet light is a temperature of 25 ° C. or more and 150 ° C. or less.   An organic electronic device using a gas barrier film produced by the method for producing a gas barrier film according to claim 1.   The organic electronic device according to claim 6, wherein the organic electronic device is an organic photoelectric conversion element.   The organic electronic device according to claim 6, wherein the organic electronic device is an organic electroluminescence element.

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