JP5849726B2 - Method for producing water vapor barrier film - Google Patents

Description

The present invention relates to a method for producing a water vapor barrier film.

Conventionally, a water vapor barrier film formed by laminating a plurality of layers including a thin film of a metal oxide such as aluminum oxide, magnesium oxide, silicon oxide on the surface of a plastic substrate or film is an article that needs to block water vapor. For example, it is widely used in packaging applications for preventing deterioration of foods, industrial products, pharmaceuticals and the like.
In addition to packaging applications, development to flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, etc. has been demanded, and many studies have been made. However, these flexible electronic devices are required to have a water vapor barrier property at a glass substrate level, so that a water vapor barrier film having sufficient performance has not been obtained yet.

As a method of forming such a water vapor barrier film, a chemical deposition method in which an organic silicon compound typified by tetraethoxysilane (TEOS) is used to form a film on a substrate while being oxidized by oxygen plasma under reduced pressure ( Gas phase methods such as plasma CVD (Chemical Vapor Deposition) and physical deposition methods (vacuum evaporation method or sputtering method) in which metal Si is evaporated using a semiconductor laser and deposited on a substrate in the presence of oxygen are known.
These inorganic vapor deposition methods have been preferably applied to the formation of inorganic films such as silicon oxide, silicon nitride, and silicon oxynitride, and the composition range of the inorganic film for obtaining a good water vapor barrier property. Many studies have been made and studies have been made on the layer structure including these inorganic films, but it has not been possible to specify a composition range or a layer structure in which the water vapor barrier property is particularly good.
Furthermore, it is very difficult to form a film having no defects by the above-described vapor phase method. For example, it is necessary to extremely reduce the film forming rate to suppress the generation of defects. For this reason, at the industrial level where productivity is required, the water vapor barrier property required for flexible electronic devices has not been obtained. Studies such as simply increasing the film thickness of the inorganic film by the vapor phase method or laminating a plurality of inorganic films have been made, but since defects grow continuously or cracks increase, the water vapor barrier property It has not improved.
In contrast, by forming multiple layers of inorganic films and organic films alternately by the vapor phase method, the total thickness of the inorganic film is ensured without continuously growing the defects, and the defect surface of each inorganic film is further improved. Studies have been made to increase the water vapor transmission path length due to the difference in the inward position, that is, to improve the water vapor barrier property by the so-called maze effect. However, at present, it cannot be said that the water vapor barrier property is sufficient, and further, it is considered difficult to put it to practical use in terms of cost because the process is complicated and the productivity is remarkably low.

As one of the methods for solving the above problems, studies have been made to improve the water vapor barrier property by modifying a coating layer formed by applying a solution of an inorganic precursor compound and drying it by heat or light. In particular, studies have been made to develop a high water vapor barrier property by using polysilazane as an inorganic precursor compound.
Polysilazane is a compound having a basic structure of — (SiH ₂ —NH) — (example of perhydropolysilazane). When polysilazane is subjected to heat treatment or wet heat treatment in an oxidizing atmosphere, it changes to silicon oxide via silicon oxynitride. At this time, since direct substitution from nitrogen to oxygen is caused by oxygen or water vapor in the atmosphere, it changes to silicon oxide with a relatively small volume shrinkage, so that there are relatively few defects in the film due to the volume shrinkage. It is known that a stable film can be obtained. By controlling the oxidizing property of the atmosphere, a relatively dense silicon oxynitride film can be obtained.
However, the formation of a dense silicon oxynitride film or silicon oxide film by thermal modification or wet heat modification of polysilazane requires a high temperature of 450 ° C. or higher, and cannot be applied to a flexible substrate such as plastic. It was.
As a means for solving such a problem, a method of forming a silicon oxynitride film or a silicon oxide film by applying vacuum ultraviolet light to a coating film formed from a polysilazane solution has been proposed.
A photon called a photon process that bonds atoms using a light energy of 100 to 200 nm called vacuum ultraviolet light (hereinafter also referred to as “VUV” or “VUV light”) having an energy larger than each interatomic bonding force of polysilazane. As a result of only the action, the oxidation reaction with active oxygen or ozone proceeds while cutting directly, so that a silicon oxynitride film or a silicon oxide film can be formed at a relatively low temperature.
Non-Patent Document 1 discloses a method for producing a water vapor barrier film by irradiating a polysilazane coating film with VUV light using an excimer lamp. However, the layer configuration and production conditions have not been studied in detail, and the water vapor barrier property of the obtained water vapor barrier film is not at all equivalent to the water vapor barrier property required for flexible electronic devices.

In Patent Document 1, water vapor is obtained by laminating two or more water vapor barrier layers irradiated with VUV light on a polysilazane coating film having a film thickness of 250 nm or less on a resin substrate having a smooth surface (surface Ra value less than 12 nm). A barrier film is disclosed. By making the polysilazane coating film a thin layer, crack generation at the time of VUV light irradiation is suppressed, and it is attempted to improve the water vapor barrier property by multilayering this to increase the water vapor barrier property. If the thickness exceeds a certain value, cracks are still generated, so that the water vapor barrier property required for the flexible electronic device cannot be obtained.
On the other hand, Patent Document 2 discloses a water vapor barrier film having a thermosetting silicon-containing organic-inorganic composite copolymer film in which polysilazane and a polysiloxane polymer are mixed. Although this organic-inorganic composite copolymer film is flexible and can suppress the occurrence of cracks, it exhibits flexibility at the expense of the water vapor barrier property of polysilazane. It is only used as an oxide layer adhesion imparting / stress relieving layer. The water vapor barrier inorganic oxide used has a visible light transmittance of less than 90%, which is not sufficient for use in flexible electronic devices.
Thus, there has been a demand for a water vapor barrier film having very high water vapor barrier properties and transparency required for flexible electronic devices and the like.

JP 2009-255040 A JP 2010-167777 A

Leibniz Institute of Surface Modification Biological Report 2008/2009: P18-P21

The present invention has been made in view of the above problems, its object is to provide a method of producing a water-vapor barrier film that have a have a high water vapor barrier properties, and transparency.

The present invention has been achieved by the following means.
1. A method for producing a water vapor barrier film in which a water vapor barrier layer and a protective layer are laminated on a substrate, comprising polysilazane, and containing 0.1 to 10 parts by mass of an amine compound with respect to 100 parts by mass of polysilazane. A step of applying the first coating liquid onto the substrate and drying, followed by irradiation with vacuum ultraviolet light to form the water vapor barrier layer; and containing polysiloxane and amine with respect to 100 parts by mass of the polysiloxane Applying a second coating liquid containing 0.1 to 10 parts by mass of the compound on the water vapor barrier layer and drying, followed by irradiating vacuum ultraviolet light to form the protective layer. A method for producing a water vapor barrier film.
2. The method for producing a water vapor barrier film according to 1 above, wherein the amine compound is an aliphatic amine compound.
3 , the amine compound is N, N-diethylethanolamine, triethylamine, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl- It is 1 , 6- diaminohexane, The manufacturing method of the water vapor | steam barrier film of said 1 or 2 characterized by the above-mentioned.
4. The water vapor barrier according to any one of 1 to 3, wherein the amine compound contained in the water vapor barrier layer is 0.15 to 15 parts by mass when the polysilazane is 100 parts by mass. A method for producing a film.
5. The water vapor barrier according to any one of 1 to 4, wherein the amine compound contained in the protective layer is 0.1 to 10 parts by mass when the polysiloxane is 100 parts by mass. A method for producing a film.
6. The water vapor barrier layer has a thickness of 50 nm or more and 1 μm or less, and the protective layer has a thickness of 50 nm or more and 10 μm or less. A method for producing a water vapor barrier film.
7, the integrated light quantity of vacuum ultraviolet light to be irradiated during formation of the water vapor barrier layer is 1000 mJ / cm ² or more 10000 mJ / cm ² or less, the integrated light quantity of vacuum ultraviolet light to be irradiated during formation of said protective layer, method for producing a water vapor barrier film according to any one of the 1 to 6, characterized in that 100 mJ / cm ² or more 10000 mJ / cm ² or less.
8. The water vapor barrier film according to any one of 1 to 7 above, wherein the base material has a linear expansion coefficient of 50 ppm / ° C. or less and a total light transmittance of 90% or more. Manufacturing method.

According to the present invention, high water vapor barrier properties have, and which has excellent transparency, it can be excellent in water resistance and heat resistance, obtaining a method for producing a water vapor barrier fill beam with a temporal stability.

It is explanatory drawing which shows an example of the water vapor | steam barrier film which concerns on this invention. It is explanatory drawing which shows an example of the water vapor | steam barrier film which concerns on this invention. It is sectional drawing which shows an example of the organic electroluminescent panel which sealed the organic electroluminescent element using the water vapor | steam barrier film.

Hereinafter, preferred embodiments for carrying out the present invention will be described with reference to the drawings. However, although various technically preferable limitations for implementing the present invention are given to the embodiments described below, the scope of the invention is not limited to the following embodiments and illustrated examples.
The water vapor barrier film (10, 11) according to the present invention comprises at least one water vapor barrier layer 2 and at least one layer covering the water vapor barrier layer 2 on a gas permeable substrate 1 such as a resin film. And a protective layer 3.
The water vapor barrier layer 2 is a layer formed by applying a first coating liquid containing polysilazane and drying it, followed by irradiation with vacuum ultraviolet light.
The protective layer 3 is a layer formed by applying a second coating solution containing polysiloxane and drying it, followed by irradiation with vacuum ultraviolet light.
Moreover, you may provide the smooth layer 4 and an anchor-coat layer in the base-material surface as an intermediate | middle layer for improving the smoothness of the base material 1, and the adhesiveness of the water vapor | steam barrier layer 2 with respect to the base material 1. FIG.
Moreover, in order to prevent the base material 1 from being scratched or soiled, a so-called bleed-out layer is suppressed so that when the base material 1 is heated, low molecular weight components such as monomers and oligomers are deposited from the inside to the surface. For this purpose, a bleed-out prevention layer 5 may be provided on the surface of the substrate.
Specifically, the water vapor barrier film 10 according to the present invention includes, for example, as shown in FIG. 1, a water vapor barrier layer 2 and a protective layer that are sequentially laminated on a base 1 and one surface of the base 1. 3 is provided.
Moreover, the water vapor | steam barrier film 11 which concerns on this invention is laminated | stacked on the smooth layer 4 and the smooth layer 4 formed in the one surface of the base material 1, the base material 1, as shown in FIG. In addition, a water vapor barrier layer 2 and a protective layer 3 are provided, and a bleed-out preventing layer 5 is provided on the other surface of the substrate 1.
Hereinafter, the structure of the water vapor | steam barrier films 10 and 11 of this invention is demonstrated in detail.

(Base material)
The gas-permeable substrate constituting the water vapor barrier film of the present invention is preferably a flexible bendable film substrate. The substrate is not particularly limited as long as it is a film-like substrate capable of holding a water vapor barrier layer and a protective layer.
Here, the base material having gas permeability in the present invention is based on JIS standard K7129 method (temperature 40 ° C., humidity 90% RH) using PERMATRAN-W3 / 33 manufactured by MOCON according to the Mocon method. It is defined that the measured water vapor transmission rate is 0.5 g / m ² / day or more.
Examples of the resin base material applicable to the base material of the water vapor barrier film include acrylic acid ester, methacrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), and polyarylate. , Polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, etc. Resin film made of resin material, heat-resistant transparent film (product name: Silplus, manufactured by Nippon Steel Chemical Co., Ltd.) with silsesquioxane having organic-inorganic hybrid structure as basic skeleton, and 2 resin films as described above Can be used consists laminated resin film is laminated over.
Among these resin films, films such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), and polycarbonate (PC) are preferably used in terms of cost and availability.
In addition, when high temperature treatment is required in the processing step for sealing the device, a transparent polyimide film having both heat resistance and transparency, for example, transparent polyimide film type HM manufactured by Toyobo Co., Ltd., Mitsubishi Gas Chemical Co., Ltd. Transparent polyimide-based film Neoprim L L-3430, etc. manufactured by Co., Ltd. can be preferably used.
As for the thickness of the base material used for this invention, about 5-500 micrometers is preferable, More preferably, it is 25-250 micrometers.
In addition, the base material using the resin material may be an unstretched film or a stretched film.
Moreover, the base material which consists of said resin material can be manufactured by a conventionally well-known general manufacturing method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Further, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). Although the draw ratio in this case can be suitably selected according to the resin used as the raw material of the base material, it is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.
Moreover, it is preferable that the linear expansion coefficient of the base material used for this invention is 50 ppm / degrees C or less, More preferably, they are 1 ppm / degrees C or more and 50 ppm / degrees C or less.
By applying a substrate having a linear expansion coefficient of 50 ppm / ° C. or less, when the water vapor barrier film of the present invention is used in a liquid crystal display device (LCD panel), it is possible to suppress the occurrence of color misregistration with respect to environmental temperature changes and the like. it can. Further, it is possible to reduce the stress load due to the base material expansion and contraction applied to the barrier film.
The linear expansion coefficient prescribed | regulated by this invention can be calculated | required in accordance with the following method, for example.
After raising the temperature of the substrate to be measured from 30 ° C. to 50 ° C. at a rate of 5 ° C. per minute in a nitrogen atmosphere using an EXSTAR TMA / SS6000 type thermal stress strain measuring device manufactured by Seiko Instruments Inc. , Hold once, raise the temperature again at a rate of 5 ° C. per minute, measure the value at 30-150 ° C., and obtain the linear expansion coefficient. Measurement is performed in a tensile mode with a load of 5 g.
The base material used in the present invention preferably has a total light transmittance of 90% or more. By applying a base material having a total light transmittance of 90% or more, high brightness can be obtained when the water vapor barrier film of the present invention is used in a liquid crystal display device (LCD panel).
The total light transmittance referred to in the present invention is determined by measuring the total transmitted light amount with respect to the incident light amount of visible light according to ASTM D-1003 standard using a spectrophotometer (visible ultraviolet spectrophotometer UV-2500PC Shimadzu Corporation). The average transmittance in the region was defined as the total light transmittance.

(Water vapor barrier layer)
In the present invention, a method of forming a polysilazane modified layer can be applied as a method of forming a water vapor barrier layer on a substrate. As a preferred embodiment of this method, a first coating solution containing polysilazane and an amine compound is coated on a substrate by a wet coating method and dried, and then the dried coating film is irradiated with vacuum ultraviolet light. This is a method of forming a water vapor barrier layer as a polysilazane modified layer. At this time, it is preferable that 0.1 to 10 parts by mass of an amine compound is contained in the first coating solution, where 100 parts by mass of polysilazane is 100. In addition, since the weight of the amine compound with respect to the polysilazane mass part is approximately 1.55 times the weight of the coating film with respect to the solid content weight in the liquid, when the polysilazane is 100 mass parts in the barrier layer, It is preferable to contain 0.15-15 mass parts of amine compounds.
“Polysilazane” used for the water vapor barrier layer is a polymer having a silicon-nitrogen bond, and SiO ₂ , Si ₃ N ₄ having a bond such as Si—N, Si—H, or N—H, and an intermediate solid solution SiO of both. a ceramic precursor inorganic polymers, such as _x N _y.
As a method of applying the first coating liquid containing the polysilazane onto a substrate or the like, a conventionally known appropriate wet coating method can be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

The coating thickness of the water vapor barrier layer can be appropriately set according to the purpose. For example, the coating thickness of the water vapor barrier layer is preferably about 10 nm to 10 μm, more preferably 50 nm to 1 μm after drying. If the thickness of the water vapor barrier layer is 50 nm or more, sufficient barrier properties can be obtained. Moreover, if the film thickness is 1 μm or less, high light transmittance can be realized, and stable coating can be performed when forming the water vapor barrier layer.
Moreover, it is preferable that a water vapor | steam barrier layer is formed through the heating process whose heating temperature is 50 to 200 degreeC. When the heating temperature is 50 ° C. or higher, sufficient barrier properties can be obtained, and when the heating temperature is 200 ° C. or lower, a highly smooth water vapor barrier layer can be formed without deformation of the substrate. A heating method using a hot plate, an oven, a furnace, or the like can be applied to this heating step. Further, the heating atmosphere may be any condition such as air, nitrogen atmosphere, argon atmosphere, vacuum, or reduced pressure with controlled oxygen concentration.

  Further, the polysilazane is preferably a compound that is ceramicized at a relatively low temperature and modified to silica so as to be applied so as not to impair the properties of the substrate. For example, the following general formula described in JP-A-8-112879 A compound having a main skeleton composed of the unit represented by (1) is preferred.

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. Represent.
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 water vapor barrier layer to be obtained.
In addition, the organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like has an alkyl group such as a methyl group, thereby improving adhesion with a base material as a base and being hard. The ceramic film made of brittle polysilazane can be provided with toughness, and even when the film thickness (average film thickness) is made thicker, the occurrence of cracks can be suppressed. Accordingly, 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. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.
As another example of polysilazane which becomes ceramic at low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with a polysilazane having a main skeleton composed of a unit represented by the general formula (1) (for example, Japanese Patent Laid-Open No. Hei. No. 5-238827), glycidol-added polysilazane obtained by reacting glycidol (for example, see JP-A-6-122852), and alcohol-added polysilazane obtained by reacting alcohol (for example, JP-A-6-240208). Gazette), metal carboxylate-added polysilazanes obtained by reacting metal carboxylates (for example, see JP-A-6-299118), and acetylacetonate complexes obtained by reacting metal-containing acetylacetonate complexes Additional polysilazanes (for example, See JP -306329), a metal fine metal particles added polysilazane obtained by adding (e.g., JP-see JP 7-196986), and the like.
As the organic solvent for preparing the first coating solution containing polysilazane, it is not preferable to use an alcohol or water-containing one having a characteristic that easily reacts with polysilazane. Therefore, specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers can be used. . Specifically, there are hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to characteristics such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.
The polysilazane concentration in the first polysilazane-containing coating solution varies depending on the film thickness of the target polysilazane coating film and the pot life of the coating solution, but is preferably about 0.2 to 35 parts by mass.
In the first coating liquid containing polysilazane, a Pt compound (for example, Pt acetylacetonate), a Pd compound (for example, Pd propionic acid), an Rh compound (for example, Pt acetylacetonate) is used as necessary in order to promote conversion into a silicon oxide compound. A metal catalyst such as Rh acetylacetonate can also be added.
An amine compound is added to the first coating liquid containing polysilazane for improving the adhesion to the protective layer. The amine compound used in the present invention includes primary amine, secondary amine or tertiary amine monomers, and polymers thereof in general, and the structure and molecular weight thereof are not particularly limited. An aromatic amine compound, an aromatic amine compound, an alicyclic amine compound, a heterocyclic amine compound, and the like.

  Examples of such amine compounds include, for example, n-propylamine, cyclopropylamine, allylamine, n-butylamine, isobutylamine, sec-butylamine, diethylamine, dimethylaminoethanol, diethanolamine, n-amylamine, tert-amylamine, isoamylamine, 2-aminopentane, cyclopentylamine, 3-aminopentane, 1,2-dimethylpropylamine, N-ethylisopropylamine, N-ethyl-n-propylamine, N-methyl Isobutylamine, N-methyl-n-butylamine, N-tert-butylethylamine, N, N-dimethylisopropylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, Ethylamine, triethanolamine, 3-dimethylaminopropionitrile, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, n-hexylamine, cyclohexaneamine, 1,3-dimethyl-n-butylamine, Diisopropylamine, diallylamine, dipropylamine, Nn-butylethylamine, N-tert-butylethylamine, Nn-butyldimethylamine, n-heptylamine, aminomethylcyclohexane, cycloheptylamine, 4-methylcyclohexylamine, 2-methylcyclohexylamine, N-methylcyclohexylamine, N, N-diethylallylamine, 3-diethylamino-1,2-propanediol, 1-diethylamino-2-propanol, n-octyl Amine, 2-aminooctane, 1,5-dimethylhexylamine, cyclooctylamine, 2-ethylhexylamine, dibutylamine, N-ethylcyclohexylamine, N-cyclohexylethanolamine, N, N-diisopropylethylamine, N, N- Dimethylcyclohexylamine, 3,3,5-trimethylcyclohexylamine, N-isopropylcyclohexylamine, tripropylamine, triallylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, N, N-diethylcyclohexylamine, N, N -(Dimethyl-n-octylamine, 3-di-n-butylamino-1-propyne, triisobutylamine, tributylamine, dicyclohexylamine, N, N-dicyclohexylmethylamine , Diheptylamine, triamylamine, triisoamylamine, N-methyldi-n-octylamine, trihexylamine, N-methyldi-n-octylamine, N, N-dimethylhexadecylamine, tri-n-heptylamine And aliphatic monoamine compounds such as tri-n-octylamine, 1,3-diaminopropane, N-methylethylenediamine, 1,3-diamino-2-propanol, 2-methyl-1,3-propanediol, diethylenetriamine, 1 , 4-diaminobutane, N-methyl-1,3-diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diaminopentane, N-methyl-2,2′-diaminodiethylamine, N- ( 2-hydroxypropyl) ethylenediamine, N, N-dimethyl-1,3-pro Diamine, N- (3-hydroxypropyl) ethylenediamine, 3-morpholinopropylamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,2-cyclohexanediamine, 3,3′-diaminodipropylamine, tri Ethylenetetramine, N, N-diethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, 2,2-tetramethyl-1,3 -Propanediamine, N, N-bis (3-aminopropyl) methylamine, N, N'-dimethyl-1,6-diaminohexane, 1,3-bis (aminoethyl) cyclohexane, 1,4-bis (amino) Methyl) cyclohexane, N, N, N ′, N′-tetramethyl-1,4-diaminobutane, N, N, N ′, N ′ Tetramethyl-1,3-diaminobutane, 1,8-diaminooctane, 4-amino-1-diethylaminopentane, N- (3-aminopropyl) cyclohexylamine, N, N, N ′, N′-tetramethyl- Aliphatic polyamines such as 1,6-diaminohexane, N, N′-diethyl-1,6-diaminohexane, 4,4′-methylenebis (cyclohexylamine) and 2,4,6-tris (dimethylaminomethyl) phenol Compounds.

  Examples of the aromatic amine compound include aniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiol, 3-aminobenzenethiol, 4-aminobenzenethiol, 2-chloroaniline, 3- Chloroaniline, 4-chloroaniline, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-iodoaniline, 3-iodoaniline, 4- Iodoaniline, o-toluidine, p-toluidine, N-methylaniline, 3,4-methylenedioxyaniline, 2-amino-p-cresol, 2-aminobenzonitrile, 3-aminobenzonitrile, 4-aminobenzonitrile 2,6-dimethylaniline, 3,5-di Tyraniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethylaniline, N, N-dimethylaniline, 2-ethylaniline, 3-ethylaniline, N-ethyl Aniline, N, N-dimethyl-3-aminophenol, 4-methoxy-2-methylaniline, 4-aminophthalonitrile, o-ethoxyaniline, p-ethoxyaniline, 2,4,6-trimethylaniline, N-isopropyl Aniline, 2- (N-methylanilino) ethanol, N-allylaniline, N-ethyl-o-toluidine, N-ethyl-p-toluidine, 4-dimethylaminobenzaldehyde, N, N-dimethyl-p-toluidine, 2- Propylaniline, 4-propylaniline, 2-isopropylaniline, 3- Sopropylaniline, 4-isopropylaniline, 1-naphthylamine, Nn-butylaniline, 2- (N-ethylanilino) ethanol, N- (2-cyanoethyl) -N-methylaniline, 1-phenyl-2-pyrrolidone, 4-butylaniline, 2-butylaniline, 4-sec-butylaniline, 4-tert-butylaniline, N, N-diethyl-m-toluidine, 4-diethylaminobenzaldehyde, N, N-diethyl-3-aminophenol, Nn-pentylaniline, N, N-diethyl-o-toluidine, N- (4-aminophenyl) piperidine, N, N-di-n-propylaniline, N, N-dimethyl-2-naphthylamine, N, N -Dimethyl-1-naphthylamine, diphenylamine, N-ethyl-1-naphthylami , 3-aminobiphenyl, 2-aminobiphenyl, 4-aminodiphenyl ether, 2-aminophenyl, 2-aminophenylphenyl sulfide, N-methyldiphenylamine, 3-methyldiphenylamine, 4-aminodiphenylmethane, 4-aminobenzophenone, N , N-diethyl-1-naphthylamine, m, m′-ditolylamine, N-benzyl-N-ethylaniline, N-phenyl-1-naphthylamine, triphenylamine, Nn-dodecylaniline, bis (4-tert- Butylphenyl) amine, 4,4′-dimethyltriphenylamine, 1,1′-dinaphthyleneamine, 1,2′-dinaphthyleneamine and N, N-dibenzylaniline, and the like, 1,4-phenylenediamine, 1,2-phenol Range amine, 1,3-phenylenediamine, 2,4-diaminotoluene, 3,4-diaminotoluene, 2,6-diaminotoluene, 2-aminobenzylamine, 3-aminobenzylamine, 4-aminobenzylamine, 2 , 5-dimethyl-1,4-phenylenediamine, 4,5-dimethyl-1,2-phenylenediamine, N, N-dimethyl-1,4-phenylenediamine, N-phenylethylenediamine, 2,4,6-trimethyl -1,3-phenylenediamine, 2,3-diaminonaphthalene, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, N, N-diethyl-1,4-phenylenediamine, tryptamine, N-1-naphthylethylenediamine N- (3-aminopropyl) -N-methylaniline, N- (2-aminoethyl) ) -N-ethyl-m-toluidine, 3,3′-diaminobenzidine, 3,3′-dihydroxybenzidine, bis (4-aminophenyl) sulfide, bis (2-aminophenyl) sulfide, bis (4-aminophenyl) ) Sulfone, bis (3-aminophenyl) sulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminobenzophenone, 3,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4-diaminobenzophenone 2,7-diaminofluorene, 4,4′-methylenebis (2-chloroaniline), o-tolidine, 4,4′-ethylenedianiline, 2,2′-ethylenedianiline, N, N-diphenylethylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, bis [4 -(Dimethylamino) phenyl] methane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-methylenebis (2-ethyl-6-methylaniline) and N, N'-di-2- Examples include aromatic polyamine compounds such as naphthyl-1,4-phenylenediamine.

  Examples of the alicyclic amine compound include pyrrolidine, 3-pyrrolidinol, 2-pyrrolidone, piperazine, 1-methylpyrrolidine, piperidine, 4-aminopiperidine, 4-hydroxypiperidine, 2-piperidone, N-ethylpyrrolidone, 1-methyl. Piperidine, 3-pipecoline, 4-pipecoline, hexamethyleneimine, 2-pipecoline, N-ethylpyrrolidone, 4- (aminomethyl) piperidine, 1- (2-aminoethyl) pyrrolidine, 4-hydroxy-1-methylpiperidine, 3,5-dimethylpiperidine, 1-ethylpiperidine, 2,6-dimethylpiperidine, 2-ethylpiperidine, 1- (2-aminoethyl) piperidine, 2-piperidineethanol, 1-methyl-2-piperidinemethanol, decahydro Isoquinoxaline, Decahi Rokinorin, 2,2,6,6-tetramethylpiperidine, 1- (3-aminopropyl) -2-pipecoline and 1-cyclohexyl piperazine, and the like.

  Examples of the heterocyclic amine compound include N-methylimidazole, pyrrole, pyrazine, pyridazine, 2-methylimidazole, 4-methylimidazole, pyridine, 1-methylpyrrole, 4-aminopyridine, 4-hydroxypyridine, and 3-hydroxy. Pyridine, 2-hydroxypyridine, 2-mercaptopyridine, 2,6-diaminopyridine, 1,2-dimethylimidazole, 2-picoline, 2,5-dimethylpyrrole, 4-cyanopyridine, 4-pyridinecarboxaldehyde, 4- Methoxypyridine, 4-pyridinemethanol, 4-picolylamine, 3-amino-4-picoline, 2-n-propyl-2-imidazoline, 2-ethyl-4-methylimidazole, 4-ethylpyridine, 3,5-lutidine 2,6-lutidine, 2-vinyl pyridine Gin, 4-vinylpyridine, 3-ethylpyridine, 2-ethylpyridine, 4- (2-aminoethyl) pyridine, 2-acetylpyridine, 3-acetylpyridine, 3-ethylpyridine, 3-pyridineacetonitrile, 2-pyridine Acetonitrile, 2- (2-aminoethyl) pyridine, 2-pyridineethanol, 2-cyano-3-methylpyridine, 4-dimethylaminopyridine, quinoxaline, 4-n-propylpyridine, 2-propylpyridine, 5-ethyl-2 -Picoline, 2,4,6-trimethylpyridine, 2,3,5-trimethylpyridine, indole, N-ethyl-4-picolylamine, 1-cyanoethyl-2-methylimidazole, 2-methylindole, isoquinoline, Quinoline, N-methylindole, 4-tert-butyl Lysine, 3-butylpyridine, 5,6,7,8-tetrahydroisoquinoline, 2-phenylimidazole, 4- (3-pentyl) pyridine, 7-methylquinoline, 4-methylquinoline, 6-methylquinoline, 1-benzyl 2-methylimidazole, carbazole, iminostilbene, 2-undecylimidazole and 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) nonene-5, etc. Is mentioned.

Here, it is preferable that the amine compound is colorless and transparent from the viewpoint that the water vapor barrier film can be used for a display. The refractive index of the amine compound is preferably 1.4 to 1.5. If the refractive index is within this range, the optical properties of the film made of polysilazane can be maintained, and therefore the transparency of the water vapor barrier film can be improved. From this viewpoint, the amine compound is N, N-diethylethanolamine, triethylamine, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl- 1,6-diaminohexane is preferred.
Specific examples of the polysilazane solution include NN120-20 manufactured by AZ Electronic Materials Co., Ltd.
The amount of the amine compound added to the polysilazane is preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.2 to 5 parts by mass, and in the range of 0.5 to 2 parts by mass. More preferably it is. Since the amine compound also acts as a curing catalyst for polysilazane, it is easy to achieve both this effect and the catalytic function if it is 0.1 to 10 parts by mass. In addition, since the weight of the amine compound with respect to the polysilazane mass part is approximately 1.55 times the weight of the coating film with respect to the solid content weight in the liquid, when the polysilazane is 100 mass parts in the barrier layer, It is preferable to contain 0.15-15 mass parts of amine compounds.

In the water vapor barrier layer formed by the first polysilazane-containing coating solution used in the present invention, the amount of moisture contained before or during the modification treatment by vacuum ultraviolet light irradiation is preferably controlled.
Examples of the water supply source that can enter the polysilazane layer (polysilazane film) before or during the modification treatment by vacuum ultraviolet light irradiation include migration from the substrate surface or absorption of water vapor in the atmosphere. . Control of moisture transferred from the substrate side into the polysilazane layer is to store the substrate in a constant temperature and humidity environment before applying the polysilazane-containing coating solution, and control the water content to a desired value. it can. The desired value varies depending on the humidity in the atmosphere described later, but is usually 1000 ppm or less, preferably 300 ppm or less as a mass.
In the step of applying and drying the first polysilazane-containing coating solution on the substrate and the like, mainly removing the organic solvent, the drying conditions can be appropriately determined by a method such as heat treatment, and the heat treatment temperature is rapid. Although it is preferable that it is high temperature from a viewpoint of a process, it is preferable to determine suitably temperature and processing time in consideration of the heat damage with respect to the base material which is a resin film. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate, the heat treatment temperature can be set to 150 ° C. or less. The treatment time is preferably set to a short time so that the solvent is removed and thermal damage to the substrate is reduced. If the heat treatment temperature is 150 ° C. or lower, the treatment time can be set within 30 minutes.
The atmosphere in the step of applying and drying the polysilazane-containing coating solution for forming a water vapor barrier layer (first coating solution) on the substrate is preferably controlled to be relatively low humidity, but the humidity in a low humidity environment is Since it changes with temperature, the relationship between temperature and humidity shows a preferable form by the definition of dew point temperature. A preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −8 ° C. (temperature 25 ° C./humidity 10%) or less, and a more preferable dew point temperature is −31 ° C. (temperature 25 ° C./temperature). Humidity 1%) or less. Moreover, you may dry under reduced pressure in order to make it easy to remove a water | moisture content. The pressure in the vacuum drying can be selected from normal pressure to 0.1 MPa.
The polysilazane modification treatment in the present invention refers to a reaction in which part or all of the polysilazane compound is converted into silicon oxide or silicon oxynitride.
For this modification treatment, a known method based on the conversion reaction of polysilazane can be selected. Formation of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a polysilazane compound requires a high temperature of 450 ° C. or higher, and is difficult to adapt to a flexible substrate using a resin film as a base material. Therefore, when producing the water vapor barrier film of the present invention, from the viewpoint of application to a plastic substrate, a method of modifying by irradiation with vacuum ultraviolet light, which allows a conversion reaction at a lower temperature, is applied.

In the method for producing a water vapor barrier film in the present invention, the dried polysilazane coating film from which moisture has been removed is modified by treatment with vacuum ultraviolet light irradiation. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperatures. It is.
This vacuum ultraviolet light irradiation excites and activates O ₂ and H ₂ O, UV absorbers, and polysilazane itself that contribute to ceramicization. And the ceramicization of the excited polysilazane is promoted, and the resulting ceramic film becomes dense. Irradiation with ultraviolet light is effective at any time after the formation of the coating film.
Any commonly used ultraviolet ray generator can be used for the vacuum ultraviolet ray irradiation treatment in the present invention. In addition, the vacuum ultraviolet light as used in the field of this invention means the ultraviolet light containing the electromagnetic wave which has a wavelength of 10-200 nm.
In the irradiation with vacuum ultraviolet light, it is preferable to set the irradiation intensity and the irradiation time within a range in which the base material carrying the pre-modified polysilazane layer to be irradiated is not damaged.
Taking a case of using a plastic film as a base material, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the base material surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the substrate and the vacuum ultraviolet irradiation lamp can be set so as to be ^2, and irradiation can be performed for 0.1 seconds to 10 minutes.
Particularly, in the present invention, the integrated light quantity of vacuum ultraviolet light when the polysilazane layer reforming to form a water vapor barrier layer, 1000 mJ / cm ² or more, preferably 10,000 / cm ² or less. If the cumulative amount of vacuum ultraviolet light is 1000 mJ / cm ² or more, a sufficient barrier property can be obtained, and if it is 10,000 mJ / cm ² or less, a water vapor barrier layer having high smoothness without deformation of the substrate is obtained. Can be formed.
In general, when the substrate temperature at the time of ultraviolet irradiation is 150 ° C. or more, when the substrate is a plastic film or the like, the properties of the substrate are impaired, for example, the substrate is deformed or its strength is deteriorated. become. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.
Examples of such vacuum ultraviolet ray generating means include an excimer lamp. In addition, when irradiating the pre-modified polysilazane layer with the generated ultraviolet light, the ultraviolet light from the generation source is reflected by the reflector plate from the viewpoint of improving the irradiation efficiency and achieving uniform irradiation. It can also be applied to the polysilazane layer.
The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. When the substrate having a polysilazane layer is in the form of a long film, it can be converted into ceramics by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. . The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although depending on the base material used and the composition and concentration of the polysilazane layer.
Moreover, it is preferable that oxygen concentration at the time of irradiating with vacuum ultraviolet light (VUV) is 300 ppm to 10000 ppm (1%), and more preferably 500 ppm to 5000 ppm. By adjusting to such an oxygen concentration range, it is possible to prevent formation of an oxygen-rich water vapor barrier layer and to prevent deterioration of barrier properties.
A dry inert gas is preferably used as a gas other than oxygen at the time of vacuum ultraviolet light (VUV) irradiation, and dry nitrogen gas is particularly preferable from the viewpoint of cost.
The oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

In the present invention, as described above, the method for modifying the polysilazane layer before modification is treatment by irradiation with vacuum ultraviolet light. The treatment by vacuum ultraviolet light irradiation uses light energy of 100 to 200 nm, preferably light energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and the bonding of atoms is called a photon process called a photon process. This is a method in which a silicon oxide film is formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by only the action. As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.
In addition, since atoms of rare gases such as Xe, Kr, Ar, and Ne are not chemically bonded to form molecules, they are called inert gases. However, a rare gas atom (excited atom) that has gained energy by discharge or the like can be combined with another atom to form a molecule. For example, when the rare gas is xenon,
e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Then, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light (vacuum ultraviolet 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. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.
In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge refers to lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. It is a similar very thin discharge called micro discharge.
In addition to dielectric barrier discharge, electrodeless field discharge is also known as a method for efficiently obtaining excimer light emission. The electrodeless field discharge is a discharge due to capacitive coupling, and is also called an RF discharge. The lamp, the electrode, and the arrangement thereof may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. In the electrodeless field discharge, a spatially and temporally uniform discharge can be obtained in this way.
The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. 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 to low-pressure mercury lamps and plasma cleaning that emit ultraviolet rays with wavelengths of 185 nm and 254 nm, the process time is shortened due to high throughput, the equipment area is reduced, and organic materials, plastic substrates, resin films, etc. that are easily damaged by heat are used. Can be irradiated.
In addition, since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy of a single wavelength is irradiated in the ultraviolet region, so that an increase in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for the irradiation to the water vapor | steam barrier film which uses resin films, such as a polyethylene terephthalate considered to be easy to be influenced by heat, as a base material.

(Protective layer)
In the present invention, a method of forming a polysiloxane modified layer can be applied as a method of forming a protective layer on the water vapor barrier layer. As a preferred embodiment of this method, a second coating solution containing polysiloxane and an amine compound is coated on the water vapor barrier layer by a wet coating method and dried, and then the dried coating film is irradiated with vacuum ultraviolet light. This is a method for forming a protective layer as a polysiloxane modified layer. Under the present circumstances, it is preferable that 0.1-10 mass parts of amine compounds are included with respect to 100 mass parts of polysiloxane.
The polysiloxane applicable to the formation of the protective layer is not particularly limited, but an organopolysiloxane represented by the following general formula (2) is particularly preferable.
In the present embodiment, an organopolysiloxane represented by the general formula (2) will be described as an example of polysiloxane.

In the general formula (2), R ^{3 to} R ⁸ each represent the same or different organic group having 1 to 8 carbon atoms. R ^{3 to} R ⁸ include either an alkoxy group or a hydroxyl group. m is 1 or more.
Examples of the organic group having 1 to 8 carbon atoms represented by R ^{3 to} R ⁸ include halogenated alkyl groups such as γ-chloropropyl group and 3,3,3-trifluoropropyl group, vinyl group, and phenyl group. , (Meth) acrylic acid ester groups such as γ-methacryloxypropyl group, epoxy-containing alkyl groups such as γ-glycidoxypropyl group, mercapto-containing alkyl groups such as γ-mercaptopropyl group, γ-aminopropyl group, etc. Isocyanate-containing alkyl groups such as aminoalkyl groups and γ-isocyanatopropyl groups, linear or branched alkyl groups such as methyl groups, ethyl groups, n-propyl groups and isopropyl groups, alicyclic alkyl groups such as cyclohexyl groups and cyclopentyl groups Group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, etc. Group, an acetyl group, a propionyl group, a butyryl group, valeryl group, etc. acyl group such as caproyl group.
Further, in the present invention, in the general formula (2), an organopolysiloxane in which m is 1 or more and the weight average molecular weight in terms of polystyrene is 1,000 to 20,000 is particularly preferable. If the weight average molecular weight in terms of polystyrene of the organopolysiloxane is 1000 or more, the protective layer to be formed is hardly cracked and can maintain the water vapor barrier property, and if it is 20,000 or less, it is formed. Curing of the protective layer is sufficient, so that sufficient hardness can be obtained as the protective layer obtained.

Examples of the organic solvent that can be used for forming the protective layer include alcohol solvents, ketone solvents, ester solvents, aprotic solvents, and the like.
Here, as the alcohol solvent, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, 2- Butoxyethanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, 1-butoxy-2-propanol, 3-methoxy-1-butanol and the like are preferable. These alcohol solvents may be used alone or in combination of two or more.
Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl. In addition to ketones, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, acetylacetone, 2,4-hexanedione, 2 , 4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl 3,5-heptanedione, 1,1,1,5,5,5 beta-diketones such as hexafluoro-2,4-heptane dione and the like. These ketone solvents may be used alone or in combination of two or more.
Examples of ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, and iso acetate. -Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, acetic acid Diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid Glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate , Diethyl malonate, dimethyl phthalate, diethyl phthalate and the like. These ester solvents may be used alone or in combination of two or more.
As aprotic solvents, acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N -Methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl Examples include 2-imidazolidinone and 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone. The above organic solvents can be used alone or in combination of two or more.
In the present invention, the organic solvent used for forming the protective layer is preferably an alcohol solvent among the above organic solvents.

An amine compound is added to the second coating liquid containing polysiloxane in order to improve the adhesion to the barrier layer and the performance of the protective layer. By adding an amine compound, a stable barrier layer property is exhibited over time.
The amine compound used in the present invention includes primary amine, secondary amine or tertiary amine monomers, and polymers thereof in general, and the structure and molecular weight thereof are not particularly limited. An aromatic amine compound, an aromatic amine compound, an alicyclic amine compound, a heterocyclic amine compound, and the like. Specifically, a compound similar to the amine compound used in the first coating solution containing the polysilazane can be used.
Here, it is preferable that the amine compound is colorless and transparent from the viewpoint that the water vapor barrier film can be used for a display. The refractive index of the amine compound is preferably 1.4 to 1.5.
If the refractive index is within this range, the optical characteristics of the film made of polysiloxane can be maintained. From this viewpoint, the amine compound is N, N-diethylethanolamine, triethylamine, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl- 1,6-diaminohexane is preferred.
The amount of the amine compound added to the polysiloxane is preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.2 to 5 parts by mass, and in the range of 0.5 to 2 parts by mass. More preferably. Since the amine compound also acts as a curing catalyst for the polysiloxane, it is easy to achieve both this effect and the catalytic function at 0.1 to 10 parts by mass.
Examples of the method for applying the second coating solution for forming the protective layer include spin coating, dipping, roller blades, and spraying methods.
The thickness of the protective layer formed by the second coating liquid for forming the protective layer is preferably in the range of 50 nm to 10 μm. If the thickness of the protective layer is 50 nm or more, barrier properties under high humidity can be ensured. Moreover, if the thickness of the protective layer is 10 μm or less, stable coating properties can be obtained when forming the protective layer, and high light transmittance can be realized.
The protective layer has a film density of usually 0.35 to 1.2 g / cm ³ , preferably 0.4 to 1.1 g / cm ³ , more preferably 0.5 to 1.0 g / cm ^3. It is. If the film density is 0.35 g / cm ³ or more, sufficient mechanical strength of the coating film can be obtained.
The protective layer in the present invention is formed by applying a second coating solution containing polysiloxane on the water vapor barrier layer by a wet coating method and drying, and then irradiating the dried coating film with vacuum ultraviolet light. It is preferable.
As the vacuum ultraviolet light used for forming this protective layer, vacuum ultraviolet light by vacuum ultraviolet light irradiation treatment similar to that described in the formation of the water vapor barrier layer can be applied.
In the present invention, the integrated light quantity of vacuum ultraviolet light when forming the protective layer by reforming polysiloxane membrane, 100 mJ / cm ² or more, preferably 10,000 / cm ² or less. A sufficient barrier performance can be obtained if the accumulated amount of vacuum ultraviolet light is 100 mJ / cm ² or more, and if it is 10,000 mJ / cm ² or less, a protective layer having high smoothness without deforming the substrate. Can be formed.
Moreover, it is preferable that the protective layer in this invention is formed through the heating process whose heating temperature is 50 degreeC or more and 200 degrees C or less. If the heating temperature is 50 ° C. or higher, sufficient barrier properties can be obtained, and if it is 200 ° C. or lower, a protective layer having high smoothness can be formed without deforming the substrate. A heating method using a hot plate, an oven, a furnace, or the like can be applied to this heating step. Further, the heating atmosphere may be any condition such as air, nitrogen atmosphere, argon atmosphere, vacuum, or reduced pressure with controlled oxygen concentration.

(Other component layers)
Next, constituent layers other than the water vapor barrier layer and the protective layer used in the water vapor barrier film of the present invention will be described.

(Anchor coat layer)
In the water vapor barrier film of the present invention, an anchor coat layer is formed on the base material from the viewpoint of improving the adhesion between the water vapor barrier layer and the base material and obtaining high smoothness as an intermediate layer as necessary. May be.
Examples of the anchor coating agent used for forming this anchor coat layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, and alkyl titanates. Can be used alone or in combination of two or more. Conventionally known additives can be added to these anchor coating agents.
The above anchor coating agent is coated on the substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and an anchor coating layer is formed by drying and removing the solvent, diluent, etc. can do.
The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ^{2 in} a dry state.

(Smooth layer)
Moreover, in the water vapor | steam barrier film of this invention, you may provide a smooth layer as an intermediate | middle layer on a base material. The smooth layer is formed on one surface of the substrate.
The smooth layer flattens the rough surface of the substrate where minute protrusions and the like exist, and prevents unevenness and pinholes from forming on the water vapor barrier layer formed on the substrate by protrusions on the substrate surface. Provided for. Such a smooth layer is formed, for example, by curing a photosensitive resin.
Examples of the photosensitive resin used for forming the smooth layer include a resin composition containing an acrylate compound having a radical reactive unsaturated bond, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, and an epoxy. Examples thereof include resin compositions in which polyfunctional acrylate monomers such as acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are dissolved. Further, any mixture of the above resin compositions can be used, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There is no particular limitation. The reactive monomer can be used as one or a mixture of two or more or as a mixture with other compounds.
The composition of the photosensitive resin contains a photopolymerization initiator. A photoinitiator can be used 1 type or in combination of 2 or more types.
The method for forming the smooth layer on the surface of the substrate is not particularly limited. For example, a spin coating method, a spray method, a blade coating method, a wet coating method such as a dip method, or a dry coating method such as a vapor deposition method. It is preferable to form by.
Moreover, when forming a smooth layer, additives, such as antioxidant, a ultraviolet absorber, a plasticizer, can be added to above-described photosensitive resin as needed. In addition, an appropriate resin or additive may be used for improving the film formability on the formed smooth layer, preventing pinholes from being formed on the film formed on the smooth layer, or the like.

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

The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. If Rt is 10 nm or more, the coating property is stable when the coating means comes into contact with the surface of the smooth layer by a coating method such as a wire bar or a wireless bar at the stage of coating the water vapor barrier layer coating liquid to be formed later. Is obtained. Moreover, if Rt is 30 nm or less, the unevenness | corrugation after apply | coating the water vapor | steam barrier layer coating liquid formed after that can be smooth | blunted.
In addition, one of preferred embodiments as an additive to be added when forming the smooth layer is a reactive silica particle in which a photosensitive group having photopolymerization reactivity is introduced into the photosensitive resin (hereinafter simply referred to as a reaction). Also referred to as silica particles). Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The photosensitive resin also 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 a thing. 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 diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By making the average particle diameter in such a range, by using it in combination with a matting agent made of inorganic particles having an average particle diameter of 1 to 10 μm, which will be described later, optical properties satisfying a good balance between antiglare property and resolution. Further, it becomes easy to form a smooth layer having both hard coat properties. From the viewpoint of making it easier to obtain such an effect, it is more preferable to use reactive silica particles having an average particle size of 0.001 to 0.01 μm.
In the present invention, the smooth layer preferably contains the inorganic particles as described above in a mass ratio of 20% to 60%. By adding 20% or more, adhesion with the water vapor barrier layer is improved. On the other hand, if it is 60% or less, curving of the film can be suppressed, cracking can be prevented when heat treatment is performed, and optical properties such as transparency and refractive index of the water vapor barrier film can be affected. There is no.
In the present invention, the polymerizable unsaturated group-modified hydrolyzable silane seems to be chemically bonded to the silica particles by generating a silyloxy group by the hydrolysis reaction of the hydrolyzable silyl group. Can be used as reactive silica particles. Examples of the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl 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.
In the present invention, the thickness of the smooth layer is 1 to 10 μm, preferably 2 to 7 μm. By making the thickness of the smooth layer 1 μm or more, the smoothness as a water vapor barrier film having a smooth layer can be easily made sufficient. Moreover, by making the thickness of the smooth layer 10 μm or less, it becomes easy to adjust the balance of the optical characteristics of the water vapor barrier film, and the water vapor barrier film when the smooth layer is provided only on one surface of the water vapor barrier film. It becomes possible to make it easy to suppress curling.

(Bleed-out prevention layer)
Moreover, in the water vapor | steam barrier film of this invention, you may form a bleed out prevention layer in the back surface side surface of a base material.
The bleed-out prevention layer is a group having a smooth layer for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the base material to the surface when the film having the smooth layer is heated to contaminate the film surface. Provided on the opposite side of the material. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.
The unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer includes a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or Mention may be made of 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 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. . 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 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.
In addition, 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.
Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like. Resins, acetal resins such as polyvinyl formal, polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonate resins, etc. Can be mentioned.
Examples of the thermosetting resin include a thermosetting urethane resin composed of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicon resin.
The ionizing radiation curable resin is cured by irradiating an ionizing radiation (ultraviolet ray or electron beam) to an ionizing radiation curable paint in which one or more of photopolymerizable prepolymer or photopolymerizable monomer is mixed. Things can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.
As photopolymerization initiators, acetophenone, benzophenone, Michler ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl)- 1-propane, α-acyloxime ester, thioxanthone and the like can be mentioned.
The bleed-out prevention layer as described above is prepared by adding a hard coating agent, a matting agent, and other components added as necessary, and adding a predetermined dilution solvent to prepare a coating solution. It can form by apply | coating to the surface of a material with 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, a method of irradiating ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 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, or the like, or This can be performed by a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.
The thickness of the bleed-out prevention layer is 1 to 10 μm, preferably 2 to 7 μm. By setting the thickness of the bleed-out prevention layer to 1 μm or more, it becomes easy to make the heat resistance as a water vapor barrier film sufficient. In addition, by adjusting the thickness of the bleed-out prevention layer to 10 μm or less, it becomes easy to adjust the balance of the optical characteristics of the water vapor barrier film, and the water vapor barrier when the smooth layer is provided on one surface of the water vapor barrier film. It becomes possible to easily suppress curling of the film.

(Organic EL panel as an electronic device)
The water vapor barrier film 10 (11) according to the present invention can be used as a sealing film for sealing electronic devices such as solar cells, liquid crystal display elements, and organic EL elements.
An example of the organic EL panel 20 which is an electronic device using the water vapor barrier film 10 (11) as a sealing film is shown in FIG.
As shown in FIG. 3, the organic EL panel 20 is formed on the water vapor barrier film 10 through the water vapor barrier film 10, the transparent electrode 6 such as ITO formed on the water vapor barrier film 10, and the transparent electrode 6. The organic EL element 7 and a counter film 9 disposed via an adhesive layer 8 so as to cover the organic EL element 7 are provided. It can be said that the transparent electrode 6 forms part of the organic EL element 7.
The transparent electrode 6 and the organic EL element 7 are formed on the surface of the water vapor barrier film 10 on which the protective layer is formed.
The counter film 9 may be a water vapor barrier film according to the present invention in addition to a metal film such as an aluminum foil. When a water vapor barrier film is used for the counter film 9, the surface on which the protective layer is formed may be attached to the organic EL element 7 with the adhesive layer 8.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<Production of base material>
[Production of substrate (a)]
As a thermoplastic resin substrate (support), a 125 μm thick polyester film (extra-low heat yield PET Q83, manufactured by Teijin DuPont Films Ltd.) that is easily bonded on both sides is used. A bleed-out prevention layer having a smooth layer formed on the opposite surface was used as the base material (a).

<Formation of bleed-out prevention layer>
A UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied to one surface side of the thermoplastic resin base material under the condition that the film thickness after drying was 4.0 μm, and then cured. As a condition, a bleed-out prevention layer was formed by performing a curing treatment for 3 minutes at 80 ° C. under a dry condition using a high-pressure mercury lamp in an air atmosphere with an irradiation energy amount of 1.0 J / cm ² .

<Formation of smooth layer>
Next, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is applied to the surface of the thermoplastic resin substrate opposite to the surface on which the bleed-out prevention layer is formed. After coating under the condition of 4.0 μm, after drying at 80 ° C. for 3 minutes, using a high pressure mercury lamp in an air atmosphere, the curing condition is irradiation and curing with an irradiation energy of 1.0 J / cm 2. Thus, a smooth layer was formed.
The surface roughness Rz measured according to the method defined in JIS B 0601 of the obtained smooth layer was about 25 nm.
The surface roughness was measured using an AFM (Atomic Force Microscope) SPI3800N DFM manufactured by SII. The measurement range of one time was 80 μm × 80 μm, the measurement location was changed, three measurements were performed, and the average of the Rz values obtained in each measurement was taken as the measurement value.

[Production of substrate (I)]
As a heat-resistant substrate, a 200 μm thick transparent polyimide film (manufactured by Mitsubishi Gas Chemical Co., Ltd., Neoprim L) with easy-adhesion processing on both sides is used. As shown below, a smooth layer is formed on both sides of the substrate. What was formed was made into the base material (I).

(Formation of smooth layer)
<Preparation of smooth layer coating solution>
8.0 g of trimethylolpropane triglycidyl ether (Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), 5.0 g of ethylene glycol diglycidyl ether (Epolite 40E manufactured by Kyoeisha Chemical Co., Ltd.), silsesquioxane having an oxetanyl group: OX-SQ- 12.0 g of H (manufactured by Toagosei Co., Ltd.), 32.5 g of 3-glycidoxypropyltrimethoxysilane, 2.2 g of Al (III) acetylacetonate, methanol silica sol (manufactured by Nissan Chemical Co., Ltd., solid content concentration 30) (Mass%) is 134.0 g, BYK333 (BIC Chemie Japan Co., Ltd., silicon surfactant) 0.1 g, butyl cellosolve 125.0 g, 0.1 mol / L hydrochloric acid aqueous solution 15.0 g is mixed sufficiently. Was stirred. This was further left standing and deaerated at room temperature to obtain a smooth layer coating solution.

<Formation of smooth layer 1>
After applying a corona discharge treatment to one surface side of the heat-resistant substrate by a conventional method, the smooth layer coating solution is applied under the condition that the film thickness after drying is 4.0 μm, and then 3 ° C. at 80 ° C. Dried for minutes. Furthermore, the heat processing for 10 minutes were performed at 120 degreeC, and the smooth layer 1 was formed.

<Formation of smooth layer 2>
A smooth layer 2 was formed on the surface of the heat resistant substrate opposite to the surface on which the smooth layer 1 was formed in the same manner as the method for forming the smooth layer 1.
As a result of measuring the surface roughness of the formed smooth layer 1 and smooth layer 2 in accordance with the method defined in JIS B 0601, it was about 20 nm in Rz. In addition, the measurement of surface roughness was performed by the method similar to having used for preparation of the said base material (a).

<< Production of Water Vapor Barrier Film 1 >> (Comparative Example)
<Formation of water vapor barrier layer>
<Preparation of polysilazane compound-containing coating solution>
A dibutyl ether solution containing 20 parts by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) was used as the polysilazane compound-containing coating solution.

(Formation of polysilazane layer)
On the base material (a), the polysilazane compound-containing coating solution was applied using a spin coater under the condition that the film thickness after drying was 200 nm. After application, it was dried at 100 ° C. for 2 minutes.
(Vacuum ultraviolet irradiation treatment)
After the polysilazane layer coating film was formed as described above, a vacuum ultraviolet ray irradiation treatment was performed according to the following method to form a water vapor barrier layer, and the water vapor barrier film 1 was produced. Details of each processing condition are shown in Table 1.
<Vacuum ultraviolet light irradiation treatment>
The polysilazane coating film was modified by subjecting the sample after the coating film was dried to vacuum ultraviolet light irradiation treatment with the following apparatus and conditions. The number of stage conveyances was set to be the integrated light amount shown in Table 1.
・ Modification processing equipment Excimer irradiation equipment MODEL: MECL-M-1-200 manufactured by M.D.
Wavelength: 172nm
Lamp filled gas: Xe
-Modification treatment conditions Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 3mm
Stage heating temperature: 100 ° C
Oxygen concentration in the irradiation device: 0.2%
Stage transport speed during excimer light irradiation: 10 mm / second The energy applied to the surface of the sample coating layer in the vacuum ultraviolet irradiation process is a 172 nm sensor using a UV integrating photometer: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics. Measurement was performed using a head.

<< Production of Water Vapor Barrier Film 2 >> (Comparative Example)
In preparation of the water vapor barrier film 1, in a dibutyl ether solution containing 20 parts by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.), Table 1 with respect to 100 parts by mass of perhydropolysilazane. Water vapor barrier film 2 in the same manner except that after adding 1 part by mass of N, N, N ′, N′-tetramethyl-1,6-diaminohexane of amine compound 2 shown, a polysilazane compound-containing coating solution was prepared. Was made. In addition, since the weight of the amine compound with respect to the polysilazane mass part is approximately 1.55 times the weight of the coating film with respect to the solid content weight in the liquid, when the polysilazane is 100 mass parts in the barrier layer, 0.15 parts by mass of the amine compound is contained. In description of Table 1, the mass part of the amine compound in a liquid is described.

<< Preparation of Water Vapor Barrier Film 3 >> (Comparative Example)
In the production of the water vapor barrier film 1, a water vapor barrier film 3 was produced by providing a protective layer on the water vapor barrier layer by the following method.
<Formation of protective layer>
(Formation of polysiloxane layer)
On the water vapor | steam barrier layer provided in the water vapor | steam barrier film 1, the said polysiloxane containing solution (JSR Co., Ltd. glassca HPC7003) was apply | coated on the conditions that the film thickness after drying was set to 1000 nm using a spin coater. After application, the film was dried at 120 ° C. for 10 minutes to provide a protective layer.

<< Preparation of Water Vapor Barrier Film 4 >> (Comparative Example)
In the production of the water vapor barrier film 2, the polysiloxane-containing solution (Glaska HPC7003 manufactured by JSR Corporation) was applied onto the water vapor barrier layer under the condition that the film thickness after drying was 1000 nm using a spin coater. Thereafter, a water vapor barrier film 4 was prepared in the same manner except that the protective layer was provided by drying at 120 ° C. for 10 minutes.

<< Preparation of Water Vapor Barrier Film 5 >> (Comparative Example)
In the production of the water vapor barrier film 3, the N, N of the amine compound 2 shown in Table 1 is added to a polysiloxane-containing solution (Glaska HPC7003 manufactured by JSR Corporation) in a polysiloxane-containing solution (100 parts by mass of polysiloxane). , N ′, N′-Tetramethyl-1,6-diaminohexane was added in the same manner except that 1 part by mass was added to form a coating solution, and a water vapor barrier film 5 was produced.

<< Preparation of water vapor barrier film 6 >> ( reference example )
In the production of the water vapor barrier film 4, the N, N of the amine compound 2 shown in Table 1 is added to the polysiloxane-containing solution (Glaska HPC7003 manufactured by JSR Corporation) in the polysiloxane-containing solution (GSRCA HPC7003 manufactured by JSR Corporation). , N ′, N′-Tetramethyl-1,6-diaminohexane was added in the same manner except that 1 part by mass was added to form a coating solution, and a water vapor barrier film 5 was produced.

<< Preparation of water vapor barrier film 7 >> (present invention)
In the production of the water vapor barrier film 6, after forming the polysiloxane layer coating film, in the same manner as the vacuum ultraviolet irradiation treatment for the polysilazane layer, except that the vacuum ultraviolet irradiation treatment to the polysiloxane layer was performed, A water vapor barrier film 7 was produced. Details of each processing condition are shown in Table 1.

<< Preparation of Water Vapor Barrier Films 8-43 >> (Invention and Reference Example )
In the production of the water vapor barrier film 7, water vapor barrier films 8 to 43 were produced in the same manner except that the substrate, amine addition, layer configuration, and vacuum ultraviolet irradiation treatment conditions shown in Table 1 were changed. In addition, the film thickness of each layer was adjusted by adjusting the quantity of the solvent of a coating liquid. For example, in the case of element No. 16, the film thickness was adjusted by diluting with the solvent dibutyl ether of the coating solution 1. Moreover, in the case of element No19, it adjusted so that the film thickness could be thickened by reducing the quantity of the solvent dibutyl ether of the coating liquid 1. FIG.

<< Evaluation 1: Evaluation of water vapor barrier property >>
(Water vapor barrier property evaluation sample preparation device)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation sample)
Using a vacuum deposition apparatus (vacuum deposition apparatus JEE-400 manufactured by JEOL Ltd.), metallic calcium was deposited on the surface of the water vapor barrier layer of the produced water vapor barrier film through a mask in a size of 12 mm × 12 mm.
Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet to perform temporary sealing. Next, the vacuum state is released, quickly transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum deposition surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX). A water vapor barrier property evaluation sample was produced by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.
The obtained sample was stored at 85 ° C. and 90% RH under high temperature and high humidity for 50 hours, and the area where metal calcium corroded relative to the metal calcium deposition area of 12 mm × 12 mm was calculated in%, and water vapor was measured according to the following criteria. Barrier properties were evaluated.
◯: Area where metal calcium was corroded is less than 1.0% Δ: Area where metal calcium was corroded is 1.0% or more and less than 5.0% ×: Area where metal calcium was corroded is 5. Table 2 shows the evaluation results obtained as described above.

<< Evaluation 2: Evaluation of change over time >>
The area where metal calcium corroded when the above water vapor barrier property evaluation sample was stored at 85 ° C. and 90% RH under high temperature and high humidity for 40 hours and 80 hours was calculated in%, respectively. Plotted in a graph to rate. The slope when connecting the origin of the graph with the point after 40 hours and the origin of the graph with the point after the lapse of 80 hours were calculated, and the temporal variability was evaluated according to the following criteria.
○: 80 hour slope / 40 hour slope value is less than 2 Δ: 80 hour slope / 40 hour slope value is 2 or more and less than 4 ×: 80 hour slope / 40 hour slope The value is 4 or more. Table 2 shows the evaluation results obtained as described above.

<< Evaluation 3: Evaluation of transparency >>
Each barrier film was evaluated for transparency using a spectrophotometer (U-3300 manufactured by HITACHI).
In the visible light region (400 to 700 nm), the case where the transmittance was 90% or more was rated as “◯”, the case where it was less than 90%, the case where it was 85% or more, and the case where it was less than 85%. The results are shown in Table 2.

<< Evaluation 4: Evaluation of base material deformability >>
When each barrier film is 10 cm × 10 cm in size and placed on a flat surface, the maximum height difference between the central portion and the corner is 5 mm or less, over 5 mm, and when 10 mm or less, Δ, 10 mm The case where it exceeded was set as x, and it was set as evaluation of substrate deformation. The results are shown in Table 2.

<< Evaluation 5: Evaluation of water resistance >>
Each barrier film was immersed in pure water at 25 ° C. for 24 hours. Further, it was then placed in a 100 ° C. thermo machine for 24 hours. Subsequently, evaluation was performed in the same manner as in the evaluations 1 to 4 of the water vapor barrier property. The results are shown in Table 2.

<< Evaluation 6: Evaluation of heat resistance >>
About the produced water vapor | steam barrier film, it heat-processed in the atmospheric condition for 10 minutes at 120 degreeC. Under the present circumstances, it hold | maintained so that a member might not contact the water-vapor barrier layer surface of a water-vapor barrier film. After the heat treatment, it was taken out into the air at room temperature and cooled to room temperature as it was. Subsequently, evaluation was performed in the same manner as in the evaluations 1 to 4 of the water vapor barrier property. The results are shown in Table 2.

DESCRIPTION OF SYMBOLS 1 Base material 2 Water vapor | steam barrier layer 3 Protective layer 4 Smooth layer 5 Bleed-out prevention layer 7 Organic EL element (electronic device)
10 Water vapor barrier film 11 Water vapor barrier film 20 Organic EL panel (electronic equipment)

Claims (8)

  A method for producing a water vapor barrier film in which a water vapor barrier layer and a protective layer are laminated on a base material, comprising polysilazane and containing 0.1 to 10 parts by mass of an amine compound with respect to 100 parts by mass of polysilazane. The coating liquid is applied onto the substrate and dried, followed by a step of irradiating vacuum ultraviolet light to form the water vapor barrier layer, and containing an amine compound with respect to 100 parts by mass of the polysiloxane. Applying a second coating solution containing 0.1 to 10 parts by mass on the water vapor barrier layer and drying, followed by irradiating with vacuum ultraviolet light to form the protective layer. A method for producing a water vapor barrier film. The method for producing a water vapor barrier film according to claim 1 , wherein the amine compound is an aliphatic amine compound. The amine compound is N, N-diethylethanolamine, triethylamine, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1, It is 6-diaminohexane, The manufacturing method of the water vapor | steam barrier film of Claim 1 or 2 characterized by the above-mentioned. The water vapor barrier film according to any one of claims 1 to 3 , wherein when the polysilazane is 100 parts by mass, the amine compound contained in the water vapor barrier layer is 0.15 to 15 parts by mass. Manufacturing method . The water vapor barrier film according to any one of claims 1 to 4 , wherein when the polysiloxane is 100 parts by mass, the amine compound contained in the protective layer is 0.1 to 10 parts by mass. Manufacturing method . The water vapor barrier layer has a thickness of at least 1μm below 50nm, the protective layer, water vapor according to any one of claims 1 to 5, characterized in that it has a 10μm film thickness of less than 50nm Barrier film manufacturing method . The integrated light quantity of vacuum ultraviolet light to be irradiated during formation of the water vapor barrier layer, 1000 mJ / cm ² or more 10000 mJ / cm ² or less, the integrated light quantity of vacuum ultraviolet light to be irradiated during formation of the protective layer, 100 mJ / method for producing a water vapor barrier film according to any one of claims 1 to 6, characterized in that cm ² or more 10000 mJ / cm ² or less. Before Kimotozai, the linear expansion coefficient of not more than is 50 ppm / ° C., and water vapor barrier film according to any one of claims 1 to 7, the total light transmittance is equal to or less than 90% Manufacturing method .

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