JP2014046272A - Method of manufacturing gas barrier film, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film which exhibits very excellent gas barrier performance as a phase difference film substrate and good productivity, and can be applied to an OLED display, provide a method of manufacturing the gas barrier film which exhibits high barrier performance, excellent bending resistance and smoothness, and has cutting suitability, and provide an electronic device using the gas barrier film.SOLUTION: In a method of manufacturing a gas barrier film having a gas barrier layer formed by irradiating with vacuum ultraviolet light after a process of applying and drying a composition containing a solvent, polysilazane, and an amine compound on a surface of a base material 0, the solvent contains 20-50 mass% of a solvent component of which a Hansen SP value distance Ra with the base material 0 is 8-14, and a boiling point is 70-110°C.

Description

  The present invention relates to a method for producing a gas barrier film and an electronic device using the gas barrier film. More specifically, the present invention is mainly used for a display material such as a package for an electronic device, a plastic substrate for a solar cell, an organic EL element, or a liquid crystal. The present invention relates to a gas barrier film, a manufacturing method thereof, and an electronic device using the gas barrier film.

  Conventionally, a gas barrier film formed by laminating a plurality of layers including a thin film of metal oxide such as aluminum oxide, magnesium oxide, silicon oxide on the surface of a plastic substrate or film is a barrier for various gases such as water vapor and oxygen. For example, it is widely used for packaging of articles that require the use of, for example, packaging 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, in these flexible electronic devices, since a gas barrier property at a glass substrate level is required, a gas barrier film having sufficient performance has not been obtained yet.

  As a method for forming such a gas barrier film, an organic silicon compound typified by tetraethoxysilane (TEOS) is used, which is grown on a substrate while being oxidized with oxygen plasma under reduced pressure (plasma CVD). Gas phase methods such as a chemical vapor deposition (chemical vapor deposition) and a physical deposition method (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 examination of the composition range of the inorganic film for obtaining good gas barrier properties. Many studies have been made on layer structures including these inorganic films. However, it has not yet been possible to specify a composition range or a layer configuration in which gas barrier properties are particularly good.

  Furthermore, it is very difficult to form a film having no defects by the above-described vapor phase method, and it is necessary to take measures such as suppressing the generation of defects by extremely reducing the film forming rate, for example. . For this reason, at the industrial level where productivity is required, the gas barrier properties required for flexible electronic devices have not been obtained. Although studies such as simply increasing the thickness of the inorganic film by the vapor phase method and laminating a plurality of inorganic films have been made, defects continue to grow or cracks increase. It has not improved.

  On the other hand, as one method for forming a gas barrier layer that does not rely on vapor phase film formation as described above, a coating film formed by applying a solution of an inorganic precursor compound on a substrate and drying it is modified by heat or light. Studies have been made to improve gas barrier properties by improving the quality. In particular, studies have been made to develop a high gas 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 into silicon oxide via silicon oxynitride. In this case, since direct substitution from nitrogen to oxygen is caused by oxygen or water vapor in the atmosphere, the volume changes to silicon oxide with relatively little volume shrinkage. It is known that a dense film can be obtained. Then, 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 should be applied to a flexible substrate such as a plastic film. Was impossible.

  As means for solving such a problem, a silicon oxynitride film or a silicon oxide film is formed by irradiating a coating film formed from a polysilazane solution with vacuum ultraviolet light (hereinafter also referred to as “VUV” or “VUV light”). There has been proposed a method for forming the.

  Only photons called photon processes are used to bond atoms using light energy having a wavelength of 100 to 200 nm called vacuum ultraviolet light (hereinafter referred to as “VUV” or “VUV light”) having an energy larger than the bonding force between each atom of polysilazane. The oxidation reaction by active oxygen or ozone can be advanced while being directly cut by the action of. Therefore, the silicon oxynitride film or the silicon oxide film can be formed at a relatively low temperature. This method is also suitable for manufacturing in a roll-to-roll system with good productivity.

Recently, development of a display using an organic thin film light emitting element (OLED) (OLED display) has been energetically advanced. In order to take advantage of the advantages of organic thin films, as for the substrates used in these displays, consideration is given to reducing the weight, preventing cracking of the substrates, replacing glass substrates with plastic substrates, and combining components. ing. Substrates for OLED displays are required to have a very high gas barrier property, also referred to as 10 ⁻⁶ g / m ² / day, in terms of water vapor transmission rate (WVTR).

In an OLED display, in addition to general surface reflection prevention to maintain screen contrast, a circularly polarizing plate is used to reduce contrast due to external light reflection (internal reflection) that occurs mainly at the interface between electrodes and organic layers and inorganic layers. In general, internal reflection prevention is performed. This circularly polarizing plate has a configuration in which a linearly polarizing plate (so-called polarizing plate) and a λ / 4 retardation plate (λ / 4 plate) are bonded to each other, and is arranged with a λ / 4 plate and a polarizing plate from the display element side. When external light is circularly polarized and the phase of the circularly polarized light is reversed during internal reflection, the internally reflected circularly polarized light (inverted phase) is converted again into linearly polarized light by the λ / 4 phase difference plate. When this is returned, the internal reflected light is confined inside the circularly polarizing plate because it cannot pass through the linearly polarizing plate (polarizer). As a result, a decrease in contrast due to internal reflection of external light is prevented, and a decrease in contrast is suppressed. The retardation film and the substrate ^{1 × 10 -5 g / m 2} / day~10 -6 g / m 2 / display substrate of the OLED element by using a day stand gas barrier film to achieve a lambda / It is possible to combine four functions. The material of the film used for such a λ / 4 plate or λ / 2 plate is polycarbonate, polycarbonate copolymer, cycloolefin resin, or cycloolefin copolymer. However, a technique for imparting a high level of gas barrier property as described above to the retardation film has not yet been reported. The following patent documents can be cited as techniques using gas barrier properties and the above-mentioned film materials.

  In Patent Document 1, a film formed of a cyclic olefin and ethylene copolymer having a glass transition temperature of 170 ° C. or higher, and a pressure-sensitive adhesive film are bonded to each other, and a predetermined film is formed on the back surface by plasma chemical vapor deposition. Forming a thick silicon oxide film, and a method for producing a gas barrier film.

  In Patent Document 2, a hard coat layer is formed by applying and curing a light or thermosetting resin composition deposited on the surface of a polycarbonate substrate, and then a chemical layer is formed on the hard coat layer. It is described to form a gas barrier layer by chemical vapor deposition (CVD) or physical vapor deposition (PVD).

  Further, Patent Document 3 describes that a ceramic composition is formed by applying a coating composition containing polysilazane and an aliphatic hydrocarbon solvent on a polycarbonate or polycarbonate copolymer film on at least one surface of the film. Yes.

  Patent Document 4 describes a gas barrier film in which a polysilazane is applied and dried and irradiated with vacuum ultraviolet light to form two gas barrier layers having different nitrogen contents.

  Patent Document 5 describes that a polysilazane layer obtained by applying and drying a solution containing polysilazane and a solvent on a substrate made of a plastic film is irradiated with VUV radiation and UV radiation.

JP 2011-79219 A JP 2004-309932 A JP-A-9-174782 JP 2011-183773 A JP 2009-503157 A

According to paragraph “0008” of Patent Document 1, a synergistic effect is obtained by forming a silicon oxide film on a film made of an addition (co) polymer of a cyclic olefin having a high glass transition temperature by a plasma chemical vapor deposition method. It is said that the water vapor barrier property can be improved. However, according to the Example of the said patent document 1, since the water-vapor-permeation rate of a gas barrier film is 0.01 g / m < ² > * day, it cannot be said that the high gas barrier property as mentioned above is satisfy | filled. Further, in Patent Document 1, since the silicon oxide film is formed by the plasma chemical vapor deposition method, there is a problem that productivity is low.

Furthermore, according to paragraphs “0004” to “0007” of Patent Document 2, the technique of Patent Document 2 solves the problem of peeling due to insufficient adhesion between the hard coat layer and the polycarbonate substrate and the deterioration of gas barrier properties due thereto. However, according to the examples, since the water vapor permeability of the gas barrier film is 0.5 g / m ² · day, it cannot be said that the high gas barrier property as described above is satisfied. Furthermore, in addition to forming a silicon oxide film by plasma CVD, there is a problem that productivity is poor because a hard coat layer is provided.

  Next, according to paragraphs “0006” to “0008” of Patent Document 3, a technique for providing an intermediate layer between polysilazane and polycarbonate was developed in order to solve the problems of modification and whitening of the polycarbonate film. As the coating process has increased and a new problem has arisen that productivity is reduced, the problem of whitening of polycarbonate film and reduction of productivity is solved by using aliphatic hydrocarbon solvent as the solvent of coating solution containing polysilazane. To do. However, since the technique of Patent Document 3 forms a ceramic layer by applying a coating solution and then processing in a high-temperature and high-humidity atmosphere, it is compared with the case where the ceramic layer is formed by irradiation with vacuum ultraviolet light. As a result, the water vapor transmission rate cannot be expected.

  On the other hand, in the technique of Patent Document 4, the gas barrier film in which two gas barrier layers having different nitrogen contents are formed has improved the water vapor barrier property, bending resistance, or smoothness, which are conventional problems. It has been confirmed. However, in the production method of Patent Document 4, when a polysilazane-containing liquid is directly applied to a polycarbonate or polycarbonate copolymer or cycloolefin resin or cycloolefin copolymer as a base material material and irradiated with vacuum ultraviolet light, the barrier film is cracked. It has been confirmed that a new problem will occur.

  Also in Patent Document 5, a polysilazane film is formed on a polyethylene base material in a wet manner, and the barrier layer is formed by oxidative conversion to a silica film by irradiation with excimer radiation, so that the barrier film is cracked. New problems arise.

  The present invention solves such a problem by newly finding a problem that a barrier film precursor is applied to a substrate by a wet method and the barrier film cracks when irradiated with vacuum ultraviolet light. is there. That is, an object of the present invention is to provide a method for producing a gas barrier film that has a very excellent gas barrier performance as a retardation film substrate and good productivity and can be applied to an OLED display. is there.

The above object of the present invention is achieved by the following configurations.
That is, the present invention is a method for producing a gas barrier film comprising a gas barrier layer formed by irradiating with vacuum ultraviolet light after applying and drying a composition containing a solvent, polysilazane and an amine compound on the surface of the substrate. There,
A gas barrier comprising a solvent component having a Hansen SP value distance Ra of 8 or more and 14 or less and a boiling point of 70 ° C. or more and 110 ° C. or less and 20% by mass or more and 50% by mass or less in the solvent. The above object is achieved by a method for producing a conductive film.

  By the manufacturing method according to the present invention, cracks of the barrier layer of the gas barrier film and the base material can be reduced.

  By the production method according to the present invention, a barrier layer is formed by applying a composition containing polysilazane to a plastic substrate having optical anisotropy, thereby having excellent productivity and very excellent barrier performance. It is possible to provide a gas barrier film having optical anisotropy and an OLED display that is lightweight and does not break like glass, and that is excellent in durability and visibility.

It is a schematic sectional drawing which shows an example of the preferable layer structure of the gas barrier film of this invention. It is a schematic sectional drawing which shows an example of the vacuum ultraviolet irradiation apparatus used for this invention. It is a schematic diagram which shows an example of the organic EL element structure of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. As a result of intensive studies in view of the above problems, the present inventor has formed a gas barrier layer formed by irradiating vacuum ultraviolet light after a step of applying and drying a composition containing a solvent, a polysilazane and an amine compound on a substrate surface. The HansenSP value distance Ra to the resin base material is 8 or more and 14 or less, and a solvent component having a boiling point of 70 ° C. or more and 110 ° C. or less is 20% by mass in the solvent. In addition to solving the new problem of cracks in the barrier film by the method for producing a gas barrier film characterized by containing 50% by mass or less, the product has a phase difference function with excellent productivity and high gas barrier performance. It has been found that a gas barrier film can be realized, and has reached the present invention.

  First, the structure of the gas barrier film according to the present invention will be described with reference to FIG. 1, each component of the gas barrier film and the manufacturing method of each structure will be described, and then the method of manufacturing the gas barrier film according to the present invention will be described. The embodiment will be described in detail. FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the gas barrier film of the present invention.

  In FIG. 1, a gas barrier film 10 according to the present invention has a first barrier layer 1 formed on a substrate 0 by a vapor deposition method or a coating method, and a gas barrier film 1 is formed on the first barrier layer 1. A barrier property formed by applying a second barrier layer 2 formed by a phase growth method or a coating method, and a protective layer forming composition containing an organic material or an inorganic material thereon, and if necessary, a modification treatment And a protective layer 3 having no layer.

  In FIG. 1, two gas barrier layers, ie, a first barrier layer and a second gas barrier layer are shown. However, in the gas barrier film according to the present invention, one or more gas barrier layers may be used, and 2 to 5 layers may be used. The barrier layer is preferably provided. In this specification, the “barrier layer” is also referred to as a gas barrier layer, and unless otherwise specified, the term “barrier layer” refers to the first barrier layer, the second barrier layer,. Includes all of the layers.

  Furthermore, the gas barrier film according to the present invention may be provided with an intermediate layer between the substrate surface and / or each barrier layer from the viewpoint of improving the adhesion of the barrier layer or protecting the barrier layer. As the intermediate layer, at least one of an intermediate layer between barrier layers, an anchor coat layer, a smooth layer, or a bleed-out prevention layer is preferable, and all of these three layers may be directly provided on the substrate. The order of lamination of the two layers is not particularly limited, but it is preferable to form a bleed-out prevention layer on one surface of the base material and form a smooth layer on the other surface. It is more preferable to laminate | stack these barrier layers, and a smooth layer may be formed in both surfaces of a base material, and also a barrier layer may be formed in both surfaces of a base material.

The “gas barrier property” as used in the present invention is a water vapor transmission rate (water vapor transmission rate) (60 ± 0.5 ° C., relative humidity (90 ± 2)% measured by a method in accordance with JIS K 7129-1992. When RH) is 1 × 10 ⁻³ g / (m ² · 24 h) or less, it is defined as having gas barrier properties. Moreover, the oxygen permeability (oxygen permeability) measured by a method according to JIS K 7126-1987 of the gas barrier film is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less (1 atm is 1. 01325 × 10 ⁵ Pa).

  In the electronic device according to the present invention, the gas barrier film of the present invention is used. Hereinafter, the details of each component of the gas barrier film of the present invention and the method for producing the component will be described.

[First barrier layer]
The first barrier layer according to the present invention has at least one selected from the group consisting of silicon oxide, silicon oxynitride, and silicon nitride, and silicon oxide, oxynitride in terms of gas barrier properties and transparency It is preferable to have at least one selected from silicon or silicon nitride, and more preferably at least one selected from silicon oxide or silicon oxynitride. The first barrier layer is desirably formed substantially or completely as an inorganic layer.

  The first barrier layer is formed by vapor deposition (chemical vapor deposition or physical vapor deposition of a metal compound) or coating. That is, when there are a plurality of barrier layers according to the present invention, at least one of them may be formed by a wet method. Due to the presence of the first barrier layer formed in this way, moisture transfer from the base material can be prevented, and the reforming process when forming the second barrier layer is likely to proceed. In addition, the first barrier layer according to the present invention is preferably formed by a coating method.

  The method for forming a barrier layer by the vapor deposition method according to the present invention can be broadly classified into a physical vapor deposition method and a chemical vapor deposition method, and the physical vapor deposition method is a substance in a gas phase. The target material, for example, a thin film such as a carbon film, is deposited on the surface of the substrate by a physical method. These methods include vapor deposition (resistance heating method, electron beam vapor deposition, molecular beam epitaxy) method, ion There are a plating method and a sputtering method. On the other hand, the chemical vapor deposition method (Chemical Vapor Deposition) supplies a raw material gas containing a target thin film component onto a substrate, and forms a film by a chemical reaction on the surface of the substrate or in the gas phase. It is a method of depositing. In addition, there is a method of generating plasma etc. for the purpose of activating chemical reaction, and known CVD methods such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, plasma CVD method, atmospheric pressure plasma CVD method, etc. In the present invention, any of them can be advantageously used. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of film forming speed and processing area. Forming the barrier layer (first or second) by chemical vapor deposition is advantageous in terms of gas barrier properties.

  For gas barrier layers obtained by plasma CVD, plasma CVD under atmospheric pressure or near atmospheric pressure, select conditions such as raw materials (also called raw materials), metal compounds, decomposition gas, decomposition temperature, input power, etc. Metal carbides, metal nitrides, metal oxides, metal sulfides, metal halides, and mixtures thereof (metal oxynitrides, metal oxyhalides, metal nitride carbides, etc.) can be formed separately.

  For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Moreover, if a zinc compound is used as a raw material compound and carbon disulfide is used as the cracking gas, zinc sulfide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  As such a raw material, as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

  However, it is preferably a compound having a vapor pressure in a temperature range of 0 ° C to 250 ° C under atmospheric pressure, and more preferably a compound exhibiting a liquid state in a temperature range of 0 ° C to 250 ° C. This is because the pressure in the plasma film forming chamber is close to atmospheric pressure, and it is difficult to send a gas into the plasma film forming chamber unless it can be vaporized under atmospheric pressure. This is because the amount fed can be managed with high accuracy. In addition, when the heat resistance of the plastic film which forms a gas barrier layer is 270 degrees C or less, it is preferable that it is a compound which has a vapor pressure from the plastic film heat resistant temperature to the temperature of 20 degrees C or less.

  The metal compound that is a raw material compound of such a vapor phase growth method is not particularly limited, and examples thereof include a silicon compound, a titanium compound, a zirconium compound, an aluminum compound, a boron compound, a tin compound, and an organometallic compound.

  Among these, as silicon compounds, silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, di Tylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, Pargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Examples thereof include cyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas. Further, the decomposition gas may be mixed with an inert gas such as argon gas or helium gas.

  A desired barrier layer can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas. The first barrier layer formed by chemical vapor deposition is preferably a metal carbide, metal nitride, metal oxide, metal halide, metal sulfide, or a composite compound thereof from the viewpoint of permeability.

Further, the first barrier layer according to the present invention is preferably a layer obtained by modifying polysilazane by vacuum ultraviolet irradiation by a coating method and converting polysilazane into silicon oxide or silicon oxynitride. In addition, the “modification treatment” in the present specification refers to a conversion reaction of polysilazane to silicon oxide or silicon oxynitride. Specifically, the gas barrier film of the present invention as a whole has a gas barrier property (water vapor permeability, 1 × 10 ⁻³ g / (m ² · 24 h) or less) is a treatment for forming an inorganic thin film at a level that can contribute to development.

  The average thickness of the first barrier layer according to the present invention is preferably 10 nm to 2 μm, and more preferably 20 nm to 1 μm.

  A range in which the average thickness is applied is preferable from the viewpoint of high barrier performance.

  As a method of forming the first barrier layer by the coating method according to the present invention, a step (1) of preparing a composition containing a solvent, a polysilazane and an amine compound, and applying and drying the composition on the substrate surface It is preferable to have a step (2) of forming the composition layer and a step (3) of forming the first barrier layer by irradiating the composition with vacuum ultraviolet light. Each step will be described below.

(About step (1))
Step (1) according to the present invention is a step of preparing a composition containing a solvent, polysilazane and an amine compound.

  The composition according to the present invention essentially contains a solvent, a polysilazane and an amine compound, and may optionally contain a metal catalyst.

  The composition ratio of the composition according to the present invention preferably includes 10000 to 250 parts by mass of a solvent and 0.1 to 10 parts by mass of an amine compound with respect to 100 parts by mass of polysilazane. More preferably, it contains 5000 to 300 parts by mass of the solvent and 0.2 to 5 parts by mass of the amine compound, and 2000 to 500 parts by mass of the solvent and 0.5 to 0.5 parts by mass of the amine compound with respect to 100 parts by mass of the polysilazane. More preferably, 2 mass is essential. Moreover, it is preferable that 0.1-5 mass parts is contained with respect to 100 mass parts of polysilazanes, and, as for the metal catalyst contained if necessary, it is more preferable to contain 0.2-2 mass parts.

<solvent>
The solvent according to the present invention has a Hansen SP value distance Ra of 8 or more and 14 or less and a boiling point of 70 ° C. or more and 110 ° C. or less with a base material to which the composition that is a precursor of the first gas barrier layer is applied. It contains 20% by mass or more and 50% by mass or less of the solvent component. That is, the solvent according to the present invention is a mixed solvent, and the solvent component contains 20% by mass of a solvent component having a Hansen SP value Ra of 8 or more and 14 or less and a boiling point of 70 ° C. or more and 110 ° C. or less. More than 50 mass% is included.

  In general, the SP value is a solubility parameter and is known as one of affinity parameters. Assuming an intermolecular force acting between a solvent and a solute, the intermolecular force is a measure of cohesive force, The SP value (δ) proposed by Hildebrand et al. Is defined by the square root of the cohesive energy density shown in the following Equation 1.

  However, the solubility parameter derived by Hildebrand's theory is based on the regular solution theory, and therefore does not match the actual solution. From this definition, the SP value is generally limited to a known solution whose boiling point can be measured, but it is estimated from a physical property value as a method of estimating the SP value that is currently known for the purpose of applying to a polymer or the like. There is a method and a method of estimating from the molecular structure. As a method of estimating from the former physical property value, a method of obtaining from latent heat of evaporation, a method by Hildebrand Rule, and the like can be mentioned. On the other hand, as a method of estimating from the latter molecular structure, there are a Hoy calculation method, a Hansen calculation method, a Small calculation method, and the like. In the present invention, the SP value according to the Hansen calculation method is used, and generally, the Hansen solubility parameter is also referred to as HSP or Hansen SP value distance.

The Hansen SP value will be briefly described. The solubility is mainly represented by a three-dimensional vector space of a polarization term (δ _P ), a dispersion term (δ _D ), and a hydrogen bond term (δ _H ). When plotted in space, the solvent will collect in the solute and form a sphere. The center of the sphere is the SP value of the solute, and the radius of the sphere is the interaction radius (R ₀ ), which indicates that a large amount of solvent dissolves when the radius is large and a small amount of solvent dissolves when the radius is small. In addition, in the case of the relationship between the solute and the solvent, or in the case of two kinds of mixed solvents, substances having high solubility or compatibility are present at a short distance, so that the difference in the interaction radius (R ₀ ) between the two solvents (ie, Hansen) The smaller the SP value distance Ra), the better the compatibility and solubility.

  Such a Hansen SP value distance, which is an index of solubility and compatibility between two substances, is defined by the following equation (1-1).

In the above formula (1-1), δ _P1 is a solute polarization term, δ _P2 is a solvent polarization term, δ _D1 is a solute dispersion term, δ _D1 is a solvent dispersion term, δ _H1 is a solute hydrogen bond term, δ _H2 is a hydrogen bond term of the solvent, and these polarization term (δ _P ), dispersion term (δ _D ), and hydrogen bond term (δ _H ) are values calculated by the substance. The numerical values of many organic compounds are known.

  The present inventor pays attention to the formula (1-1), and a new problem that a barrier film is cracked when a polysilazane-containing coating solution is directly applied to a substrate and irradiated with vacuum ultraviolet light is that the substrate and the barrier The relationship between the compatibility with the layer and the solvent used in the coating solution was found. That is, if the Hansen SP value distance Ra between the base material and a solvent component contained in a predetermined amount in the solvent used in the coating solution is 8 or more and 14 or less, the base material and the barrier can be dissolved by appropriately dissolving the base material. It is considered that the adhesion with the layer can be secured.

  More specifically, when a gas barrier film is produced by a conventional coating method, the polysilazane which is a precursor of the barrier layer is often dissolved in a dibutyl ether or xylene solution from the viewpoint of the solubility and storage stability of the polysilazane. It was. However, the polycarbonate-based resin and cycloolefin-based resin used as the base material are easily cracked. Furthermore, since the SP value of a dibutyl ether or xylene solution and a polycarbonate resin or cycloolefin resin is close and solvent resistance is low, polysilazane is applied as it is with these solvents, and high barrier reforming by vacuum ultraviolet rays is performed. Then, the base material is deformed and cracks are generated not only in the barrier layer but also in the base material. However, by adding a predetermined amount of a solvent component having a Hansen SP value distance Ra of 8 or more and 14 or less to the solvent used in the coating solution, the SP value distance from the substrate is differentiated. Therefore, it was confirmed that the low solvent resistance of the substrate can be reduced to some extent.

  When the SP value of such a dibutyl ether or xylene solution is close to that of a polycarbonate resin or a cycloolefin resin, the polycarbonate or polycarbonate copolymer polymer (PC), cycloolefin polymer (COP), It is generally known that cycloolefin copolymer polymer (COC) has low resistance to ether solvents and aromatic solvents. As shown below, this is because the SP value distance (Ra) of dibutyl ether and xylene and polycarbonate or polycarbonate copolymer polymer, cycloolefin polymer, cycloolefin copolymer is as follows: People are thinking.

  Therefore, using the above formula (1-1), the following formula (1-2) was derived by paying attention to the Hansen SP value distance Ra between the solvent and the substrate.

  The Hansen SP value distance between the substrate according to the present invention and the solvent component contained in the solvent is calculated by the following equation (1).

(In the above formula (1-2), dD1 is a dispersion term of the evaporation energy of the resin used for the substrate, dP1 is a polarization term of the evaporation energy of the resin used for the substrate, and dH1 is used for the substrate. The hydrogen bond term of the evaporation energy of the resin being used, dD2 is the dispersion term of the evaporation energy of the solvent component, dP2 is the polarization term of the evaporation energy of the solvent component, and dH2 is the hydrogen bond term of the evaporation energy of the solvent component)
Here, the various parameters “dD1, dP1, dH1, dD2, dP2, and dH2” in Formula (1-2) are based on the literature (“HANSEN” if the material of the base material to be used and the solvent component to be used are determined. SOLUBILITY PARAMETERS A User's Handbook Second Edition CRC Press Taylor & Francis Group (hereinafter referred to as Document 1), pages 345-510) and software (Hansen Solbid PSP). 12)) already contains many specific numerical values. Further, on page 18 of the document 1, the polarization term (δ _P ), the dispersion term (δ _D ), and the hydrogen bond term (δ _H ) have the temperature dependency represented by the following formula (2), and Since the polarization term (δ _P ) represented by the following formula (3) is described on page 16 of the document, it can be easily calculated if the material of the base material to be used and the solvent component to be used are determined. .

Regarding the Hansen SP value distance according to the present invention, many organic materials are described in Document 1, “Polymer Hand Book (4th edition) Chapter VII Solidity Parameter Values”, “SP value basics / applications and calculation methods (information mechanisms)”. The SP value of the solvent is described. In particular, many organic solvents and polymers, polarization terms of organic substances, dispersion terms, and hydrogen bonding terms are described on pages 345 to 510 of the document 1. By substituting such a numerical value into equation (1), the Hansen SP value distance between the two substances can be calculated. In addition, all references 1 are cited in the present specification, and all the references are within the scope of the present invention. From the above, referring to this document, δ _D , δ _P and δ _H of various organic substances can be calculated.

  Furthermore, the Hansen SP value distance can be calculated by inputting the structural formula of the liquid into the HSP software. Specifically, it can be calculated by software developed by Hansen et al. (Software name: Hansen Solubility Parameter in Practice (HSPIP v3.1.12)). Based on an estimation method using a neural network method called Y-MB with the software, when a molecular structure is input as a molecular linear notation Smiles formula or MOL file, the molecule is automatically decomposed into atomic groups. Hansen solubility parameter values and molecular volumes can be calculated.

  When a composition containing polysilazane, a solvent, and an amine compound according to the present invention is applied to a base material, dibutyl ether or xylene alone as a solvent has a high Hansen SP value distance Ra and a high boiling point. When the polysilazane reforming treatment is applied, which will be described later, and is irradiated with vacuum ultraviolet rays, the gas barrier layer and the substrate itself are cracked, resulting in deterioration of the gas barrier properties. I believe. The present inventors use a solvent containing a solvent component having an SP value distance of 8 to 14 and a boiling point of 70 ° C. to 110 ° C. in a solvent ratio of 20 to 50% by mass, thereby appropriately increasing the base material. It has been found that excellent gas barrier performance can be obtained without cracking the gas barrier layer and the base material itself while dissolving the surface and maintaining the adhesion between the base material and the gas barrier layer.

  The Hansen SP value distance Ra between the substrate and the solvent component according to the present invention is 8 to 14, and preferably 8.5 to 13.5.

  If the Hansen SP value distance Ra is less than 8, the effect of suppressing dissolution of the substrate is small, and if it exceeds 14, the adhesion between the substrate and the gas barrier layer decreases.

  The boiling point of the solvent component according to the present invention is 70 ° C to 110 ° C, preferably 75 to 105 ° C. When the boiling point is lower than 70 ° C., the solvent used in combination is volatilized quickly, and when it exceeds 110 ° C., the drying rate is reduced, and the effect of suppressing the dissolution of the base material is reduced.

  Moreover, the solvent which concerns on this invention contains 20-50 mass% of solvent components based on this invention, and it is preferable to contain 25-45 mass%.

  When the content of the solvent component in the solvent is less than 20% by mass, the drying rate is slowed, and when it exceeds 50% by mass, the effect of suppressing the dissolution of the base material becomes too small and the adhesion is lowered.

  The solvent component according to the present invention is not particularly limited as long as the Hansen SP value distance Ra to the substrate is 8 to 14 and the boiling point is 70 ° C. to 110 ° C., but is an alcohol solvent that easily reacts with polysilazane. And avoiding moisture. For example, 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, preferably aliphatic carbonization Hydrogen and alicyclic hydrocarbons, specifically 2,2,4-trimethylpentane (isooctane), n-heptane and cyclohexane are preferred.

  The solvent according to the present invention is a mixed solvent of a solvent component having a Hansen SP value distance Ra of 8 to 14 and a boiling point of 70 ° C. to 110 ° C. with another solvent and the above-described base material. is there. Examples of the other solvent include hydrocarbons such as xylene, pentane, hexane, cyclohexane, toluene, solvesso, and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane, and tetrahydrofuran. It is done.

  Therefore, the solvent according to the present invention is a mixed solvent of the above solvent and the above solvent component, and particularly preferable mixed solvents include dibutyl ether and 2,2,4-trimethylpentane (isooctane), dibutyl ether and n. -Heptane, dibutyl ether and cyclohexane.

According to the document 1, 2,2,4-trimethylpentane (dispersion term (δ _D ) = 14.1, polarization term (δ _P ) = 0, hydrogen bond term (δ _H ) = 0, molar volume. = 166.1), n-heptane dispersion term ((δ _D ) = 15.3, polarization term (δ _P ) = 0, hydrogen bond term (δ _H ) = 0, molar volume = 147.4), cyclohexane ( (Δ _D ) = 16.8, polarization term (δ _P ) = 0, hydrogen bond term (δ _H ) = 0.2, molar volume = 108.7).

<Polysilazane>
The polysilazane according to the present invention is a polymer having a silicon-nitrogen bond, and is a ceramic precursor such as SiO ₂ , Si ₃ N ₄ composed of Si—N, Si—H, N—H, etc., and both intermediate solid solutions SiO _x N _y. A structure having a unit represented by the following general formula (1) is preferred.

In the general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms). An alkenyl group (preferably an alkenyl group having 2 to 5 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms), an aryl group (preferably an aryl group having 6 to 14 carbon atoms) ), An alkylsilyl group (preferably a silyl group having 3 to 16 carbon atoms), an alkylamino group (preferably an alkylamino group having 3 to 32 carbon atoms) or an alkoxy group (preferably an alkoxy having 1 to 30 carbon atoms) Group).

In the general formula (1), the alkyl group in R ¹ , R ² and R ³ includes both a linear or branched alkyl group. Specific examples of the alkyl group having 1 to 30 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. N-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2 -Dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2- Ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-t-butyl-2-methylpropylene Group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, Examples include an n-pentacosyl group, an n-hexacosyl group, an n-heptacosyl group, an n-octacosyl group, and an n-triacontyl group.

  Examples of the alkenyl group having 2 to 5 carbon atoms include vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, and 2-pentenyl group. .

  Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

  The aryl group having 6 to 14 carbon atoms is not particularly limited, and examples thereof include non-condensed hydrocarbon groups such as a phenyl group, a biphenyl group, and a terphenyl group; a pentarenyl group, an indenyl group, a naphthyl group, an azulenyl group, and a heptaenyl group. Group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylenyl group, pyrenyl group, Examples thereof include condensed polycyclic hydrocarbon groups such as a chrycenyl group and a naphthacenyl group.

  Specific examples of the alkylsilyl group having 3 to 16 carbon atoms include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, t-butyldimethylsilyl group, methyldiphenylsilyl group, t-butyldiphenylsilyl group and the like. It is done.

  The alkylamino group having 3 to 32 carbon atoms is not particularly limited, and examples thereof include dimethylamino group, diethylamino group, diisopropylamino group, methyl-tert-butylamino group, dioctylamino group, didecylamino group, and dihexadecyl. An amino group, a di-2-ethylhexylamino group, a di-2-hexyldecylamino group, etc. are mentioned.

  Examples of the alkoxy group having 1 to 30 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group. Decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, eicosyloxy group, Henecosyloxy group, docosyloxy group, tricosyloxy group, tetracosyloxy group, pentacosyloxy group, hexacosyloxy group, heptacosyloxy group, octacosyloxy group, triacontyloxy group, etc. Is mentioned.

In the present invention, from the viewpoint of denseness as a gas barrier film to be obtained, the polysilazane according to the present invention is preferably such that at least one of R ¹ , R ² and R ³ is a hydrogen atom, In (1), perhydropolysilazane in which all of R ^1, R ² and R ³ are hydrogen atoms is particularly preferred. The perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings.

  The polysilazane represented by the general formula (1) preferably has a number average molecular weight (Mn) of about 600 to 2000 (in terms of polystyrene). The number average molecular weight can be measured by gel permeation chromatography (GPC).

  Further, the polysilazane according to the present invention may be either liquid or solid, and its state varies depending on the molecular weight. In addition, the polysilazane according to the present invention may be a product produced by a known synthesis method or a commercially available one, and the polysilazane according to the present invention is currently marketed in a solution state dissolved in an organic solvent. The commercial product can be used as it is as a polysilazane-containing coating solution.

  In the composition according to the present invention, 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, so that it adheres to the base material as a base. Therefore, the ceramic film made of polysilazane which is hard and brittle can be provided with toughness, and even when the (average) film thickness is increased, the occurrence of cracks can be suppressed. Therefore, these perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  In addition, in order to apply the polysilazane according to the present invention so as not to damage the film substrate, a compound that is ceramicized at a relatively low temperature and modified to silica is preferable in addition to perhydropolysilazane. As another example, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with a polysilazane having a main skeleton composed of the unit represented by the general formula (1) (see, for example, JP-A No. 5-23827) Glycidol-added polysilazane obtained by reacting glycidol (see, for example, JP-A-6-122852), alcohol-added polysilazane obtained by reacting with alcohol (see, for example, JP-A-6-240208), metal carboxylic acid Metal carvone obtained by reacting salt Salt-added polysilazane (for example, see JP-A-6-299118), acetylacetonate complex-added polysilazane (for example, see JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal fine particles And metal fine particle-added polysilazane obtained by adding (for example, see JP-A-7-196986).

  The polysilazane concentration in the polysilazane-containing composition according to the present invention is preferably about 0.2 to 35% by mass, although it varies depending on the film thickness of the target barrier layer and the pot life of the coating solution.

<Amine compound>
The amine compound according to the present invention is used for promoting modification to a silicon oxide compound, and examples of the amine compound include N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine, and triethylamine. 3-morpholinopropylamine, N, N, N ′, N ′,-tetramethyl-1,3-diaminopropane, N, N, N ′, N ′,-tetramethyl-1,6-diaminohexane, -Piperidine ethanol, 4-piperidinol, etc. are mentioned. For example, as a solution containing polysilazane in an amine compound, AQUAMICA NAX120-20, NN120-20, NL120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, manufactured by AZ Electronic Materials Co., Ltd. SP140 etc. are mentioned.

  The amine compound according to the present invention is preferably in the range of 0.1 to 10 mass%, more preferably in the range of 0.2 to 5 mass%, based on polysilazane.

  When the amount of the amine compound in the composition according to the present invention is within the above range, excessive silanol formation due to rapid progress of the reaction, reduction in membrane density, increase in membrane blood vessels, and the like can be suppressed.

<Metal catalyst>
Examples of the metal catalyst added to the composition according to the present invention as needed include Pt compounds, Pd compounds, Rh compounds and the like, and specifically include Pt acetylacetonate, palladium propionate, and Rh acetylacetonate. It is done.

(About step (2))
The step (2) according to the present invention is a step (2) in which the composition layer prepared in the above step (1) is applied to the substrate surface and dried to form a composition layer.

  Any appropriate wet coating method may be employed as a method of applying the composition to the surface of the substrate according to the present invention. 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 film thickness of the composition layer, which is a film obtained by drying the coating film of the composition, can be appropriately set according to the purpose. For example, the composition layer preferably has a thickness after drying of from 10 nm to 2 μm, more preferably from 20 nm to 1000 nm, and even more preferably from 40 nm to 500 nm.

  The method of drying after coating the composition on the surface of the substrate according to the present invention is preferably drying the coating film of the composition by heat treatment. Specifically, for example, a method of heating a coating film by contacting a substrate with a heating element such as a heat block, a method of heating an atmosphere with an external heater such as a resistance wire, an infrared region such as an IR heater There are no particular limitations on the method using the above light. Moreover, you may select suitably the method which can maintain the smoothness of the coating film containing polysilazane.

  The temperature of the coating film during drying by heat treatment is preferably adjusted appropriately in the range of 60 ° C to 120 ° C, more preferably in the range of 65 ° C to 110 ° C. When the temperature is lower than 60 ° C., the drying rate is slowed, and the effect of suppressing the dissolution of the substrate is reduced. Moreover, if it exceeds 120 degreeC, base material itself will deform | transform and it will become easy to crack a gas barrier layer.

  The heating time is preferably in the range of 30 seconds to 5 minutes, more preferably in the range of 30 seconds to 4 minutes.

  The substrate according to the present invention is preferably a resin substrate and is a support that can be elongated, and can hold a barrier layer having a gas barrier property (also referred to simply as “barrier property”) described later. It is. Moreover, it is preferable that it is a polymer film which has a negative wavelength dispersion property that the retardation in a film surface becomes so small that it becomes a short wavelength. Further, it is particularly preferable to use a polymer film whose in-plane retardation (Ro) is controlled to be λ / 4 with respect to light having a wavelength of 550 nm. In this specification, “the in-plane phase difference (Ro) is λ / 4 with respect to light having a wavelength of 550 nm” means that the value of Ro obtained by the following formula is 148 ± 10 nm.

  In the formula, d represents the film thickness (nm) of the substrate, nx represents the maximum refractive index in the plane of the film substrate (also referred to as the refractive index in the slow axis direction), and ny represents a retardation in the film plane. Refractive index in the direction perpendicular to the phase axis. In addition, Ro is measured at a measurement wavelength of 550 nm in an environment of 23 ° C. and 55% RH using KOBRA-21ADH (Oji Scientific Instruments) as an automatic birefringence meter.

  Reflection light generated at the interface and metal electrode inside the light emitting element is prevented from coming out of the gas barrier substrate according to the present invention due to the retardation of the polarizing plate and λ / 4, so that the display contrast is reduced by the internal reflection light. Can be suppressed.

  Specifically, external light incident from the viewing-side surface passes through the transmission axis of a linear polarizing plate (polarizer) to become linearly polarized light in only one direction, and this linearly polarized light is converted into a λ / 4 retardation plate. The light is converted into circularly polarized light by passing through, reflected by the interface inside the display element or the metal electrode, and returned to linearly polarized light by passing through the λ / 4 retardation plate again. At this time, the reflected light inside the display element is linearly polarized light having an angle different by 90 ° because the phase difference is shifted by λ / 2 from the linearly polarized light when incident. Therefore, it is absorbed by the absorption axis of the linear polarizing plate (polarizer), and the outgoing of the reflected light is prevented. In order to achieve this object, the angle between the absorption axis of the linear polarizing plate (polarizer) and the slow axis of the film substrate (λ / 4 retardation plate) is within 45 ° ± 5 °, In particular, it is preferable to arrange it within 45 ° ± 1 °.

  In order that the total retardation of all the layers closer to the display device than the polarizing plate is approximately λ / 4 with respect to light having a wavelength of 550 nm, the gas barrier film having optical anisotropy of the present invention, When an arbitrary polymer film is present, it is preferable that the total retardation of all the polymer films is approximately λ / 4 with respect to light having a wavelength of 550 nm.

  This is because, for example, the retardation of the optically anisotropic gas barrier film according to the present invention is λ / 4 with respect to light having a wavelength of 550 nm, and other polymer films have no retardation. it can.

  Here, since the light with a wavelength of 550 nm is the light with the highest visibility, the internal reflection can be most effectively suppressed by such a configuration. However, not only for light with a wavelength of 550 nm but also for other wavelengths in the visible light region, the retardation of all layers including the film substrate except the linear polarizing plate (polarizer) is the same as above. It is preferably approximately λ / 4 (Ro = 148 ± 10 nm). Since a general polymer film has a positive wavelength dispersion that increases a phase difference with respect to light having a shorter wavelength, it is not possible to set the total phase difference of all layers to approximately λ / 4 over the entire visible light region. Have difficulty. However, by using a polymer film having wavelength dispersibility (that is, reverse wavelength dispersibility) in which the phase difference is small with respect to light having a shorter wavelength, as disclosed in JP 2000-137116 A, The total retardation of all layers can be approximately λ / 4 over the entire visible light region.

  In the present invention, as a linear polarizing plate (polarizer), not only an absorption type polarizing plate obtained by stretching a polymer film dyed with a dye, but also a plurality of retardation films so that their slow axis directions are orthogonal to each other. It is also possible to use a reflective polarizing plate obtained by alternately laminating. Here, in such a reflective polarizing plate, the refractive index of each layer is substantially the same for one polarized light, thereby preventing the reflection of incident light at the interface between the layers, and For the other polarization, the refractive index of each layer is different, so that incident light can be reflected back at the interface of the retardation film. Or the wire grid polarizing plate which has arrange | positioned the metal fine wire of a width | variety smaller than a wavelength size continuously on a film can also be used as a linearly-polarizing plate (polarizer) in this invention. In the present invention, as the polarizing plate, not only the linear polarizing plate as described above but also a circular polarizing plate that separates right circularly polarized light and left circularly polarized light can be used.

  As a constituent material of a film base material having such reverse wavelength dispersion and capable of imparting optical characteristics as a λ / 4 retardation plate, polycarbonate (PC), cycloolefin polymer (COP), cycloolefin copolymer (COC) ), And one or more selected from the group consisting of cellulose derivatives such as cellulose acetate propionate (CAP). Then, these materials are stretched to align the polymer molecules and form a film, or a liquid crystal material is aligned so as to exhibit desired optical properties on a substrate made of a film that does not develop a retardation. A cured film can be used as the film substrate.

  Of these, polycarbonate (PC) or cycloolefin polymer (COP) is preferably used as the substrate of the present invention from the viewpoints of cost, availability, and gas barrier properties. Examples of the polycarbonate (PC) film having a function as a λ / 4 retardation plate include Pure Ace WR manufactured by Teijin Chemicals. Examples of the cycloolefin polymer (COP) film include ZEONOR film manufactured by ZEON Corporation, and F film manufactured by Gunze Corporation. These can be easily obtained.

  In the substrate having optical anisotropy used in the present invention, the refractive index with respect to sodium d-line (589 nm) is preferably 1.57 to 1.62. If this refractive index is 1.57 or more, the birefringence is maintained at a sufficiently high value. On the other hand, if the refractive index is 1.62 or less, the reflectivity does not become too large and sufficient light transmission is ensured.

  The base material having optical anisotropy used in the present invention has a ratio (R450 / R550) of the phase difference R450 measured at a wavelength of 450 nm to the phase difference R550 measured at a wavelength of 550 nm (0.75 to 1.1). It is preferable that If the ratio is within this range, an ideal phase difference characteristic can be obtained. For example, when producing a circularly polarizing plate using the film substrate having this optical anisotropy as a λ / 4 retardation plate, it is possible to provide an ideal λ / 4 retardation plate in the visible region, A polarizing plate and a display device having a neutral hue with less wavelength dependency can be realized. In order to obtain this effect more stably, the ratio (R450 / R550) is more preferably 0.76 to 0.98, and particularly preferably 0.77 to 0.95. The “substrate having optical anisotropy” here means that the refractive index is different in the in-plane direction or in the in-plane direction and the thickness direction.

Furthermore, the photoelastic coefficient of the substrate having optical anisotropy used in the present invention is preferably 40 × 10 ⁻¹² Pa ⁻¹ or less. If the photoelastic coefficient is 40 × 10 ⁻¹² Pa ⁻¹ or less, the stress at the time of bonding when the film base material is bonded to a linear polarizing plate (polarizer) as a retardation film and mounted on a display device. As a result, a partial stress is applied to the retardation film due to the viewing environment or the heat of the backlight, causing a non-uniform retardation change, resulting in a significant deterioration in image quality. From such a viewpoint, the base material according to the present invention preferably has a photoelastic coefficient of 40 × 10 ⁻¹² Pa ⁻¹ or less, and more preferably 35 × 10 ⁻¹² Pa ⁻¹ or less.

  The average thickness of the substrate according to the present invention is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

  Moreover, it is preferable that the base material which concerns on this invention is transparent. According to such a form, it is possible to obtain a transparent gas barrier film by making the gas barrier unit formed on the substrate transparent. As a result, it can also be used to produce a transparent substrate such as an organic EL element. Here, “the substrate is transparent” means that the light transmittance of visible light (400 to 700 nm) is 80% or more.

  In addition, the substrate used in the present invention may be subjected to corona treatment on the surface before forming the barrier layer.

(About step (3))
Step (3) according to the present invention is a step of forming a barrier layer by irradiating the composition layer formed in the above step (2) with vacuum ultraviolet light. That is, at least a part of polysilazane is modified into silicon oxynitride by the step (3). Therefore, in the first barrier layer according to the present invention, when the barrier layer is formed by irradiating the composition layer with vacuum ultraviolet light, the polysilazane in the composition undergoes a conversion reaction to silicon oxide or silicon oxynitride. In this way, gas barrier properties can be expressed. Further, the conversion reaction to silicon oxide or silicon oxynitride uses ultraviolet rays that can be converted at a lower temperature from the viewpoint of adaptation to a resin base material.

  Here, an estimation mechanism in which a coating film containing polysilazane is modified in the vacuum ultraviolet light irradiation step to obtain a specific composition of SiOxNy will be described by taking perhydropolysilazane as an example.

Perhydropolysilazane can be represented by a composition of “— (SiH ₂ —NH) n—”. When the modified composition is represented by SiOxNy, an external oxygen source is required to achieve x> 0. This is because (i) oxygen and moisture contained in the polysilazane coating solution, (ii) coating drying Oxygen and moisture taken into the coating film from the atmosphere in the process, (iii) Oxygen and moisture taken into the coating film from the atmosphere in the vacuum irradiation process, ozone, singlet oxygen, (iv) Vacuum ultraviolet light irradiation process Oxygen and moisture that move into the coating film as outgas from the substrate side due to heat applied in step (v) When the vacuum ultraviolet light irradiation step is performed in a non-oxidizing atmosphere, the non-oxidizing atmosphere When moving from an oxygen atmosphere to an oxidizing atmosphere, oxygen, moisture and the like taken into the coating film from the atmosphere become an oxygen source.

On the other hand, with regard to y, the condition under which nitriding proceeds from oxidation of Si is considered to be very special, so basically 1 is the upper limit.
Also, from the relationship of Si, O, N bond, x, y are basically in the range of 2x + 3y ≦ 4. In the state of y = 0 where the oxidation has progressed completely, the coating film contains silanol groups, and there are cases where 2 <x <2.5.

  The reaction mechanism presumed to produce silicon oxynitride and further silicon oxide from perhydropolysilazane in the vacuum ultraviolet light irradiation step will be described below.

(1) Dehydrogenation and accompanying Si-N bond formation Si-H and N-H bonds in perhydropolysilazane are relatively easily cleaved by excitation with vacuum ultraviolet light irradiation, and in an inert atmosphere, Si In some cases, Si dangling bonds, which are considered to be recombined as -N, may be formed). That is, it is cured as a SiNy composition without being oxidized. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H ₂ .

(2) Formation of Si—O—Si Bonds by Hydrolysis / Dehydration Condensation Si—N bonds in perhydropolysilazane are hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. Two Si—OHs are dehydrated and condensed to form Si—O—Si bonds and harden. This is a reaction that occurs even in the air, but during vacuum ultraviolet light irradiation in an inert atmosphere, water vapor generated as outgas from the substrate by the heat of irradiation is considered to be the main moisture source. When the water is excessive, Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO _2.1 to SiO _2.3 is obtained.

(3) Direct oxidation by singlet oxygen, formation of Si—O—Si bond When a suitable amount of oxygen is present in the atmosphere during irradiation with vacuum ultraviolet light, singlet oxygen having very strong oxidizing power is formed. H or N in the perhydropolysilazane is replaced with O to form a Si—O—Si bond and harden. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

(4) Oxidation with Si-N bond cleavage by vacuum ultraviolet light irradiation / excitation Since the energy of vacuum ultraviolet light is higher than the bond energy of Si-N in perhydropolysilazane, the Si-N bond is cleaved and It is considered that when an oxygen source such as oxygen, ozone or water is present, it is oxidized to form a Si—O—Si bond or a Si—O—N bond. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

  Adjustment of the composition of the silicon oxynitride of the layer obtained by irradiating the layer containing polysilazane with vacuum ultraviolet light can be performed by appropriately controlling the oxidation state by appropriately combining the above oxidation mechanisms (1) to (4). it can. Note that the scope of the present invention is not limited by the above mechanism.

Therefore, in the vacuum ultraviolet light irradiation step of the present invention, the illuminance of the vacuum ultraviolet rays received by the composition layer is preferably 1 mW / cm ^{2 to} 10 W / cm ² at least once, and 30 mW / cm ^{2 to} 200 mW / cm. more preferably ^2, and more preferably than ^{50mW / cm 2 ~160mW / cm 2} .

If the irradiation intensity is less than 1 mW / cm ² , the conversion efficiency may be greatly reduced. If the irradiation intensity is higher than 10 W / cm ² , the coating film may be ablated or the substrate may be damaged. Come.

Irradiation energy amount of the vacuum ultraviolet light according to the present invention is preferably 10 to 10000 mJ / cm ^2, more preferably 100~8000mJ / cm ^2, more preferably 200~6000mJ / cm ² Even more preferably, it is 500 to 5000 mJ / cm ² . It is less than ^{(ML1~7.3000mJ / cm 2) 10mJ /} cm 2, an insufficient conversion reaction, cracking or by excessive conversion reaction exceeds 10000 mJ / cm ^2, coming out concerns thermal deformation of the substrate .

  In the vacuum ultraviolet ray in the step (3) according to the present invention, it is preferable to form the first barrier layer by a modification treatment that irradiates the vacuum ultraviolet ray having a wavelength component of 200 nm or less.

  Examples of the vacuum ultraviolet light source according to the present invention include a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, and an excimer lamp (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. )), UV light laser, and the like. Among them, a rare gas excimer lamp is preferably used.

  In addition, although the ultraviolet-ray said by this invention generally refers to the electromagnetic wave which has a wavelength of 10-400 nm, in the case of ultraviolet irradiation processes other than the vacuum ultraviolet-ray (10-200 nm) process mentioned later, Preferably it is 200-400 nm Use ultraviolet light. Moreover, it is preferable to set irradiation intensity and irradiation time in the range which does not receive damage to the base material which carry | supports the 1st barrier layer irradiated for ultraviolet irradiation.

  In addition, the composition layer may be heat-treated at the same time as the irradiation with vacuum ultraviolet rays in order to promote the reaction (also referred to as oxidation reaction, conversion treatment, or modification treatment). As the heat treatment method, the same method as the heat treatment in which the coating film is dried to form the composition layer is employed.

  In the atmosphere of vacuum ultraviolet light irradiation according to the present invention, the composition layer is preferably irradiated with ultraviolet rays at a temperature of 40 to 120 ° C. for 5 seconds to 10 minutes.

[Second barrier layer]
The second barrier layer according to the present invention is preferably formed on the first barrier layer.

  The second barrier layer according to the present invention has at least one selected from the group consisting of silicon oxide, silicon oxynitride, and silicon nitride, and silicon oxide, oxynitride in terms of gas barrier properties and transparency. It is preferable to have at least two selected from silicon or silicon nitride, and more preferably at least one selected from silicon oxide or silicon oxynitride. The second barrier layer is preferably formed substantially or completely as an inorganic layer.

  It is formed on the first barrier layer by a vapor phase growth method (a metal compound is subjected to chemical vapor deposition or physical vapor deposition) or a coating method. That is, when there are a plurality of barrier layers according to the present invention, at least one of them may be formed by a coating method, and when the first barrier layer is formed by a coating method, the first barrier layer A vapor phase growth method (chemical vapor deposition or physical vapor deposition of a metal compound) or a coating method can be employed on the top, but in the present invention, the second barrier layer is preferably formed by a coating method. . In the case where the second barrier layer is formed on the first barrier layer by a vapor deposition method or a coating method, the method and conditions described in the above-mentioned “first barrier layer” column can be used. It is omitted here.

  In the present invention, the first barrier layer and the second barrier layer are more preferably formed by a coating method.

  The average thickness of the second barrier layer according to the present invention is preferably 10 nm to 2 μm, more preferably 20 nm to 1 μm.

  From the viewpoint of high barrier performance, which is the range where the average thickness is applied.

  As a method for forming the second barrier layer by the coating method according to the present invention, a step (4) of preparing a composition containing a solvent, polysilazane and an amine compound, and coating the composition on the first barrier layer It is preferable to have a step (5) of forming the composition layer by drying and a step (6) of forming a second barrier layer by irradiating the composition with vacuum ultraviolet light. Each step will be described below.

(About step (1))
Step (4) according to the present invention is a step of preparing a composition containing a solvent, polysilazane and an amine compound, and a metal catalyst may be added as necessary.

  That is, step (4) according to the present invention is the same method as step (1) above, and each component (solvent, polysilazane, amine compound, and metal catalyst) that can be used in step (1) and the composition thereof The range of the ratio is the same as the range of each component (solvent, polysilazane, amine compound, and metal catalyst) that can be used in step (4) and the range of the composition ratio. Therefore, here, the solvent (including sp distance characteristics of the mixed solvent), polysilazane, amine compound and metal catalyst used in the step (4) according to the present invention and the composition ratio range thereof are incorporated with the above step (1). Omitted.

  Further, the composition obtained in the step (1) and the composition obtained in the step (4) may be the same or different.

(About step (5))
The step (5) according to the present invention is a step of forming a composition layer by applying and drying the composition prepared in the step (4) on the first barrier layer.

  That is, the step (5) according to the present invention is the same as the above step (2) except that the composition prepared in the above step (4) is applied on the first barrier layer. The process (5) according to the invention is incorporated and omitted.

(About step (6))
The step (6) according to the present invention is a step of forming a barrier layer by irradiating the composition layer formed on the first barrier layer in the step (5) with vacuum ultraviolet light. That is, at least a part of polysilazane is modified into silicon oxynitride by the step (6).

  Therefore, the step (6) according to the present invention is the same as the above step (3) except that the composition layer formed on the first barrier layer is irradiated with vacuum ultraviolet light. The process (5) according to the above is incorporated and omitted.

(Surface roughness of the second barrier layer: smoothness)
The surface roughness (Ra) of the surface on the vacuum ultraviolet irradiation side of the second barrier layer according to the present invention is preferably 10 nm or less, more preferably 1 nm or less. When the surface roughness is in the range specified above, when used as a resin substrate for electronic devices, the smooth film surface with few irregularities improves the light transmission efficiency and reduces the leakage current between the electrodes. This is preferable because the conversion efficiency is improved. The surface roughness (Ra) of the barrier layer according to the present invention can be measured by the following method.

  The surface roughness is calculated from an uneven sectional curve continuously measured with an AFM (Atomic Force Microscope), for example, DI3100 manufactured by Digital Instruments, with a detector having a stylus with a minimum tip radius. This is a roughness related to the amplitude of fine irregularities measured by a stylus many times in a section whose measurement direction is several tens of μm.

[Middle layer]
In the gas barrier film according to the present invention, other layers (intermediate layers) other than the barrier layer may be appropriately formed between the substrate surface and / or the barrier layer. For example, an anchor coat layer (an easy-adhesion layer) may be formed for the purpose of improving the adhesion of a hybrid layer or the like to the substrate surface. The anchor coating agent that can be used is not particularly limited, but a silane coupling agent is used from the viewpoint of obtaining a high adhesion by forming a thin film at a monomolecular level to a nano level and forming a molecular bond at the layer interface. Is preferred. In addition, an intermediate layer between the barrier layers may be formed for the purpose of protecting the barrier layer. In addition, a stress relaxation layer made of a resin or the like, a smoothing layer for smoothing the surface of the substrate, a bleedout prevention layer for preventing bleedout from the substrate or the like can be provided. Furthermore, a back coat layer may be provided on the substrate for the purpose of improving the curl balance of the gas barrier layer, device fabrication process resistance, handling suitability, and the like. In addition, when an intermediate | middle layer is provided in the said base material, a gas barrier layer is normally arrange | positioned on an intermediate | middle layer. Hereinafter, various intermediate layers according to the present invention will be described.

(Intermediate layer between barrier layers)
In the present invention, as a method for forming an intermediate layer between barrier layers between the respective barrier layers, a method for forming a polysiloxane modified layer can be applied. In this method, a polysiloxane-containing coating solution is applied onto the barrier layer by a wet coating method and dried, and then the dried coating film is irradiated with vacuum ultraviolet rays to form a polysiloxane-modified layer. The polysiloxane modified layer exhibits a function as an intermediate layer between the barrier layers.

  Moreover, it is more preferable that the coating liquid for forming an intermediate layer used for forming the intermediate layer between the barrier layers contains (A) polysiloxane and (B) an organic solvent.

  The polysiloxane applicable to the formation of the intermediate layer between the barrier layers according to the present invention is not particularly limited, but an organopolysiloxane represented by the following general formula (2) is particularly preferable.

  First, a system using an organopolysiloxane represented by the general formula (2) as (A) polysiloxane will be described.

In the general formula (a), R ^{3 to} R ⁸ represent the same or different organic groups 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.

  Furthermore, in the general formula (a) according to the present invention, 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 (B) applicable to the present invention include alcohol solvents, ketone solvents, amide solvents, ester solvents, aprotic solvents, and the like.

  Here, as alcohol solvents, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, 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 and the like are preferable.

  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 amide solvents include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide 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.

  (B) As the organic solvent, alcohol solvents are preferable among the above organic solvents.

  Examples of the method for applying the intermediate layer forming coating solution between the barrier layers include spin coating, dipping, roller blades, and spraying.

  The thickness of the intermediate layer between the barrier layers formed by the intermediate layer forming coating solution between the barrier layers (after the modification treatment) is preferably in the range of 100 nm to 10 μm. If the film thickness of the intermediate layer between the barrier layers is 100 nm or more, the barrier property under high humidity can be secured, and if it is 10 μm or less, stable coating properties can be obtained when forming the intermediate layer between the barrier layers. And high light transmittance can be realized.

The intermediate layer between the barrier layers according to the present invention has a film density of usually 0.35 to 1.2 g / cm ³ , preferably 0.4 to 1.1 g / cm ³ , and more preferably 0.5 to 1. 0 g / cm ³ . If the film density is 0.35 g / cm ³ or more, sufficient mechanical strength of the coating film can be obtained.

  The intermediate layer between the barrier layers according to the present invention is formed by applying a coating solution containing polysiloxane onto the barrier layer by a wet coating method and drying, and then irradiating the dried coating film with vacuum ultraviolet rays. .

As the vacuum ultraviolet light used for the formation of the intermediate layer between the barrier layers according to the present invention, the same vacuum ultraviolet light irradiation treatment as described in the formation of the first barrier layer can be applied. It that case, the integrated light quantity of vacuum ultraviolet light for forming the intermediate layer of the barrier layers by reforming polysiloxane layer according to the present invention, 500 mJ / cm ² or more and 10,000 / cm ² or less Is preferred. A sufficient barrier performance can be obtained if the accumulated amount of vacuum ultraviolet light is 500 mJ / cm ² or more, and if it is 10,000 mJ / cm ² or less, a highly smooth barrier layer without deformation of the substrate. The intermediate layer can be formed.

  In addition, the intermediate layer between the barrier layers according to the present invention is preferably formed through a heating process in which the heating temperature is 50 ° C. or higher and 200 ° C. or lower before irradiation with vacuum ultraviolet light as a pretreatment. If the heating temperature is 50 ° C. or more, sufficient barrier properties can be obtained, and if it is 200 ° C. or less, an intermediate layer between barrier layers having high smoothness can be formed without deforming the substrate.

  As a heating method used in the heating step, a hot plate, an oven, a furnace, or the like can be used. As a heating atmosphere, an atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. It can be carried out.

  The intermediate layer between the barrier layers according to the present invention has a function of covering the barrier layer and preventing damage to the (gas) barrier layer in the barrier film. It can also prevent damage to the layer.

  For example, after forming a polysiloxane coating film on the pre-modified polysilazane coating film formed during the barrier layer forming step, and simultaneously irradiating the polysilazane coating film and the polysiloxane coating film with vacuum ultraviolet light, The barrier layer and the intermediate layer may be formed simultaneously by performing heat treatment at 100 ° C. or higher and 250 ° C. or lower. In addition, a polysiloxane coating film is formed on the polysilazane coating film that has been subjected to vacuum ultraviolet light irradiation treatment, and after the vacuum ultraviolet light irradiation treatment is performed on the polysiloxane coating film, a heating step of 100 ° C. or higher and 250 ° C. or lower is performed. And a barrier layer and an intermediate layer may be formed.

  As described above, when heat treatment at 100 ° C. or higher is performed with the polysilazane coating film (barrier layer) covered with the intermediate layer (polysiloxane coating film), minute cracks are formed in the barrier layer due to the thermal stress caused by the heat treatment. Can be prevented, and the water vapor barrier property of the barrier layer can be stabilized.

(Anchor coat layer)
On the surface of the substrate according to the present invention, an anchor coat layer may be formed as an intermediate layer for the purpose of improving the adhesion with the first barrier layer. Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One or two or more can be used in combination. Among these, an epoxy resin is particularly preferable. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated 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 (dry state).

(Smooth layer)
Furthermore, a smooth layer may be provided as an intermediate layer on the surface of the substrate according to the present invention. In particular, the surface preferably has a pencil hardness defined by JIS K 5600-5-4 of H or higher. Further, it is preferable to provide a smooth layer such that the surface roughness of the intermediate layer is 10 nm <Rt (p) <30 nm at the maximum cross-sectional height Rt (p) defined by JIS B 0601: 2001.

  Although the film thickness of the smooth layer is not limited, the film thickness of the smooth layer is preferably 0.1 μm to 10 μm, in order to cover the unevenness of the substrate surface to form a smooth surface and ensure flexibility, and 0.5 μm ˜6 μm is a more preferable range.

  In particular, when the second barrier layer is formed by modifying the polysilazane coating film on the first barrier layer by a coating method as in the present invention, the second barrier layer is a defect of the first barrier layer. While having the merit of repair and smoothing the surface, the first barrier layer receives the stress due to the shrinkage in the process of reforming from the coating film to the high density inorganic film with high gas barrier properties. May occur, and there is a demerit that the configuration of the present invention may not be fully utilized.

  As a result of intensive studies by the present inventors, a layer under the first barrier layer is provided with a smooth layer such that the maximum surface height difference Rt is 10 nm <Rt <30 nm. It was found that the stress can be prevented from being concentrated on the first barrier layer, and the effect of the configuration of the present invention can be exhibited most.

  Furthermore, the higher inorganic component of the smooth layer is preferable from the viewpoint of the adhesion between the first barrier layer and the substrate and the hardness of the smooth layer, and the composition ratio of the entire smooth layer is 10% by mass or more. Is preferable, and 20% by mass or more is more preferable. The smooth layer may be an organic-inorganic hybrid composition such as a mixture of an organic resin binder (photosensitive resin) and inorganic particles, or may be an inorganic layer that can be formed by a sol-gel method or the like.

  The smooth layer also flattens the rough surface of the transparent resin film substrate where protrusions and the like are present, or unevenness and pinholes generated in the transparent first barrier layer due to the protrusions present on the transparent resin film substrate. Is provided to fill and flatten. Such a smooth layer is basically formed by curing a thermosetting resin or a photosensitive resin.

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

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used in order to improve the film formability and prevent the generation of pinholes in the film.

  As described above, 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 it is smaller than 10 nm, the coating property may be impaired 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 in the step of coating a silicon compound described later. . Moreover, when larger than 30 nm, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of μm many times. Specifically, the measurement range for one time is 80 μm × 80 μm, and measurement is performed three times by changing the measurement location.

In the present invention, the thickness of the smooth layer is 0.1 to 10 μm, preferably 1 to 6 μm. When the thickness is 1 μm or more, the smoothness of the film having a smooth layer is sufficient, and the surface hardness is easily improved. By setting the thickness to 10 μm or less, the balance of optical properties of the smooth film can be easily adjusted. When the smooth layer is provided only on one surface of the transparent polymer film, curling of the smooth film can be easily suppressed.

(Bleed-out prevention layer)
In the gas barrier film of the present invention, a bleed-out preventing layer can be provided as an intermediate layer. The bleed-out prevention layer is used for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the film base material to the surface when the film having the smooth layer is heated and contaminate the contact surface. It is provided on the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  In addition, since the film undergoes large film shrinkage during the reforming treatment, it is preferable to suppress the lateral deformation and prevent cracking. For this purpose, a so-called hard coat layer having a high surface hardness or elastic modulus can be provided, but the bleed-out preventing layer can also serve as the hard coat layer.

  The unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer as a hard coat agent is a polyunsaturated compound having two or more polymerizable unsaturated groups in the molecule. Examples thereof include organic compounds and unit price unsaturated organic compounds having one polymerizable unsaturated group in the molecule.

  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. .

  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. In particular, it is preferable to contain a thermosetting resin.

  The bleed-out prevention layer as described above is prepared as a coating solution by mixing a hard coating agent, a matting agent, and other components as necessary, and appropriately using a diluent solvent as necessary. It can be formed by coating the film surface with a conventionally known coating method and then curing it by irradiating with ionizing radiation.

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

  The average film thickness of the bleed-out prevention layer in the present invention is 1 to 10 μm from the viewpoints of improving heat resistance as a film, facilitating adjustment of the balance of optical characteristics of the film, and preparing curl of a gas barrier film. The thickness is preferably 2 to 7 μm.

[Protective layer]
The gas barrier film 10 according to the present invention may have a protective layer 3 on the barrier layer as necessary. The protective layer is also referred to as an overcoat layer, and may have a function of protecting the barrier layer from moisture and maintaining gas barrier properties.

  As the protective layer according to the present invention, it is preferable to use an organic-inorganic composite resin layer using an organic resin such as an organic monomer, oligomer or polymer, or a monomer, oligomer or polymer of siloxane or silsesquioxane having an organic group. it can. These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. It is preferable to apply a light irradiation treatment or a heat treatment to the layer formed by coating from the organic resin composition coating solution to be cured. Here, the “crosslinkable group” is a group that can crosslink the binder polymer by a chemical reaction that occurs during light irradiation treatment or heat treatment. The chemical structure of the organic resin or organic-inorganic composite resin having a specific polymerizable group or crosslinkable group is not particularly limited. For example, as the functional group capable of addition polymerization, an ethylenically unsaturated group, an epoxy group / oxetanyl group, etc. Of the cyclic ether group. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group, a thiol group, a halogen atom, an onium salt structure etc. are mentioned, for example. Among these, an ethylenically unsaturated group is preferable and includes functional groups described in paragraphs 0130 to 0139 of JP2007-17948A.

  The protective layer according to the present invention may contain an inorganic material as necessary. When an inorganic material is contained, the elastic modulus of the protective layer generally increases. Therefore, the elastic modulus of the protective layer can be adjusted to a desired value by appropriately adjusting the content ratio of the inorganic material.

  As the inorganic material, inorganic fine particles having a number average particle diameter of 1 to 200 nm are preferable, and inorganic fine particles having a number average particle diameter of 3 to 100 nm are more preferable. As the inorganic fine particles, metal oxides are preferable from the viewpoint of transparency.

  In the protective layer, a so-called coupling agent can be used alone or mixed with other materials. The coupling agent is not particularly limited, such as a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, but a silane coupling agent is preferable from the viewpoint of the stability of the coating solution.

  Further, the protective layer according to the present invention is prepared as a coating solution by using the organic resin (composition), the inorganic material, and other components as necessary, and appropriately using a diluting solvent as necessary. It is preferable to form the coating solution by applying the coating solution to the surface of the substrate by a conventionally known coating method and then curing it by irradiating with ionizing radiation. In addition, as a method of irradiating with ionizing radiation, 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 are irradiated. Alternatively, the irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

  The protective layer can also be cured by irradiation with the above-described excimer lamp. When the gas barrier layer and the protective layer are applied and formed on the same line, the overcoat layer is preferably cured by irradiation with an excimer lamp.

  Furthermore, as the protective layer according to the present invention, a method for forming the above-described polysiloxane modified layer of the intermediate layer may be applied.

[Gas barrier film]
In the gas barrier film according to the present invention, the base material, the first barrier layer, the second barrier layer, and the protective layer are preferably laminated sequentially, and the protective layer preferably has no gas barrier property. .

  The gas barrier film according to the present invention is a film base (retardation film) having optical anisotropy, particularly a film base which is a λ / 4 retardation plate used for a circularly polarizing plate, and the side of the film base. Thus, the gas barrier unit includes a first barrier layer containing an inorganic substance and a second barrier layer obtained by modifying a coating film formed by applying polysilazane. Moreover, the structure which has the gas barrier property unit mentioned above on both surfaces of the base material may be sufficient.

  As an advantage when the gas barrier film of the present invention is used, for example, by using the gas barrier film of the present invention as a display-side substrate of an OLED display, it is possible to achieve a significant reduction in thickness by combining members. Considering the simplest configuration, the configuration on the display side of the current OLED display element is display side glass substrate / adhesive layer / λ / 4 plate / adhesive layer / polarizing plate. In contrast, by using the gas barrier film of the present invention, the gas barrier film / adhesive layer / polarizing plate of the present invention can be obtained, and the thickness of this portion can be reduced to about 30%. is there. Furthermore, as described above, the gas barrier film of the present invention does not break like glass, and can be a great advantage particularly when applied to a display device mounted on a mobile device, as the weight is reduced.

  The average thickness of the gas barrier film according to the present invention is preferably 5 to 500 μm, and more preferably 25 to 250 μm. In this specification, a laminate (not including a base material) in which a first barrier layer, a second barrier layer, and a protective layer are sequentially laminated is referred to as a “gas barrier layer unit”.

  In this invention, the structure which has arrange | positioned the gas barrier layer unit on both surfaces of a base material may be sufficient. Also in this case, the gas barrier layer units (first barrier layer, second barrier layer, and protective layer) formed on both surfaces of the substrate may be the same or different. By forming gas barrier units on both sides, dimensional changes due to moisture absorption and desorption of the base film itself under severe conditions of high temperature and high humidity are suppressed, stress on the gas barrier unit is reduced, and device durability Improves. Moreover, when using heat resistant resin for a base material, since the effect which provides a gas-barrier unit on both front and back side is large, it is preferable. In other words, heat-resistant resins represented by polyimide and polyetherimide are non-crystalline, so the water absorption is larger than that of crystalline PET and PEN, and the dimensional change of the substrate due to humidity is larger. End up. By providing the gas barrier unit on both the front and back sides of the base material, the dimensional change of the base material at both high temperature and high humidity can be suppressed.

  In particular, when used as a flexible display, the process temperature may exceed 200 ° C. in the array production process, and it is preferable to use a high heat resistant substrate. Furthermore, in addition to the high heat-resistant substrate, the gas barrier film according to the present invention may be provided between the substrate and the first barrier layer and / or between each barrier layer (for example, the first barrier layer, for example). An intermediate layer (an intermediate layer between the barrier layers, an anchor coat layer, a smooth layer, and / or a bleed-out prevention layer) may be provided between the first barrier layer and the second barrier layer.

[Preferred production method of gas barrier film]
The method for producing a gas barrier film according to the present invention includes a step of preparing a composition containing a solvent, polysilazane and an amine compound, and a step of forming the composition layer by applying and drying the composition on a substrate. And a step of irradiating the composition with vacuum ultraviolet light to form a barrier layer, wherein the solvent has a Hansen SP value Ra of 8 or more and 14 or less and a boiling point of 70 ° C. or more with the substrate. It is a mixed solvent containing 20 mass% or more and 50 mass% or less of the solvent component which is 110 degrees C or less.

  Thereby, since the solvent of the composition contains a solvent component having a Hansen SP value distance Ra of 8 or more and 14 or less and a boiling point of 70 ° C. or more and 110 ° C. or less when the composition layer is dried. In addition, since it has an appropriate SP value distance with polysilazane and the like contained in the base material and the barrier layer, it has moderate compatibility with the base material and the adjacent barrier layer, so that adhesion can be secured. Conceivable.

  In the method for producing a gas barrier film, applying the composition on the substrate may be on the substrate, and it is not necessary to directly contact the composition and the substrate, as shown in FIG. When a plurality of barrier layers are provided, it is not necessary to form all the barrier layers by the production method, and it is sufficient to produce a gas barrier film by forming at least one barrier layer by the production method. However, when a plurality of barrier layers are provided, it is preferable to perform the first barrier layer formed on the most base side by the manufacturing method, and it is particularly preferable to form all the barrier layers by the manufacturing method.

  The form of the method for producing the gas barrier film by carrying out the first barrier layer formed on the most substrate side by the production method of the present invention is the above-mentioned step (1), step (2), and step (3). ), And all the barrier layers are formed by the production method of the present invention to produce a gas barrier film in the steps (1), (2) and (3). After forming one barrier layer, the steps (4) to (6) may be repeated as necessary. Moreover, what is necessary is just to form an intermediate | middle layer and a protective layer in the said process (1)-(6) suitably, when forming the intermediate | middle layer and protective layer mentioned above.

  Therefore, for example, a preferred embodiment of the method for producing a gas barrier film according to the present invention shown in FIG. 1 includes a step (1) of preparing a composition containing a solvent, a polysilazane and an amine compound, and the composition on the substrate surface. Applying and drying a product to form the composition layer (2), and irradiating the composition with vacuum ultraviolet light to form a first barrier layer (3), and A second barrier layer is formed on the first barrier layer by a coating method or a vapor deposition method.

[Method for measuring characteristic values of gas barrier film]
Each characteristic value of the gas barrier film of the present invention can be measured according to the following method.

(Measurement of film density)
X-ray reflectivity measuring device: Rigaku Electric thin film structure evaluation device ATX-G
X-ray source target: Copper (1.2kW)
Measurement: The X-ray reflectivity curve is measured using a four-crystal monochromator, a density distribution profile model is created and fitted, and the density distribution in the film thickness direction can be calculated.

(Measurement of water vapor transmission rate (WVTR))
Various methods have been proposed for measuring the water vapor transmission rate according to the method B described in JIS K 7129 (1992). For example, the cup method, dry / wet sensor method (Lassy method), infrared sensor method (mocon method) can be mentioned as representatives, but as the gas barrier properties improve, these methods may reach the measurement limit. A method is also proposed.

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

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

  3. HTO method (General Atomics, USA) A method of calculating water vapor permeability using tritium.

  4). Method proposed by A-Star (Singapore) (International Publication No. 2005/95924) A material whose electrical resistance is changed by water vapor or oxygen (for example, Ca, Mg) is used for the sensor, and the electrical resistance change and its inherent 1 / F The method of calculating water vapor transmission rate from a fluctuation component.

  In the gas barrier film of the present invention, the method for measuring the water vapor transmission rate is not particularly limited, but in the present invention, the water vapor transmission rate measurement method was measured by the following Ca method.

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

  The obtained sample with both sides sealed was stored at 60 ° C. and 90% RH under high temperature and high humidity, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water was calculated.

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

Water vapor permeability of the gas barrier film of the present invention, preferably as low as possible, for example, is preferably 0.001~0.00001g ^/ m 2 · 24h, with 0.0001~0.00001g ^/ m 2 · 24h More preferably.

(Measurement of oxygen permeability)
Using an oxygen permeability measuring device (model name, “Oxytran” (registered trademark) (“OXTRAN” 2/20)) manufactured by MOCON, USA, under conditions of a temperature of 23 ° C. and a humidity of 0% RH , Measured based on the B method (isobaric method) described in JIS K7126 (1987). Further, the measurement is performed once for each of the two test pieces, and the average value of the two measured values is set as the oxygen permeability value.

The oxygen permeability of the gas barrier film of the present invention is preferably as low as possible. For example, it is more preferably less than 0.001 g / m ² · 24 h · atm (below the detection limit).

[Packaging form of gas barrier film]
The gas barrier film of the present invention can be continuously produced and wound into a roll form (so-called roll-to-roll production). In that case, it is preferable to stick and wind up a protective sheet on the surface in which the gas barrier layer was formed. In particular, when the gas barrier film of the present invention is used as a sealing material for organic thin film devices, it often causes defects due to dust (for example, particles) adhering to the surface, and a protective sheet is applied in a place with a high degree of cleanliness. It is very effective to prevent the adhesion of dust. In addition, it is effective in preventing scratches on the gas barrier layer surface that enters during winding.

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

[Use of gas barrier film]
The gas barrier film of the present invention is mainly a package for electronic devices, etc., or a gas barrier film used for display materials such as organic EL elements, solar cells, plastic substrates such as liquid crystals, and various device resins using the gas barrier film. It can be applied to substrates and various device elements.

  The gas barrier film according to the present invention can be preferably applied as various sealing materials and films. Hereinafter, as an example of an electronic device including the gas barrier film according to the present invention, the use relating to the organic light emitting device will be described in detail.

  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 Gas Barrier Film 1-1 >>
[Preparation of substrate]
Pure Ace WR-S (film thickness 50 μm) made of Teijin Kasei Co., Ltd. made of polycarbonate resin was used as a polymer film having a λ / 4 retardation.

[Formation of the first barrier layer]
"Preparation of a composition containing polysilazane"
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) and N, N, N ′, N ′,-tetramethyl-1,6 as an amine catalyst -A dibutyl ether solution containing 1% by mass of diaminohexane and 19% by mass of perhydropolysilazane (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) was mixed at a mass ratio of 4: 1, and butyl ether and 2 The solid content of the coating solution was adjusted to 5 mass% so that the solvent mass ratio of 2,4-trimethylpentane was 65:35. Furthermore, the composition (coating liquid 1) according to the present invention was prepared by appropriately adjusting the solvent addition amount according to the set film thickness.

“Formation of composition layer in first barrier layer”
On the said board | substrate, the composition (coating liquid 1) was apply | coated on the conditions from which the average film thickness after drying was set to 250 nm with a spin coater. The drying condition was 80 ° C. for 2 minutes.

"Vacuum UV irradiation treatment"
After forming the composition layer in the first barrier layer as described above, the first barrier layer was formed by performing a vacuum ultraviolet ray irradiation treatment of 5000 mJ / cm ² according to the following method.

(Vacuum UV irradiation treatment and conditions)
The vacuum ultraviolet irradiation was performed using the apparatus shown in the schematic sectional view of FIG. In FIG. 2, reference numeral 11 denotes an apparatus chamber, which is supplied with appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) and exhausted from a gas discharge port (not shown). In addition, the water vapor can be removed to maintain the oxygen concentration at a predetermined concentration. Reference numeral 12 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, and reference numeral 13 denotes an excimer lamp holder that also serves as an external electrode. Reference numeral 14 denotes a sample stage. The sample stage 14 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 11 by a moving means (not shown). Further, the sample stage 14 can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 15 denotes a sample on which a polysilazane compound coating layer is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 3 mm. Reference numeral 16 denotes a light shielding plate, which prevents the vacuum ultraviolet light from being applied to the coating layer of the sample during the aging of the Xe excimer lamp 12. The energy applied to the surface of the sample coating layer in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using an ultraviolet integrated light meter: C8026 / H8025UV POWER METER manufactured by Hamamatsu Photonics. In the measurement, the sensor head is installed at the center of the sample stage 14 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 11 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the process, and the sample stage 14 was moved at a speed of 0.5 m / min for measurement. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 12, an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement. After aging for 10 minutes, the irradiation distance was 3 mm, the oxygen concentration was 0.1%, the maximum illuminance was 130 mW / cm ² , and the cumulative irradiation energy was 5000 mJ / cm ² . The temperature of the sample stage 14 was set to 60 ° C., and the moving speed V of the sample stage 14 was set to 10 mm / min. Note that, as described above, the vacuum ultraviolet irradiation was performed after aging for 10 minutes in the same manner as the irradiation energy measurement.

[Formation of Second Barrier Layer]
"Preparation of a composition containing polysilazane"
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) and N, N, N ′, N ′,-tetramethyl-1,6 as an amine catalyst -A dibutyl ether solution containing 1% by mass of diaminohexane and 19% by mass of perhydropolysilazane (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) was mixed at a mass ratio of 4: 1, and butyl ether and 2 The solid content of the coating solution was adjusted to 5 mass% so that the solvent mass ratio of 2,4-trimethylpentane was 65:35. Furthermore, the composition (coating liquid 1) according to the present invention was prepared by appropriately adjusting the solvent addition amount according to the set film thickness.

“Formation of composition layer in second barrier layer”
On the first barrier layer, the composition (coating solution 1) was applied by a spin coater under the condition that the average film thickness after drying was 100 nm. The drying condition was 80 ° C. for 2 minutes.

"Vacuum UV irradiation treatment"
After forming the composition layer in the second barrier layer as described above, a vacuum ultraviolet ray irradiation treatment of 2000 mJ / cm ² is performed on the first barrier layer according to the method of the first barrier layer. A second barrier layer was formed.

(Vacuum UV irradiation treatment and conditions)
A second barrier layer was formed under the same conditions as the vacuum ultraviolet irradiation conditions in the formation of the first barrier layer except that the irradiation energy was 2000 mJ / cm ² .

(Formation of protective layer)
<Preparation of protective layer coating solution>
“Glaska HPC7003” and “Glaska HPC404H” manufactured by JSR Corporation were mixed at a ratio of 10: 1. Next, this mixed solution was diluted twice with butanol, and 5.0% of butyl cellosolve was further added to the mixed solution to prepare a coating solution for forming a protective layer. The solid content of this coating solution for forming a protective layer is 10%.

"Formation of polysiloxane layer"
On the second barrier layer, a coating liquid for forming a protective layer containing the polysiloxane compound was applied by a spin coater to form a polysiloxane layer. Drying conditions were 120 ° C. and 20 minutes.

<Polysiloxane layer modification treatment: vacuum ultraviolet irradiation treatment>
After the polysiloxane layer is formed as described above, a vacuum ultraviolet ray irradiation apparatus having the same structure as that used in the first barrier layer modification process is used to form the first barrier layer. A protective layer was formed in the same manner except that the cumulative amount of ultraviolet light was changed to 1500 mJ / cm ² .

<< Production of Gas Barrier Films 1-2 to 1-9 and 1-12, 1-13 >>
Preparation of gas barrier film sample 1-1 except that the solvent and mixing ratio of the base material and composition (coating liquid) were changed to the solvent and mixing ratio of the base material and composition (coating liquid) shown in Table 1. Similarly, production of gas barrier films 1-2 to 1-9 and 1-12 and 1-13 was produced.

<< Production of Gas Barrier Films 1-10 and 1-11 >>
The solvent and mixing ratio of the base material and the composition (coating liquid) were changed to the solvent and mixing ratio of the base material and the composition (coating liquid) shown in Table 1, and the composition (coating liquid) containing polysilazane was spin coated. After the coating, without vacuum ultraviolet irradiation treatment, as described in JP-A-9-174782, it was treated at 130 ° C. for 2 minutes, further at 100 ° C. for 1 hour, and further at a high temperature of 80 ° C. and 80% RH. A first barrier layer and a second barrier layer were formed by treatment in a high humidity atmosphere for 1 hour. Moreover, formation of the protective layer produced gas barrier film 1-10 and 1-11 similarly to the sample of gas barrier film 1-1.

<Evaluation of water vapor barrier properties>
Samples with and without bending treatment were prepared from the samples of the gas barrier films 1-1 to 1-13 prepared above, and the water vapor transmission rate was measured by the following method. The bending treatment was performed a total of 200 bending treatments, 100 times each on the inside and outside of the gas barrier surface with a curvature of 50 mmφ.

<Apparatus used for water vapor barrier evaluation>
Vapor deposition device: JEOL Ltd. vacuum vapor deposition device JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
<Raw materials used for evaluation of water vapor barrier properties>
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impervious metal: Aluminum (average φ: 3-5 mm, granular)
[Preparation of water vapor barrier property evaluation sample]
Using the above vacuum deposition apparatus (vacuum deposition apparatus JEE-400 manufactured by JEOL Ltd.), metal calcium was deposited in a size of 12 mm × 12 mm through a mask on the surface side where the barrier layer of each of the produced barrier films was formed. At this time, the deposited film thickness was set to 80 nm.

  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, the air is quickly transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum vapor-deposited surface via a sealing ultraviolet curable resin (manufactured by Nagase ChemteX). Each of the samples for water vapor barrier property evaluation was produced by curing and adhering the resin to perform main sealing.

[Measurement of water vapor barrier properties]
Each of the obtained water vapor barrier property evaluation samples was stored at 60 ° C. in a high-temperature and high-humidity environment of 90% RH, and the state in which metallic calcium was corroded with respect to the storage time was observed. Observation is performed every hour for up to 6 hours, every 3 hours for up to 24 hours, every 6 hours for up to 48 hours thereafter, and every 12 hours thereafter, 12 mm x 12 mm metal The area where metallic calcium corroded relative to the calcium deposition area was calculated in%. The time when the area where the metal calcium corrodes becomes 1% is obtained by interpolating from the observation result by a straight line, and the metal calcium vapor deposition area, the amount of water vapor corroding the metal calcium for the area of 1%, and the time required for it. From the relationship, the water vapor transmission rate (WVTR) of each gas barrier film was calculated. The results are shown in Table 2 below.

  As shown in Table 2 above, it is confirmed that the gas barrier film obtained by the production method of the present invention has a very high barrier property. Further, it is confirmed that the water vapor barrier property is not deteriorated even when the bending treatment is performed.

Example 2
<< Production of organic EL element >>
Using each gas barrier film (1-1 to 1-13) produced in Example 1 as a sealing film, an organic EL element as shown in FIG. 3 was produced as an example of an electronic device according to the following method. .
<Preparation of organic EL element>
(Formation of first electrode layer)
On the protective layers of the samples 1-1 to 1-13 of the gas barrier film 21, ITO (indium tin oxide) having a thickness of 150 nm is formed by sputtering, and patterned by photolithography. An electrode layer 22 was formed. The pattern was such that the light emission area was 50 mm square.

(Formation of hole transport layer)
On the first electrode layer 22 of each gas barrier film 21 on which the first electrode layer is formed, the following hole transport layer forming coating solution is applied by extrusion coating in an environment of 25 ° C. and 50% RH. After coating, the hole transport layer 23 was formed by drying under the following conditions. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

Before coating the hole transport layer forming coating solution, the sample was subjected to a cleaning surface modification treatment using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm ² and a distance of 10 mm. The charge removal treatment was performed using a static eliminator with weak X-rays.

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

(Drying and heat treatment conditions)
After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment. The back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using the apparatus, and the hole transport layer 23 was formed.

(Formation of the light emitting layer 24)
Subsequently, on the hole transport layer 23 of each gas barrier film on which the hole transport layer 23 is formed, the following white light emitting layer forming coating solution is applied by an extrusion coater and then dried to form the light emitting layer 24. did. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

(Preparation of white light emitting layer forming coating solution)
The host material HA is 1.0 g, the dopant material DA is 100 mg, the dopant material DB is 0.2 mg, the dopant material DC is 0.2 mg, and dissolved in 100 g of toluene to form a white light emitting layer. It was prepared as a coating solution.

(Application conditions)
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.

(Drying and heat treatment conditions)
After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., and then a temperature of 130 ° C. Then, the light emitting layer 24 was formed.

(Formation of the electron transport layer 25)
Subsequently, on the light emitting layer 24 of each gas barrier film on which the light emitting layer 24 was formed, the following electron transport layer forming coating solution was applied by an extrusion coater and then dried to form the electron transport layer 25. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

(Application conditions)
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.

(Preparation of coating solution for electron transport layer formation)
The electron transport layer was prepared by dissolving EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.

(Drying and heat treatment conditions)
After applying the electron transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 200 ° C. to form the electron transport layer 25.

(Formation of electron injection layer 26)
Subsequently, an electron injection layer 26 was formed on the electron transport layer 25 of each gas barrier film on which the electron transport layer 25 was formed.
First, the substrate was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. The electron injection layer 26 having a thickness of 3 nm was formed by heating cesium fluoride prepared in advance in a tantalum vapor deposition boat in a vacuum chamber.

(Formation of the second electrode layer 27)
Subsequently, on the electron injection layer 26 of each gas barrier film in which the electron injection layer 26 is formed, the second electrode is formed under a vacuum of 5 × 10 ⁻⁴ Pa except for a portion to be a take-out electrode on the first electrode layer. Using aluminum as a material for forming the electrode layer, a mask pattern was formed so as to have a light emission area of 50 mm square by vapor deposition so as to have an extraction electrode, and a second electrode layer 27 having a thickness of 100 nm was formed. .

(Cutting)
Each sample formed up to the second electrode layer 27 was moved again to a nitrogen atmosphere, and cut to a prescribed size using an ultraviolet laser to produce an organic EL element.

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

  Pressure bonding conditions: Pressure bonding was performed at a temperature of 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.

(Sealing)
A sealing member was bonded to the organic EL element to which the electrode lead (flexible printed circuit board) was connected using a commercially available roll laminating apparatus, and samples 1 to 13 of the organic EL element were produced. As a sealing member, a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) and a polyethylene terephthalate (PET) film (12 μm thick) adhesive for dry lamination (two-component reaction type urethane adhesive) (The thickness of the adhesive layer is 1.5 μm) was prepared. At this time, for bonding the sealing member, a thermosetting adhesive was applied uniformly at a thickness of 20 μm along the bonding surface (shiny surface) of the aluminum foil using a dispenser to form an adhesive layer 28. Moreover, the following epoxy adhesives were used as a thermosetting adhesive.

Bisphenol A diglycidyl ether (DGEBA)
Dicyandiamide (DICY)
Epoxy adduct curing accelerator Thereafter, the sealing substrate is closely attached and arranged so as to cover the joint between the take-out electrode and the electrode lead, and pressure bonding conditions using a pressure roll, pressure roll temperature 120 ° C., pressure 0.5 MPa. The device was tightly sealed at an apparatus speed of 0.3 m / min.

<< Evaluation of organic EL elements >>
The durability of the samples 1 to 13 of the organic EL devices produced above was evaluated according to the following method.

<Durability evaluation>
(Accelerated deterioration processing)
Each sample of the organic EL device produced above was subjected to an accelerated deterioration treatment for 400 hours in an environment of 60 ° C. and 90% RH, and then evaluated for the following black spots together with the organic EL device not subjected to the accelerated deterioration treatment. Went.

(Evaluation of sunspots)
A current of 1 mA / cm ² was applied to each of the organic EL element sample subjected to the accelerated deterioration treatment and the organic EL element not subjected to the accelerated deterioration treatment to emit light continuously for 24 hours. A part of the panel was enlarged with Moritex Corporation MS-804 and lens MP-ZE25-200), and photographing was performed. The photographed image was cut out in a 2 mm square, the black spot generation area ratio was determined, the element deterioration resistance rate was calculated according to the following formula, and the durability was evaluated according to the following criteria. If the evaluation rank was ◎ or ◯, it was determined that the characteristic was practically preferable.

A: The element deterioration resistance rate is 90% or more. B: The element deterioration resistance ratio is 60% or more and less than 90%. Δ: The element deterioration resistance ratio is 20% or more and less than 60%. The deterioration resistance rate is less than 20%.

  The results obtained as described above are shown in Table 2 below.

  As shown in Table 3 above, it was confirmed that the gas barrier film obtained by the production method of the present invention has a very high barrier property that can be used as a sealing film for organic EL elements. It was.

10: gas barrier film 0: base material 1: first barrier layer 2: second barrier layer 3: protective layer 11: device chamber 12: Xe excimer lamp 13: excimer lamp holder 14 also serving as an external electrode: sample stage 15: Sample 16: Light shielding plate 21: Gas barrier film 22: First electrode layer 23: Hole transport layer 24: Light emitting layer 25: Electron transport layer 26: Electron injection layer 27: Second electrode layer 28: Adhesive layer 29 : Aluminum foil / PET film composite sealing member

Claims (5)

A method for producing a gas barrier film comprising a gas barrier layer formed by irradiating vacuum ultraviolet light after applying and drying a composition containing a solvent, a polysilazane and an amine compound on a substrate surface,
A gas barrier comprising a solvent component having a Hansen SP value distance Ra of 8 or more and 14 or less and a boiling point of 70 ° C. or more and 110 ° C. or less and 20% by mass or more and 50% by mass or less in the solvent. For producing a conductive film.   The gas barrier film according to claim 1, wherein the resin substrate is a polycarbonate having optical anisotropy, a polycarbonate copolymer film having optical anisotropy, a cycloolefin resin, or a cycloolefin copolymer resin film. Method.   The method for producing a gas barrier film according to claim 1 or 2, wherein the solvent component is at least one selected from the group consisting of 2,2,4-trimethylpentane, n-heptane, and cyclohexane.   4. The method for producing a gas barrier film according to claim 1, wherein the drying temperature in the drying step is 60 ° C. or higher and 120 ° C. or lower. The amine compounds include N, N-diethylethanolamine, triethylamine, N, N ′, N′-tetramethyl-1,3-diaminopropane, and N, N ′, N′-tetramethyl-1,6-diamino. It is at least 1 selected from the group which consists of hexane, The manufacturing method of the gas barrier film of any one of Claims 1-4.