JPWO2014119754A1 - Gas barrier film, method for producing the same, and electronic device using the same - Google Patents

Abstract

A barrier layer formed by vapor deposition of an inorganic compound on at least one surface of the substrate, and a barrier layer formed by vapor deposition of at least the inorganic compound on the substrate; A barrier layer formed by applying a solution containing a polysilazane compound, formed on the same side surface as the formed film, and applying a solution containing the polysilazane compound. The formed barrier layer contains at least one element selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table (excluding silicon and carbon). The provision of a gas barrier film having excellent gas barrier performance and excellent storage stability in a high temperature and high humidity environment, particularly excellent adhesion and bending resistance.

Description

  The present invention relates to a gas barrier film, a method for producing the same, and an electronic device using the same. More specifically, the present invention relates to a gas barrier film having high gas barrier properties and excellent stability, a method for producing the same, and an electronic device using the same.

  Conventionally, in the fields of food, packaging materials, pharmaceuticals, etc., in order to prevent the permeation of gases such as water vapor and oxygen, it is relatively simple to provide an inorganic film such as a metal or metal oxide vapor deposition film on the surface of a resin substrate. Gas barrier films having a structure have been used.

  In recent years, such a gas barrier film that prevents permeation of water vapor, oxygen, and the like is being used in the field of electronic devices such as liquid crystal display elements (LCD), solar cells (PV), and organic electroluminescence (EL). In order to give such an electronic device the property of being flexible and light and difficult to break, a gas barrier film having a high gas barrier property is required instead of a hard and easily broken glass substrate.

  As a measure for obtaining a gas barrier film applicable to an electronic device, a barrier layer is formed on a substrate such as a film by a plasma CVD method (Chemical Vapor Deposition method) on a resin substrate. And a method of forming a barrier layer by applying a surface treatment (modification treatment) after applying a coating liquid containing polysilazane as a main component on a substrate.

  For example, in Japanese Patent Application Laid-Open No. 2009-255040, a liquid containing polysilazane is used for the purpose of achieving both the thickening of the barrier layer for obtaining high gas barrier properties and the suppression of cracks in the thickened barrier layer. A technique for laminating a thin film on a substrate by repeating a process of forming a polysilazane film using a wet coating method and a process of irradiating the polysilazane film with vacuum ultraviolet rays twice or more is disclosed.

  Japanese Patent Application Laid-Open No. 2012-148416 discloses a gas barrier film having improved scratch resistance by adding a transition metal to a silicon-containing film.

  Japanese Patent Application Laid-Open No. 63-191832 describes a method of obtaining polyaluminosilazane by heat-reacting polysilazane and aluminum alkoxide as a material for a film having high hardness and excellent heat resistance and oxidation resistance.

  In the gas barrier films described in JP 2009-255040 A and JP 2009-255040 A, the barrier layer is formed by modifying the polysilazane film by irradiating it with vacuum ultraviolet rays. However, since the barrier layer is modified from the surface side irradiated with vacuum ultraviolet rays, oxygen and moisture do not enter the barrier layer, and there is an unreacted (unmodified) region that can generate ammonia by hydrolysis. It remains. This unreacted (unmodified) region reacts gradually in a high temperature and high humidity environment to produce a by-product, and the diffusion of this by-product may cause the barrier layer to be deformed or broken. As a result, there is a problem that the gas barrier property is gradually lowered.

  Furthermore, in order to obtain higher gas barrier properties, it is necessary to increase the amount of ultraviolet light for modifying the polysilazane film and to stack a plurality of barrier layers. However, as the progress of modification and the number of layers increase and the film thickness increases, the productivity decreases and the internal contraction stress in the film increases, and the flexibility (flexibility) is a characteristic of a flexible gas barrier film. There is also a problem that durability against physical stress such as bending is lowered.

  Therefore, the present invention has been made in view of the above circumstances, and has a high durability and excellent gas barrier performance, and is a gas barrier film having excellent storage stability in a high-temperature and high-humidity environment, particularly excellent adhesion and folding resistance. The purpose is to provide.

  The present inventor has intensively studied to solve the above problems. As a result, in a gas barrier film having a barrier layer formed by vapor deposition of an inorganic compound and a barrier layer formed by coating a solution containing a polysilazane compound, the barrier layer formed by coating contains a specific element. Thus, the present inventors have found that the above problem can be solved, and have completed the present invention.

  That is, the present invention provides a substrate, a barrier layer formed by vapor deposition of an inorganic compound on at least one surface of the substrate, and by vapor deposition of at least the inorganic compound of the substrate. A gas barrier film formed by applying a solution containing a polysilazane compound, formed on the same side surface as the formed barrier layer, and containing the polysilazane compound. The barrier layer formed by applying the solution is at least one selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table (however, silicon and carbon are added). A gas barrier film containing the element of

  In addition, the present invention includes a step of forming a layer by vapor-depositing an inorganic compound on a substrate, and a polysilazane compound and a long-period type on the layer formed by vapor-depositing an inorganic compound. Apply and apply a solution containing a compound containing at least one element selected from the group consisting of elements of Groups 2, 13 and 14 of the periodic table (except for silicon and carbon). It is a method for producing a gas barrier film, comprising a step of forming a film and a step of modifying the coating film by irradiating it with vacuum ultraviolet rays.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of the barrier layer formed by vapor phase film-forming of the inorganic compound which concerns on this invention, 101 is a plasma CVD apparatus, 102 is a vacuum chamber, 103 is a cathode electrode, 105 is a susceptor, 106 is a heat medium circulation system, 107 is an evacuation system, 108 is a gas introduction system, 109 is a high frequency power source, and 110 is a base material. And 160 is a heating / cooling device. It is a schematic diagram which shows an example of the other manufacturing apparatus used for formation of the barrier layer formed by vapor-phase film-forming of an inorganic compound, 1 is a gas barrier film, 2 is a base material, 3 is an inorganic compound , 31 is a manufacturing apparatus, 32 is a delivery roller, 33, 34, 35 and 36 are transport rollers, and 39 and 40 are film forming rollers. Yes, 41 is a gas supply pipe, 42 is a plasma generating power source, 43 and 44 are magnetic field generators, and 45 is a winding roller. It is a schematic diagram showing an example of a vacuum ultraviolet irradiation apparatus, 21 is an apparatus chamber, 22 is a Xe excimer lamp, 23 is an excimer lamp holder that also serves as an external electrode, 24 is a sample stage, and 25 is A sample in which a layer is formed, and 26 is a light shielding plate.

  A film (barrier layer) in which a solution containing a polysilazane compound is applied on a layer formed by vapor deposition (vapor deposition), and the coating film is irradiated with vacuum ultraviolet rays from an excimer lamp etc. When trying to repair the defect of the deposited film, the defect was not fully repaired. This is because the adhesion force at the interface between the deposited film itself and the film itself applied with a solution containing a polysilazane compound and irradiated with vacuum ultraviolet rays from an excimer lamp or the like is not sufficient. It was a cause and a big problem.

  In the method for producing a gas barrier film, which comprises applying a solution containing a polysilazane compound and then subjecting the coating film to irradiation with vacuum ultraviolet rays from an excimer lamp or the like to form a barrier layer. Since it is formed from the surface layer irradiated with ultraviolet rays, oxygen and moisture do not enter inside the barrier layer, and oxidation inside the barrier layer and even to the interface of the deposited film does not proceed, leaving unmodified and unstable. There was a problem that the performance fluctuated, particularly under high temperature and high humidity. Although attempts have been made to increase the amount of light and proceed with modification, there was a problem that dangling bonds formed on the surface as light was applied, and the amount of light absorbed by the surface increased, resulting in poor modification efficiency. .

  According to the gas barrier film of the present invention, the barrier layer formed by applying a solution containing a polysilazane compound is at least one selected from the group consisting of elements of Group 2, Group 13, and Group 14. By containing elements (except silicon and carbon), the modification of the film proceeds uniformly to the interface with the barrier layer formed by vapor deposition (evaporation) of the inorganic compound. The adhesion with the barrier layer formed by the phase film formation is greatly improved, and the barrier performance is stably exhibited. Furthermore, it has become possible to construct a highly resistant gas barrier film that does not change its barrier property under wet heat storage.

  The gas barrier film according to the present invention has a specific additive element in a barrier layer formed by application of a solution containing a polysilazane compound, so that the regularity of the film is lowered and the melting point is lowered. Light improves the flexibility of the film or melts the film. By improving the flexibility of the film or melting the film, defects are repaired to form a dense film, which is considered to improve the gas barrier property. In addition, the fluidity is increased by improving the flexibility of the membrane or melting the membrane, so that oxygen is supplied to the inside of the membrane and the reforming proceeds to the inside of the membrane. It is considered that the barrier layer has high resistance. Furthermore, the barrier layer formed by applying a solution containing a polysilazane compound is preferably formed by a modification treatment with active energy rays, for example. The gas barrier property can be improved by the reforming treatment. Here, in the barrier layer that does not contain the additive element, when the active energy ray is irradiated, the dangling bond increases, or the absorbance at 250 nm or less increases, and the active energy ray gradually penetrates into the film. Only the film surface is modified. On the other hand, the barrier layer formed by applying the solution containing the polysilazane compound in the gas barrier film of the present invention contains a specific additive element, but the reason is not clear, but as it is irradiated with active energy rays. Since the absorbance on the low wavelength side is reduced, the modification is uniformly performed from the surface of the barrier layer to the inside, and further to the interface with the barrier layer formed by vapor deposition (deposition) of an inorganic compound. As a result, it is considered that the adhesion force at the interface between the barrier layer formed by vapor deposition of the inorganic compound and the barrier layer formed by applying the solution containing the polysilazane compound is remarkably improved. As a result, it is considered that a highly resistant gas barrier film that does not easily denature in a high temperature and high humidity environment is formed. In addition, at least one of a barrier layer formed by vapor deposition of an inorganic compound or a barrier layer formed by applying a solution containing a polysilazane compound is formed by a modification treatment by, for example, vacuum ultraviolet irradiation. It is preferable. When the barrier layer formed by vapor deposition of an inorganic compound is irradiated with an active energy ray such as vacuum ultraviolet rays and modified, foreign matter is generated by the vacuum ultraviolet light energy, ozone generated by the energy, active oxygen, etc. Is decomposed and oxidized to repair defects as a barrier layer and improve surface uniformity to improve the coating uniformity of a solution containing a polysilazane compound, resulting in improved gas barrier properties. .

  The barrier layer formed by vapor deposition of an inorganic compound is preferably a vapor deposition layer containing nitrogen atoms. In particular, in a configuration including a barrier layer formed by vapor deposition (vapor deposition) containing nitrogen atoms and a barrier layer formed by applying a solution containing a specific additive element and containing a polysilazane compound, a vacuum is applied. Vacuum ultraviolet irradiation at the interface between a barrier layer formed by vapor deposition (deposition) of an inorganic compound and a barrier layer formed by applying a solution containing a polysilazane compound during the modification treatment by ultraviolet irradiation As a result, a barrier film with little change in performance can be obtained in a high temperature and high humidity environment.

  Furthermore, after the gas barrier film is formed by post-treatment, oxygen and moisture enter the film due to heat and humidity in the barrier layer formed by coating, and a solution containing a polysilazane compound is applied. Oxidation proceeds to the inside of the barrier layer and the interface with the barrier layer formed by vapor deposition (deposition) of an inorganic compound, and the number of unmodified portions in the barrier layer formed by coating is reduced. A gas barrier film with good performance can be obtained.

  Hereinafter, preferred embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment.

  In the present specification, “X to Y” indicating a range means “X or more and Y or less”, and “weight” and “mass”, “wt%” and “mass%”, “part by weight” and “ “Part by mass” is treated as a synonym.

<Gas barrier film>
The gas barrier film of the present invention has a substrate, a barrier layer formed by vapor deposition of an inorganic compound, and a barrier layer formed by applying a solution containing a polysilazane compound. The gas barrier film of the present invention may further contain other members. The barrier layer formed by applying a solution containing a polysilazane compound is at least one selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table ( Except for silicon and carbon). The gas barrier film of the present invention is, for example, other between the substrate and any barrier layer, on any barrier layer, or on the other surface of the substrate on which no barrier layer is formed. You may have a member. Here, the other members are not particularly limited, and members used for conventional gas barrier films can be used similarly or appropriately modified. Specific examples include a barrier layer containing silicon, carbon, and oxygen, a smooth layer, an anchor coat layer, a bleed-out prevention layer, a protective layer, a functional layer such as a moisture absorption layer and an antistatic layer, and the like.

  In the present invention, each of the barrier layers may exist as a single layer or may have a laminated structure of two or more layers.

  Furthermore, in this invention, each said barrier layer should just be formed in the same surface of at least one of a base material. For this reason, the gas barrier film of the present invention has both a form in which each of the above barrier layers is formed on one side of the substrate and a form in which each of the above barrier layers is formed on both sides of the base. Include.

(Base material)
In the gas barrier film according to the present invention, a plastic film or a sheet is usually used as a substrate, and a film or sheet made of a colorless and transparent resin is preferably used. If the plastic film used is a film that can hold a barrier layer (a barrier layer formed by vapor deposition of an inorganic compound and a barrier layer formed by application of a solution containing a polysilazane compound), the material, thickness, etc. There is no restriction | limiting in particular, According to a use purpose etc., it can select suitably. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  When the gas barrier film according to the present invention is used as a substrate of an electronic device such as an organic EL element, the base material is preferably made of a material having heat resistance. Specifically, for example, a resin base material having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 ° C. or more and 300 ° C. or less is used.

  When the gas barrier film according to the present invention is used in combination with a polarizing plate, the gas barrier film is preferably arranged so that any barrier layer of the gas barrier film faces the inside of the cell. More preferably, the barrier layer of the gas barrier film is disposed on the innermost side of the cell (adjacent to the element).

  Since the gas barrier film according to the present invention is used as an electronic device such as an organic EL element, the substrate is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.

  However, even when the gas barrier film according to the present invention is used for display applications, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the base material. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.

  The thickness of the base material used for the gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the application, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. As the functional layer, in addition to those described above, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably employed.

The substrate preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.

At least on the side of the substrate on which the barrier layer is provided, various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and lamination of a primer layer described later are performed. It is preferable to combine the above treatments as necessary.

[Barrier layer (dry barrier layer) formed by vapor deposition of inorganic compound]
The barrier layer (dry barrier layer) formed by vapor deposition of an inorganic compound contains an inorganic compound. The inorganic compound contained in the barrier layer formed by vapor deposition of an inorganic compound is not particularly limited, and examples thereof include metal oxides, metal nitrides, metal carbides, metal oxynitrides, and metal oxycarbides. . Among these, oxides, nitrides, carbides, oxynitrides or oxycarbides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta in terms of gas barrier performance Are preferably used, and an oxide, nitride or oxynitride of a metal selected from Si, Al, In, Sn, Zn and Ti is more preferable, and in particular, an oxide of at least one of Si and Al, Nitride or oxynitride is preferred. Specific examples of suitable inorganic compounds include composites such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, titanium oxide, or aluminum silicate. You may contain another element as a secondary component.

  The content of the inorganic compound contained in the barrier layer formed by vapor deposition of the inorganic compound is not particularly limited, but may be 50% by weight or more in the barrier layer formed by vapor deposition of the inorganic compound. It is preferably 80% by weight or more, more preferably 95% by weight or more, particularly preferably 98% by weight or more, and 100% by weight (that is, vapor phase film formation of an inorganic compound). It is most preferable that the barrier layer formed by (1) is made of an inorganic compound.

A barrier layer formed by vapor deposition of an inorganic compound contains an inorganic compound and thus has a gas barrier property. Here, when the gas barrier property of the barrier layer formed by vapor deposition of an inorganic compound is calculated with a laminate in which the barrier layer formed by vapor deposition of an inorganic compound is formed on a base material, The transmittance (WVTR) is preferably 0.1 g / (m ² · day) or less, more preferably 0.01 g / (m ² · day) or less, and 1 × 10 ⁻³ g / (m ² · day) or less, more preferably 1 × 10 ⁻⁴ g / (m ² · day) or less.

  The thickness of the barrier layer formed by vapor deposition of an inorganic compound is not particularly limited, but is preferably 50 to 600 nm, and more preferably 100 to 500 nm. If it is such a range, it will be excellent in high gas barrier performance, bending tolerance, and cutting processability. Further, the barrier layer formed by vapor deposition of the inorganic compound may be composed of two or more layers, and the total thickness of the barrier layer formed by vapor deposition of the inorganic compound in this case is not particularly limited. However, it is preferable that it is about 100-2000 nm. With such a thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending.

  A barrier layer formed by vapor deposition of an inorganic compound may be formed between a base material and a barrier layer formed by applying a solution containing a polysilazane compound, and the base material contains a polysilazane compound. However, it is preferably formed between the base material and the barrier layer formed by applying a solution containing a polysilazane compound. That is, it is preferably formed to include a base material, a barrier layer formed by vapor deposition of an inorganic compound, and a barrier layer formed by applying a solution containing a polysilazane compound in this order. . By doing so, the gas barrier property can be further improved.

  The vapor deposition (vapor deposition) method for forming a barrier layer formed by vapor deposition of an inorganic compound is not particularly limited. Existing thin film deposition technology can be used. For example, vapor deposition methods such as vapor deposition, reactive vapor deposition, sputtering, reactive sputtering, and chemical vapor deposition can be used.

  The reactive vapor deposition method is a method in which a reactive gas is introduced into a vacuum vessel and atoms and molecules evaporated from the evaporation source are reacted and deposited, and an excitation source such as plasma is introduced to promote the reaction. You can also. As typical raw materials, silicon, silicon nitride, silicon oxide, silicon oxynitride, or the like is used as a deposition source, and nitrogen, hydrogen, ammonia, oxygen, or the like is used as a reactive gas.

  The sputtering method is a method of depositing constituent atoms of a sputtered target on a substrate by utilizing a sputtering phenomenon in which high-energy ions accelerated by an electric field are incident on a target and the constituent atoms of the target are knocked out. The reactive sputtering method is a method in which a reactive gas is introduced into a vacuum vessel and reacted with constituent atoms of a sputtered target to be deposited on a substrate. As typical raw materials, silicon, silicon nitride, silicon oxide, silicon oxynitride or the like is used as a target material, and nitrogen, hydrogen, ammonia, oxygen or the like is used as a reactive gas.

  The chemical vapor deposition (CVD) method is a method of depositing a film by a chemical reaction on the surface of the substrate or in the vapor phase by supplying a raw material gas containing a target thin film component onto the substrate. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. The CVD method is a more promising method because it can form a film at a high speed and has a better coverage with respect to a substrate than a sputtering method or the like. In particular, a catalytic chemical vapor deposition method (Cat-CVD) using a very high temperature catalyst as an excitation source and a plasma chemical vapor deposition method (PECVD) method using plasma as an excitation source are preferable methods. Hereinafter, these methods will be described in detail.

(Cat-CVD method)
In Cat-CVD, material gas is allowed to flow into a vacuum vessel with a wire made of tungsten or the like, and the material gas is contacted and decomposed by a wire that is energized and heated by a power source, and the generated reactive species is deposited on a substrate. It is a method to make it.

For example, when depositing silicon nitride, monosilane, ammonia, or hydrogen is used as the material gas. In the case of depositing silicon oxynitride, oxygen is added in addition to the above material gas. As a condition example, a tungsten wire (eg, Φ0.5 length: 2.8 m) as a catalyst body is heated to 1800 ° C., and monosilane, ammonia, and hydrogen (4/200/200 sccm) are circulated as material gases. The film is deposited on a substrate whose temperature is adjusted to 100 ° C. while maintaining the pressure at 10 Pa. Of the reactive species generated by the decomposition reaction on the catalyst body, the main deposition species are SiH ₃ ^* and NH ₂ ^* , and H ^* is a reaction auxiliary species on the film surface. In particular, by adding hydrogen, a large amount of H ^* can be generated and the deposition rate is reduced, but it is believed to promote the reaction for removing H derived from Si—H bonds and N—H bonds in the film. .

(PECVD method)
The PECVD method was generated by flowing a material gas into a vacuum vessel equipped with a plasma source, generating electric discharge plasma in the vacuum vessel by supplying power from the power source to the plasma source, and causing the material gas to decompose and react with the plasma. This is a method of depositing reactive species on a substrate. As a plasma source method, capacitively coupled plasma using parallel plate electrodes, inductively coupled plasma, microwave excitation plasma using surface waves, or the like is used.

  A barrier layer formed by vapor phase deposition of an inorganic compound obtained by vacuum plasma CVD, plasma CVD under atmospheric pressure or near atmospheric pressure is a metal compound or decomposition gas that is a raw material (also referred to as a raw material). It is preferable because the target compound can be produced by selecting conditions such as the decomposition temperature and input power.

  For example, if a silicon compound is used as a raw material compound and oxygen is used as the decomposition gas, silicon oxide 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 a raw material compound, it is preferable to use a silicon compound, a titanium compound, and an aluminum compound. These raw material compounds can be used alone or in combination of two or more.

  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. Moreover, the silicon compound which is a raw material compound used in the case of formation of the barrier layer which satisfy | fills the requirements of (i)-(iii) which are the suitable forms mentioned later is mentioned.

  Examples of the titanium compound include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisoporooxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium. Examples thereof include diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, and butyl titanate dimer.

  Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyl dialumonium tri-s-butoxide. Can be mentioned.

  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, and water vapor. Further, the decomposition gas may be mixed with an inert gas such as argon gas or helium gas.

  A barrier layer formed by vapor deposition of a desired inorganic compound can be obtained by appropriately selecting a source gas containing a source compound and a decomposition gas. The barrier layer formed by vapor deposition of an inorganic compound formed by a CVD method is a layer containing an oxide, nitride, oxynitride, or oxycarbide.

  Hereinafter, a vacuum plasma CVD method, which is a preferred form among the CVD methods, will be specifically described.

  FIG. 1 is a schematic view showing an example of a vacuum plasma CVD apparatus used for forming a barrier layer formed by vapor deposition of an inorganic compound according to the present invention.

  In FIG. 1, a vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface inside the vacuum chamber 102. Further, a cathode electrode 103 is disposed on the ceiling side inside the vacuum chamber 102 at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102. A heat medium is disposed in the heat medium circulation system 106. The heat medium circulation system 106 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 160 having a storage device is provided.

  The heating / cooling device 160 is configured to measure the temperature of the heat medium, heat or cool the heat medium to a stored set temperature, and supply the heat medium to the susceptor 105. The supplied heat medium flows inside the susceptor 105, heats or cools the susceptor 105, and returns to the heating / cooling device 160. At this time, the temperature of the heat medium is higher or lower than the set temperature, and the heating and cooling device 160 heats or cools the heat medium to the set temperature and supplies the heat medium to the susceptor 105. Thus, the cooling medium circulates between the susceptor and the heating / cooling device 160, and the susceptor 105 is heated or cooled by the supplied heating medium having the set temperature.

  The vacuum chamber 102 is connected to an evacuation system 107, and before the film formation process is started by the vacuum plasma CVD apparatus 101, the inside of the vacuum chamber 102 is evacuated in advance and the heat medium is heated from room temperature. The temperature is raised to a set temperature, and a heat medium having the set temperature is supplied to the susceptor 105. The susceptor 105 is at room temperature at the start of use, and when a heat medium having a set temperature is supplied, the susceptor 105 is heated.

  After circulating the heat medium at the set temperature for a certain time, the base material 110 as a film formation target is carried into the vacuum chamber 102 while maintaining the vacuum atmosphere in the vacuum chamber 102 and placed on the susceptor 105.

  A number of nozzles (holes) are formed on the surface of the cathode electrode 103 facing the susceptor 105.

  The cathode electrode 103 is connected to a gas introduction system 108. When a CVD gas is introduced from the gas introduction system 108 to the cathode electrode 103, the CVD gas is ejected from the nozzle of the cathode electrode 103 into the vacuum chamber 102 in a vacuum atmosphere.

  The cathode electrode 103 is connected to a high frequency power source 109, and the susceptor 105 and the vacuum chamber 102 are connected to the ground potential.

  When a CVD gas is supplied from the gas introduction system 108 into the vacuum chamber 102, a high-frequency power source 109 is activated while a heating medium having a constant temperature is supplied from the heating / cooling device 160 to the susceptor 105, and a high-frequency voltage is applied to the cathode electrode 103, Plasma of the introduced CVD gas is formed. When the CVD gas activated in the plasma reaches the surface of the substrate 110 on the susceptor 105, a barrier layer formed by vapor deposition of an inorganic compound as a thin film grows on the surface of the substrate 110.

  The distance between the susceptor 105 and the cathode electrode 103 at this time is set as appropriate.

  The flow rates of the raw material gas and the cracked gas are appropriately set in consideration of the raw material gas, the cracked gas type, and the like. In one embodiment, the flow rate of the source gas is 30 to 300 sccm, and the flow rate of the decomposition gas is 100 to 1000 sccm.

  During the growth of the thin film, a heating medium having a constant temperature is supplied from the heating / cooling device 160 to the susceptor 105, and the susceptor 105 is heated or cooled by the heating medium, and a thin film is formed while being maintained at a constant temperature. Generally, the lower limit temperature of the growth temperature when forming a thin film is determined by the film quality of the thin film, and the upper limit temperature is determined by the allowable range of damage to the thin film already formed on the substrate 110. The lower limit temperature and upper limit temperature vary depending on the material of the thin film to be formed, the material of the thin film already formed, etc., but the lower limit temperature is 50 ° C. or more in order to ensure the film quality with high gas barrier properties, and the upper limit temperature is the base material. It is preferable that it is below the heat-resistant temperature.

  The correlation between the film quality of the thin film formed by the vacuum plasma CVD method and the film formation temperature, and the correlation between the damage to the film formation target (base material 110) and the film formation temperature are obtained in advance, and the lower limit temperature and the upper limit temperature are determined. It is determined. For example, the temperature of the substrate 110 during the vacuum plasma CVD process is preferably 50 to 250 ° C.

  Furthermore, the relationship between the temperature of the heat medium supplied to the susceptor 105 and the temperature of the base material 110 when plasma is formed by applying a high frequency voltage of 13.56 MHz or higher to the cathode electrode 103 is measured in advance, and vacuum In order to maintain the temperature of the base material 110 between the lower limit temperature and the upper limit temperature during the plasma CVD process, the temperature of the heat medium supplied to the susceptor 105 is required.

  For example, a lower limit temperature (here, 50 ° C.) is stored, and a heat medium whose temperature is controlled to a temperature equal to or higher than the lower limit temperature is set to be supplied to the susceptor 105. The heat medium refluxed from the susceptor 105 is heated or cooled, and a heat medium having a set temperature of 50 ° C. is supplied to the susceptor 105. For example, as a CVD gas, a mixed gas of silane gas, ammonia gas, and nitrogen gas is supplied, and the SiN film is formed in a state in which the base material 110 is maintained at a temperature condition that is higher than the lower limit temperature and lower than the upper limit temperature.

  Immediately after startup of the vacuum plasma CVD apparatus 101, the susceptor 105 is at room temperature, and the temperature of the heat medium returned from the susceptor 105 to the heating / cooling apparatus 160 is lower than the set temperature. Therefore, immediately after the activation, the heating / cooling device 160 heats the refluxed heat medium to raise the temperature to the set temperature, and supplies it to the susceptor 105. In this case, the susceptor 105 and the base material 110 are heated and heated by the heat medium, and the base material 110 is maintained in the range of the lower limit temperature or higher and the upper limit temperature or lower.

  When a thin film is continuously formed on the plurality of base materials 110, the susceptor 105 is heated by heat flowing from the plasma. In this case, since the heat medium recirculated from the susceptor 105 to the heating / cooling device 160 is higher than the lower limit temperature (50 ° C.), the heating / cooling device 160 cools the heat medium and converts the heat medium at the set temperature into the susceptor. It supplies to 105. Thereby, a thin film can be formed, maintaining the base material 110 in the range below minimum temperature and below maximum temperature.

  Thus, the heating / cooling device 160 heats the heating medium when the temperature of the refluxed heating medium is lower than the set temperature, and cools the heating medium when the temperature is higher than the set temperature. In addition, a heat medium having a set temperature is supplied to the susceptor, and as a result, the substrate 110 is maintained in a temperature range between the lower limit temperature and the upper limit temperature.

  When the thin film is formed to a predetermined thickness, the substrate 110 is unloaded from the vacuum chamber 102, the undeposited substrate 110 is loaded into the vacuum chamber 102, and a heat medium having a set temperature is supplied in the same manner as described above. While forming a thin film.

  As a preferred embodiment of a barrier layer (dry barrier layer) formed by vapor deposition of an inorganic compound according to the present invention, the barrier layer formed by vapor deposition of an inorganic compound has carbon as a constituent element. Preferably, silicon, and oxygen are included. A more preferable form is a layer that satisfies the following requirements (i) to (iii).

(I) Relationship between the distance (L) from the barrier layer surface in the film thickness direction of the barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atom ratio of silicon) A silicon distribution curve showing the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (oxygen atomic ratio), and the L and silicon atoms, In the carbon distribution curve showing the relationship between the oxygen atom and the ratio of the amount of carbon atoms to the total amount of carbon atoms (carbon atom ratio), a region of 90% or more (upper limit: 100%) of the thickness of the barrier layer And in the order of (atomic ratio of oxygen), (atomic ratio of silicon), (atomic ratio of carbon) (atomic ratio is O>Si>C);
(Ii) the carbon distribution curve has at least two extreme values;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve (hereinafter also simply referred to as “C _max −C _min difference”) is 3 at% or more.

  First, the barrier layer preferably has (i) the distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer and the amount of silicon atoms relative to the total amount of silicon atoms, oxygen atoms, and carbon atoms. The silicon distribution curve showing the relationship with the ratio of silicon (atomic ratio of silicon), and the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen) In the carbon distribution curve showing the relationship between the oxygen distribution curve and the ratio of the amount of carbon atoms to the total amount of L and silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon), the thickness of the barrier layer In the region of 90% or more (upper limit: 100%), (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in this order (atomic ratio is O> Si> C). When said condition (i) is satisfy | filled, the gas-barrier property and flexibility of the obtained gas-barrier film will become favorable. Here, in the carbon distribution curve, the relationship of the above (atomic ratio of oxygen), (atomic ratio of silicon) and (atomic ratio of carbon) is at least 90% or more (upper limit: 100%) of the thickness of the barrier layer. ) And more preferably at least 93% or more (upper limit: 100%). Here, “at least 90% or more of the thickness of the barrier layer” does not need to be continuous in the barrier layer, and only needs to satisfy the above-described relationship at a portion of 90% or more.

  Preferably, in the barrier layer, (ii) the carbon distribution curve has at least two extreme values. The barrier layer preferably has at least three extreme values in the carbon distribution curve, more preferably at least four extreme values, but may have five or more. When the extreme value of the carbon distribution curve is 2 or more, the gas barrier property when the obtained gas barrier film is bent is improved. The upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 or less, more preferably 25 or less, for example. Since the number of extreme values is also caused by the film thickness of the barrier layer, it cannot be specified unconditionally.

  Here, in the case of having at least three extreme values, the distance from the surface of the barrier layer in the film thickness direction of the barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value. The absolute value of the difference of (L) (hereinafter, also simply referred to as “distance between extreme values”) is preferably 200 nm or less, more preferably 100 nm or less, and particularly preferably 75 nm or less. preferable. With such a distance between extreme values, there are portions having a large carbon atom ratio (maximum value) in the barrier layer at an appropriate period, so that appropriate flexibility is imparted to the barrier layer, and the gas barrier film Generation of cracks during bending can be more effectively suppressed / prevented. In this specification, the “extreme value” refers to the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer. Further, in this specification, the “maximum value” is a point where the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from an increase to a decrease when the distance from the surface of the barrier layer is changed, And the value of the atomic ratio of the element at the position where the distance from the surface of the barrier layer in the thickness direction of the barrier layer from the point is further changed within the range of 4 to 20 nm than the value of the atomic ratio of the element at that point. It means a point that decreases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element should be reduced by 3 at% or more in any range. Similarly, the “minimum value” in this specification is a point in which the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from decrease to increase when the distance from the surface of the barrier layer is changed. In addition, the atomic ratio value of the element at a position where the distance from the surface of the barrier layer in the thickness direction of the barrier layer from the point is further changed by 4 to 20 nm is 3 at%. This is the point that increases. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent. Although not limited, in consideration of the flexibility of the barrier layer, the effect of suppressing / preventing cracks, thermal expansion, and the like, the thickness is preferably 10 nm or more, and more preferably 30 nm or more.

Further, preferably, the barrier layer has (iii) an absolute value of a difference between a maximum value and a minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter, also simply referred to as “C _max −C _min difference”) of 3 at. % Or more. When the absolute value is 3 at% or more, the gas barrier property is good even when the obtained gas barrier film is bent. The C _max -C _min difference is more preferably 5 at% or more, further preferably 7 at% or more, and particularly preferably 10 at% or more. By setting it as the said _{Cmax- Cmin} difference, gas barrier property can be improved more. In the present specification, the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values. Here, the upper limit of the C _max -C _min difference is not particularly limited, but it is preferably 50 at% or less, and 40 at% or less in consideration of the effect of suppressing / preventing crack generation during bending of the gas barrier film. It is more preferable that

  In the present invention, the oxygen distribution curve of the barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and more preferably has at least three extreme values. When the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved. The upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the thickness of the barrier layer, and it cannot be defined unconditionally. In the case of having at least three extreme values, a difference in distance from the surface of the barrier layer in the film thickness direction of the barrier layer at one extreme value of the oxygen distribution curve and an extreme value adjacent to the extreme value. Are preferably 200 nm or less, more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks during bending of the gas barrier film can be more effectively suppressed / prevented. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, but considering the improvement effect of crack generation suppression / prevention when the gas barrier film is bent, the thermal expansion property, etc. The thickness is preferably 10 nm or more, and more preferably 30 nm or more.

In addition, in the present invention, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the barrier layer (hereinafter also simply referred to as “O _max −O _min difference”) is 3 at% or more. Is preferably 6 at% or more, more preferably 7 at% or more. When the absolute value is 3 at% or more, the gas barrier property when the obtained gas barrier film is bent is further improved. Here, the upper limit of the O _max -O _min difference is not particularly limited, but is preferably 50 at% or less, and is preferably 40 at% or less in consideration of the effect of suppressing / preventing crack generation when the gas barrier film is bent. It is more preferable that

In the present invention, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of the barrier layer (hereinafter also simply referred to as “Si _max -Si _min difference”) is 10 at% or less. Is preferable, 7 at% or less is more preferable, and 3 at% or less is further preferable. When the absolute value is 10 at% or less, the gas barrier property of the obtained gas barrier film is further improved. The lower limit of Si _max -Si _min difference, because the effect of improving the crack generation suppression / prevention during bending of Si _max -Si _min as gas barrier property difference is small film is high, is not particularly limited, and gas barrier property In consideration, it is preferably 1 at% or more, and more preferably 2 at% or more.

In the present invention, the total amount of carbon and oxygen atoms with respect to the thickness direction of the barrier layer is preferably substantially constant. Thereby, a barrier layer exhibits moderate flexibility, and the crack generation at the time of bending of a gas barrier film can be more effectively suppressed / prevented. More specifically, the ratio of the total amount of oxygen atoms and carbon atoms to the distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer and the total amount of silicon atoms, oxygen atoms, and carbon atoms ( In the oxygen-carbon distribution curve showing the relationship with the oxygen / carbon atomic ratio), the absolute value of the difference between the maximum value and the minimum value of the oxygen-carbon atomic ratio in the oxygen-carbon distribution curve (hereinafter simply referred to as “OC _max -OC _min difference ") is preferably less than 5 at%, more preferably less than 4 at%, and even more preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property of the obtained gas barrier film is further improved. The lower limit of the OC _max -OC _min difference, since preferably as OC _max -OC _min difference is small, but is 0 atomic%, it is sufficient if more than 0.1 at%.

  The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. Thus, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time in this way, the etching time generally correlates with the distance (L) from the surface of the barrier layer in the film thickness direction of the barrier layer in the film thickness direction. Therefore, “Distance from the surface of the barrier layer in the film thickness direction of the barrier layer” is the distance from the surface of the barrier layer calculated from the relationship between the etching rate and the etching time adopted in the XPS depth profile measurement. can do. The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve can be prepared under the following measurement conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ );
Etching rate (converted to SiO ₂ thermal oxide film): 0.05 nm / sec;
Etching interval (SiO ₂ equivalent value): 10 nm;
X-ray photoelectron spectrometer: Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific;
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval.

  In the present invention, the thickness (dry film thickness) of the barrier layer is not particularly limited when the above (i) to (iii) are satisfied, but the thickness of the barrier layer is preferably 20 to 3000 nm, and preferably 50 to 2500 nm. It is more preferable that it is 100-1000 nm. With such a thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending. In addition, when a barrier layer is comprised from 2 or more layers, it is preferable that each barrier layer has thickness as mentioned above. In addition, the thickness of the entire barrier layer when the barrier layer is composed of two or more layers is not particularly limited, but the thickness of the entire barrier layer (dry film thickness) is preferably about 1000 to 2000 nm. With such a thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending.

  In the present invention, the barrier layer is substantially uniform in the film surface direction (direction parallel to the surface of the barrier layer) from the viewpoint of forming a barrier layer having a uniform and excellent gas barrier property over the entire film surface. Preferably there is. Here, the barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon are measured at any two measurement points on the film surface of the barrier layer by XPS depth profile measurement. When a distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the maximum and minimum values of the carbon atomic ratio in each carbon distribution curve The absolute values of the differences are the same as each other or within 5 at%.

  Furthermore, in the present invention, it is preferable that the carbon distribution curve is substantially continuous. Here, the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. In the relationship between the distance (x, unit: nm) from the surface of the barrier layer in the film thickness direction of at least one of the barrier layers, and the atomic ratio of carbon (C, unit: at%), Satisfying the condition expressed by the following formula 3.

  In the gas barrier film according to the present invention, the barrier layer that satisfies all of the above conditions (i) to (iii) may include only one layer, for example, or may include two or more layers. Furthermore, when two or more such barrier layers are provided, the materials of the plurality of barrier layers may be the same or different.

  In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atomic ratio, the oxygen atomic ratio, and the carbon atomic ratio are in the region of 90% or more of the thickness of the barrier layer (i ), The atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier layer is preferably 20 to 45 at%, More preferably, it is 25 to 40 at%. Further, the atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier layer is preferably 45 to 75 at%, and more preferably 50 to 70 at%. . Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier layer is preferably 0 to 25 at%, and more preferably 1 to 20 at%. .

  In the present invention, the method for forming the barrier layer is not particularly limited, and the conventional method and the method can be applied in the same manner or appropriately modified. The barrier layer is preferably formed by a chemical vapor deposition (CVD) method, particularly a plasma chemical vapor deposition method (plasma CVD, PECVD (plasma-enhanced chemical vapor deposition), hereinafter, also simply referred to as “plasma CVD method”). It is more preferable that the substrate is formed by a plasma CVD method in which a base material is disposed on a pair of film forming rollers and a plasma is generated by discharging between the pair of film forming rollers.

  Further, the arrangement of the barrier layer is not particularly limited, but it may be arranged on the substrate.

  Hereinafter, a method for forming a barrier layer on a substrate using the plasma CVD method preferably used in the present invention will be described below.

[Method of forming a barrier layer formed by vapor deposition of an inorganic compound]
The barrier layer formed by vapor deposition of the inorganic compound of the gas barrier film according to the present invention is preferably formed on the surface of the substrate. As a method for forming a barrier layer formed by vapor deposition of an inorganic compound on the surface of the substrate, it is preferable to employ a plasma CVD method from the viewpoint of gas barrier properties. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

  Further, when plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and each of the pair of film forming rollers is used. More preferably, the substrate is disposed and discharged between a pair of film forming rollers to generate plasma. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible not only to produce a thin film efficiently because it is possible to form a film on the surface part of the base material existing in the film while simultaneously forming a film on the surface part of the base material present on the other film forming roller. Compared with the plasma CVD method using no roller, the film formation rate can be doubled, and a film having substantially the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled, and it is efficient. It is possible to form a layer that satisfies all of the above conditions (i) to (iii).

  Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably includes an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation. In the gas barrier film of the present invention, the barrier layer is preferably a layer formed by a continuous film forming process.

  Moreover, it is preferable that the gas barrier film which concerns on this invention forms the said barrier layer on the surface of the said base material by a roll-to-roll system from a viewpoint of productivity. Further, an apparatus that can be used when manufacturing the barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and the pair of film forming processes. It is preferable that the apparatus has a configuration capable of discharging between rollers. For example, when the manufacturing apparatus shown in FIG. 2 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible.

  Hereinafter, a method for forming a barrier layer formed by vapor deposition of an inorganic compound will be described in more detail with reference to FIG. FIG. 2 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing a barrier layer formed by vapor deposition of an inorganic compound. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

  The manufacturing apparatus 31 shown in FIG. 2 includes a delivery roller 32, transport rollers 33, 34, 35, and 36, film formation rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a film formation roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge into the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 39 and 40) so that the central axis may become substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 39 and 40), the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled. And according to such a manufacturing apparatus, it is possible to form the barrier layer 3 on the surface of the base material 2 by the CVD method, and the barrier layer component is formed on the surface of the base material 2 on the film forming roller 39. While depositing, the barrier layer component can also be deposited on the surface of the substrate 2 also on the film forming roller 40, so that the barrier layer can be efficiently formed on the surface of the substrate 2.

  Inside the film forming roller 39 and the film forming roller 40, magnetic field generators 43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  The magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating device 43 provided on one film forming roller 39 and a magnetic field generating device provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between them and the magnetic field generators 43 and 44 form a substantially closed magnetic circuit. By providing such magnetic field generators 43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell near the opposing surface of each film forming roller 39 and 40, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

  The magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity. By providing such magnetic field generators 43 and 44, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 43 and 44 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 2 is excellent in that the barrier layer 3 that is a deposited film can be efficiently formed.

  As the film forming roller 39 and the film forming roller 40, known rollers can be appropriately used. As such film forming rollers 39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameters of the film forming rollers 39 and 40 are preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

  In such a manufacturing apparatus 31, the base material 2 is arrange | positioned on a pair of film-forming roller (The film-forming roller 39 and the film-forming roller 40) so that the surface of the base material 2 may respectively oppose. By disposing the base material 2 in this manner, when the plasma is generated by performing discharge in the facing space between the film formation roller 39 and the film formation roller 40, the base existing between the pair of film formation rollers is present. Each surface of the material 2 can be formed simultaneously. That is, according to such a manufacturing apparatus, a barrier layer component is deposited on the surface of the substrate 2 on the film forming roller 39 and further deposited on the film forming roller 40 by plasma CVD. Therefore, the barrier layer can be efficiently formed on the surface of the substrate 2.

  As the feed roller 32 and the transport rollers 33, 34, 35, and 36 used in such a manufacturing apparatus, known rollers can be appropriately used. The winding roller 45 is not particularly limited as long as it can wind the gas barrier film 1 having the barrier layer 3 formed on the substrate 2, and a known roller may be used as appropriate. it can.

  Further, as the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the source gas or the like at a predetermined speed can be appropriately used.

  The gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. As described above, by providing the gas supply pipe 41 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 39 and the film formation roller 40. It is excellent in that the film formation efficiency can be improved.

  Furthermore, as the plasma generating power source 42, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. Moreover, as such a plasma generating power source 42, it becomes possible to perform plasma CVD more efficiently, so that the applied power can be set to 100 W to 10 kW, and the AC frequency is set to 50 Hz to 500 kHz. More preferably, it is possible to do this. As the magnetic field generators 43 and 44, known magnetic field generators can be used as appropriate. Furthermore, as the base material 2, in addition to the base material used in the present invention, a material in which the barrier layer 3 is previously formed can be used. As described above, the barrier layer 3 can be thickened by using the substrate 2 having the barrier layer 3 formed in advance.

  Using such a manufacturing apparatus 31 shown in FIG. 2, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport of the film (base material) The barrier layer according to the present invention can be produced by appropriately adjusting the speed. That is, using the manufacturing apparatus 31 shown in FIG. 2, a discharge is generated between the pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. Thus, the film-forming gas (raw material gas or the like) is decomposed by plasma, and the barrier layer 3 is formed on the surface of the base material 2 on the film-forming roller 39 and the surface of the base material 2 on the film-forming roller 40 by plasma CVD. Formed by law. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the film forming rollers 39 and 40, and the plasma is converged on the magnetic field. For this reason, when the base material 2 passes through the point A of the film forming roller 39 and the point B of the film forming roller 40 in FIG. 2, the maximum value of the carbon distribution curve is formed in the barrier layer. On the other hand, when the substrate 2 passes through the points C1 and C2 of the film forming roller 39 and the points C3 and C4 of the film forming roller 40 in FIG. It is formed. For this reason, five extreme values are usually generated for two film forming rollers. Further, the distance between the extreme values of the barrier layer (the difference between the distance (L) from the surface of the barrier layer in the thickness direction of the barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (Absolute value) can be adjusted by the rotation speed of the film forming rollers 39 and 40 (base material transport speed). In such film formation, the substrate 2 is conveyed by the delivery roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. Thus, the barrier layer 3 is formed.

  As the film forming gas (such as source gas) supplied from the gas supply pipe 41 to the facing space, source gas, reaction gas, carrier gas, and discharge gas may be used alone or in combination of two or more. The source gas in the film-forming gas used for forming the barrier layer 3 can be appropriately selected and used according to the material of the barrier layer 3 to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of characteristics such as handling of the compound and gas barrier properties of the resulting barrier layer. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the barrier layer 3.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By not excessively increasing the ratio of the reactive gas, the barrier layer 3 formed is excellent in that excellent barrier properties and bending resistance can be obtained. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

Hereinafter, as the film forming gas, hexamethyldisiloxane (organosilicon compound, HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and one containing oxygen (O ₂ ) as a reaction gas are used. Taking a case of producing a silicon-oxygen-based thin film as an example, a suitable ratio of the raw material gas and the reactive gas in the film forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen system When the thin film is produced, a reaction represented by the following reaction formula 1 occurs by the film forming gas, and silicon dioxide is generated.

  In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, a uniform silicon dioxide film is formed when oxygen is contained in the film forming gas in an amount of 12 moles or more per mole of hexamethyldisiloxane and a uniform silicon dioxide film is formed (a carbon distribution curve exists). Therefore, it becomes impossible to form a barrier layer that satisfies all of the above conditions (i) to (iii). Therefore, in the present invention, when the barrier layer is formed, the amount of oxygen is set to a stoichiometric ratio of 12 with respect to 1 mole of hexamethyldisiloxane so that the reaction of the above reaction formula 1 does not proceed completely. It is preferable to make it less than a mole. In the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas Even if the (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane (flow rate), the reaction cannot actually proceed completely, and the oxygen content is reduced. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is changed to the hexamethyldioxide raw material. (It may be about 20 times or more the molar amount (flow rate) of siloxane). Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the barrier layer, and the above conditions (i) to (iii) It is possible to form a barrier layer satisfying all of the above) and to exhibit excellent gas barrier properties and flex resistance in the obtained gas barrier film. From the viewpoint of use as a flexible substrate for devices that require transparency, such as organic EL elements and solar cells, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas The lower limit of (flow rate) is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.

  Moreover, although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5 Pa-50 Pa.

  In such a plasma CVD method, in order to discharge between the film forming roller 39 and the film forming roller 40, an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used. The electric power to be applied to the power source can be adjusted as appropriate according to the type of the raw material gas, the pressure in the vacuum chamber, etc. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed, and if it is 10 kW or less, the amount of heat generated during film formation can be suppressed, and the substrate during film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.

  Although the conveyance speed (line speed) of the base material 2 can be appropriately adjusted according to the type of raw material gas, the pressure in the vacuum chamber, and the like, it is preferably in the range of 0.25 to 100 m / min. More preferably, it is in the range of 5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient thickness as a barrier layer, without impairing productivity.

  As described above, as a more preferable aspect of this embodiment, the barrier layer according to the present invention is formed by a plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is characterized by doing. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently produce a barrier layer having both the barrier performance and the barrier performance. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

(Modification treatment by vacuum ultraviolet irradiation of the barrier layer formed by vapor deposition of inorganic compounds)
The barrier layer formed by vapor deposition of the inorganic compound is preferably formed by a modification treatment by vacuum ultraviolet irradiation. Excimer treatment is preferably performed on the formed film as a modification treatment of vacuum ultraviolet irradiation.

  A known method can be used for excimer treatment (vacuum ultraviolet light treatment), but it will be the same as described later “Modification treatment of barrier layer formed by applying a solution containing polysilazane compound and vacuum ultraviolet light irradiation treatment” The vacuum ultraviolet light treatment is preferable, and further, the vacuum ultraviolet light treatment with energy of light having a wavelength of 100 to 180 nm is preferred.

  In the excimer treatment applied to the barrier layer formed by vapor deposition of an inorganic compound, the oxygen concentration when irradiating with vacuum ultraviolet light (VUV) is preferably 300 ppm to 50000 ppm (5%), more preferably 500 ppm to 10000 ppm. By adjusting to such an oxygen concentration range, the amount of vacuum ultraviolet light received by the barrier layer formed by vapor deposition of an inorganic compound is not significantly impaired, and oxygen in the atmosphere is activated to generate ozone and oxygen radicals. Can be generated moderately. In addition, it is preferable to use dry inert gas as gas other than these oxygen at the time of vacuum ultraviolet light (VUV) irradiation, and dry nitrogen gas is especially preferable from a viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

  When foreign substances such as organic substances are present on the surface of the barrier layer formed by vapor deposition of an inorganic compound, this leads to a decrease in gas barrier properties, or when the obtained gas barrier film is used as a base material for an organic EL element However, there is a concern that a non-light emitting point called a dark spot frequently occurs due to the occurrence of a short circuit of the electrode due to the protrusion of the foreign matter.

  However, by excimer treatment, foreign matter is decomposed and oxidized and removed by the vacuum ultraviolet light energy, ozone generated by the energy, active oxygen, etc., so that defects as a barrier layer can be repaired or the surface smoothed. By improving the property, the coating uniformity of the solution containing the polysilazane compound can be improved, and as a result, the barrier property is improved.

  The illuminance and the irradiation energy amount of vacuum ultraviolet rays are not particularly limited, but the same range as the vacuum ultraviolet irradiation treatment of the barrier layer formed by applying a solution containing a polysilazane compound can be preferably used.

(Post-processing)
The barrier layer formed by vapor deposition of an inorganic compound may be subjected to post-treatment after film formation or after modification with vacuum ultraviolet rays. Here, the post-treatment can be performed in the same manner as the post-treatment in the barrier layer formed by applying a solution containing a polysilazane compound described later.

[Barrier layer formed by applying a solution containing a polysilazane compound]
The barrier layer formed by applying a solution containing a polysilazane compound is formed on one surface of the substrate or on the barrier layer formed by vapor deposition of the inorganic compound. , A film having gas barrier properties, and at least one element selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table (excluding silicon and carbon) A silicon-containing film containing

  Examples of elements (additive elements) of Group 2, Group 13, and Group 14 of the long-period periodic table contained in the barrier layer formed by applying a solution containing a polysilazane compound include, for example, beryllium (Be), boron (B), magnesium (Mg), aluminum (Al), calcium (Ca), gallium (Ga), germanium (Ge), strontium (Sr), indium (In), tin (Sn), barium (Ba), thallium (Tl), lead (Pb), radium (Ra) and the like.

  Among these elements, aluminum (Al), indium (In), gallium (Ga), magnesium (Mg), calcium (Ca), germanium (Ge) and boron (B) are preferable, and aluminum (Al) or boron (B ) Is more preferred, and aluminum (Al) is most preferred. Group 13 elements such as boron (B), aluminum (Al), gallium (Ga), and indium (In) have a trivalent valence, and the valence is insufficient compared to the tetravalent valence of silicon. Therefore, the flexibility of the film is increased. Due to this improvement in flexibility, defects are repaired, the barrier layer becomes a dense film, and gas barrier properties are improved. In addition, due to the increased flexibility, oxygen is supplied to the inside of the barrier layer to become a silicon-containing film (barrier layer) that has been oxidized to the inside of the film, and a silicon-containing film that has high oxidation resistance when the film is formed (Barrier layer).

  The additive element may be present alone or in the form of a mixture of two or more.

  The barrier layer formed by applying a solution containing a polysilazane compound preferably has a chemical composition represented by the following chemical formula (1), and has the relationship of the following mathematical formula (1) and the following mathematical formula (2). Satisfied.

  In the chemical formula (1), x is an atomic ratio of oxygen to silicon. The x is preferably 1.1 to 3.1, more preferably 1.2 to 2.7, and most preferably 1.3 to 2.6.

  In the chemical formula (1), y is an atomic ratio of nitrogen to silicon. The y is preferably 0.001 to 0.51, more preferably 0.01 to 0.39, and most preferably 0.03 to 0.37.

  In the chemical formula (1), M is at least one element (additive element) selected from the group consisting of Group 2, Group 13, and Group 14 elements of the long-period periodic table excluding carbon and silicon. is there. A barrier layer formed by applying a solution containing these additive elements and containing a polysilazane compound has a reduced film regularity, a lower melting point, and is melted by heat or light during the film-forming process. Is repaired to form a denser film, and the gas barrier property is considered to be improved. In addition, since the fluidity is increased by melting, oxygen is supplied to the inside of the barrier layer to form a silicon-containing film (barrier layer) that has been oxidized to the inside of the film. It is thought that it is a contained film (barrier layer). In addition, when the silicon-containing film (barrier layer) to which the additive element is not added is irradiated with energy rays, the dangling bonds increase or the absorbance at 250 nm or less increases, and the active energy rays gradually increase. It becomes difficult to penetrate into the silicon-containing film (barrier layer), and only the surface of the silicon-containing film (barrier layer) is modified. On the other hand, in the gas barrier film of the present invention, the barrier layer formed by applying a solution containing a polysilazane compound has no clear reason, but the absorbance on the lower wavelength side decreases as the active energy ray is irradiated. Therefore, it is considered that the silicon-containing film (barrier layer) is modified from the surface to the inside, and is a film resistant to high temperature and high humidity environment. Moreover, it is thought that the said additional element also has a function as a catalyst in the modification | reformation by active energy ray irradiation of polysilazane, and it is thought that the below-mentioned reforming reaction advances more efficiently by adding an additional element.

  In the chemical formula (1), z is an atomic ratio of the additive element to silicon, and is preferably 0.01 to 0.3. When z is 0.01 or more, the effect of addition tends to be manifested. On the other hand, if z is 0.3 or less, the gas barrier property of the barrier layer is lowered, and it is possible to suppress the occurrence of coloring problems depending on the type of element. This z becomes like this. Preferably it is 0.02-0.25, More preferably, it is 0.03-0.2.

  Furthermore, it is preferable that the barrier layer formed by applying a solution containing a polysilazane compound satisfies the relationship of the above mathematical formulas 1 and 2.

  In Formula 1 and Formula 2, X = x / (1+ (az / 4)), Y = y / (1+ (az / 4)) (where a is the valence of the element M).

  X and Y in Formula 1 and Formula 2 above represent silicon and an additive element as the main skeleton, and represent the ratio of silicon and oxygen atoms and the ratio of nitrogen atoms to the main skeleton. Therefore, Y / (X + Y) in Equation 1 above represents the ratio of nitrogen to the total amount of oxygen and nitrogen, and affects the oxidation stability, transparency, flexibility, etc. of the barrier layer.

  Y / (X + Y) is preferably in the range of 0.001 to 0.25. If Y / (X + Y) is 0.001 or more, the flexibility is high and it is easy to cope with the deformation of the base material. On the other hand, if it is 0.25, since the nitrogen abundance ratio is relatively small, it can be suppressed that the nitrogen portion is oxidized and the barrier property is lowered under high temperature and high humidity. In order to be more stable in a high temperature and high humidity environment, Y / (X + Y) is preferably 0.001 to 0.25, and more preferably 0.02 to 0.20.

Moreover, 3Y + 2X in the above mathematical formula 2 is preferably in the range of 3.30 to 4.80. If 3Y + 2X is 3.30 or more, this indicates that the main skeleton is not deficient in oxygen and nitrogen atoms, and the silicon deficient in oxygen and nitrogen atoms is present as unstable Si radicals. The proportion of Since it can suppress that such Si radical reacts with water vapor | steam, it can prevent that a barrier layer changes with time and moist heat resistance falls. On the other hand, if 3Y + 2X is 4.80 or less, oxygen atoms and nitrogen atoms do not become excessive, so the proportion of terminal groups such as —OH groups and —NH ₂ groups in the main skeleton composed of silicon and additive elements is reduced. The intermolecular network is dense and the gas barrier property is improved. 3Y + 2X is preferably 3.30 to 4.80, more preferably 3.32 to 4.40.

  Note that a representing the valence of the additive element in X and Y is a compound containing an additive element used in a method for forming a barrier layer formed by applying a solution containing a polysilazane compound described later (hereinafter simply added). The valence of the additive element in the element compound) is also adopted as it is. When there are a plurality of additive elements, the sum total weighted based on the molar ratio of the additive elements is adopted.

  The barrier layer having the above composition preferably has an etching rate of 0.1 to 40 nm / min when immersed in a 0.125 wt% hydrofluoric acid aqueous solution at a temperature of 25 ° C. More preferably, it is min. If it is this range, it will become a barrier layer excellent in the balance of gas-barrier property and flexibility. In addition, the measuring method of an etching rate can be measured by the method as described in Unexamined-Japanese-Patent No. 2009-111029, More specifically, it can be measured by the method as described in the below-mentioned Example.

  Regarding the chemical composition represented by the chemical formula (1) and the relationship between the mathematical formulas 1 and 2, the types and amounts of the polysilazane compound and the additive element compound used when forming the barrier layer, and the polysilazane compound and the additive element compound are used. It can control by the conditions at the time of modify | reforming the layer containing this. Below, the formation method of the barrier layer formed by apply | coating the solution containing a polysilazane compound is demonstrated.

[Method for Forming Barrier Layer Formed by Applying Solution Containing Polysilazane Compound]
A layer formed by applying a solution containing a polysilazane compound is formed by vapor deposition of a solution containing a polysilazane compound and an additive element compound on a substrate and an inorganic compound formed on the substrate. It is formed by applying on a barrier layer.

(Polysilazane compound)
The “polysilazane compound” used in the present invention is a polymer having a silicon-nitrogen bond in its structure, SiO ₂ having a bond such as Si—N, Si—H, or N—H, Si ₃ N ₄ , and Ceramic intermediate inorganic polymers such as both intermediate solid solutions SiO _x N _y .

  The polysilazane compound has few defects such as film formability and cracks, few residual organic substances, high gas barrier performance, and barrier performance is maintained even when bent and under high temperature and high humidity conditions.

In order to apply the film without damaging the film substrate, a polysilazane compound that is modified to SiO _x N _y at a relatively low temperature is preferable, as described in JP-A-8-112879.

  As such a polysilazane compound, those having the following structure can be preferably used.

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R ₁ , R ₂ and R ₃ may be the same or different. Here, as an alkyl group, a C1-C8 linear, branched or cyclic alkyl group is mentioned. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. Moreover, as an aryl group, a C6-C30 aryl group is mentioned. More specifically, non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. Can be mentioned. Examples of the (trialkoxysilyl) alkyl group include an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specifically, 3- (triethoxysilyl) propyl group, 3- (trimethoxysilyl) propyl group and the like can be mentioned. The substituent optionally present in R _{1 to} R ₃ is not particularly limited, and examples thereof include an alkyl group, a halogen atom, a hydroxyl group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxyl group (—COOH), a nitro group (—NO ₂ ) and the like. In addition, the substituent which exists depending on the case does not become the same as R < ₁ > -R < ₃ > to substitute. For example, when R _{1 to} R ₃ are alkyl groups, they are not further substituted with an alkyl group. Of these, R ₁ , R ₂ and R ₃ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

  In the general formula (I), n is an integer, and the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. preferable.

In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

  Alternatively, polysilazane has a structure represented by the following general formula (II).

In the general formula (II), R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

  In the general formula (II), n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that Note that n ′ and p may be the same or different.

Of the polysilazanes of the general formula (II), R _{1 ′} , R _{3 ′} and R _{6 ′} each represent a hydrogen atom, and R _{2 ′} , R _{4 ′} and R _{5 ′} each represent a methyl group; R _{1 '} , R _3' and R _{6 '} each represents a hydrogen atom, R _2' and R _{4 '} each represents a methyl group and R _5' represents a vinyl group; R _{1 '} , R _3' and R ₄ A compound in which _' and R _6' each represent a hydrogen atom and R _{2 '} and R _5' each represents a methyl group is preferred.

  Alternatively, polysilazane has a structure represented by the following general formula (III).

In the general formula (III), R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R _{1 "} , R _2" , R _{3 "} , R _4" , R _{5 "} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

  In the general formula (III), n ″, p ″ and q are integers, and the polysilazane having a structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ″, p ″, and q may be the same or different.

Of the polysilazanes of the general formula (III), R _{1 ″} , R _{3 ″} and R _{6 ″} each represent a hydrogen atom, and R _{2 ″} , R _{4 ″} , R _{5 ″} and R _{8 ″} each represent a methyl group. , R _{9 ″} represents a (triethoxysilyl) propyl group, and R _{7 ″} represents an alkyl group or a hydrogen atom.

  On the other hand, the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard. The ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, these perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

  Polysilazane is commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a solution containing a polysilazane compound. As a commercial item of polysilazane solution, AZ Electronic Materials Co., Ltd. Aquamica (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110 NP140, SP140 and the like.

  Another example of the polysilazane that can be used in the present invention is not limited to the following. For example, a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827) or glycidol is reacted. Glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting alcohol (Japanese Patent Laid-Open No. 6-240208), metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal obtained by adding metal fine particles Fine particle added polysila Emissions, such as (JP-A-7-196986), and a polysilazane ceramic at low temperatures.

(Additive element compounds)
The kind of additive element compound is not particularly limited.

  Examples of aluminum compounds include anosoclase, alumina, aluminosilicate, aluminate, sodium aluminate, alexandrite, ammonium leucite, yttrium / aluminum garnet, feldspar, osarizawa stone, omphacite, pyroxene, sericite , Gibbstone, sanidine, sapphire, aluminum oxide, aluminum hydroxide oxide, aluminum bromide, aluminum twelve boride, aluminum nitrate, muscovite, aluminum hydroxide, lithium aluminum hydride, cedar, spinel, diaspore, arsenic Aluminum, Peacock (pigments), plagioclase, jadeite, cryolite, amphibole, aluminum fluoride, zeolite, Brazilite, vesuvite, B-alumina solid electrolyte, petotite, sodalite, organoaluminum compound Spodumene, lepidolite, aluminum sulfate, beryl, chlorite, epidote, aluminum phosphide, aluminum phosphate, and the like.

  Magnesium compounds include: zinc green coconut, magnesium sulfite, magnesium benzoate, carnalite, magnesium perchlorate, magnesium peroxide, talc, dolomite, olivine, magnesium acetate, magnesium oxide, serpentine, magnesium bromide, nitric acid Examples include magnesium, magnesium hydroxide, spinel, ordinary amphibole, ordinary pyroxene, magnesium fluoride, magnesium sulfide, magnesium sulfate, and rhododendron.

  Calcium compounds include: Araleite, Calcium Sulfite, Calcium Benzoate, Egyptian Blue, Calcium Chloride, Calcium Chloride Hydroxide, Calcium Chlorate, Ash Chromium Meteorite, Scheelite, Ashite Calcium perphosphate, calcium cyanamide, calcium hypochlorite, calcium cyanide, calcium bromide, calcium biperphosphate, calcium oxalate, calcium bromate, calcium nitrate, calcium hydroxide, hornblende, ordinary pyroxene, Calcium fluoride, fluorapatite, calcium iodide, calcium iodate, johansen pyroxene, calcium sulfide, calcium sulfate, chlorite, chlorite, chlorite, apatite, apatite, calcium phosphate and the like.

  Examples of the gallium compound include gallium oxide (III), gallium hydroxide (III), gallium nitride, gallium arsenide, gallium iodide (III), and gallium phosphate.

  Examples of the boron compound include boron oxide, boron tribromide, boron trifluoride, boron triiodide, sodium cyanoborohydride, diborane, boric acid, trimethyl borate, borax, borazine, borane, and boronic acid.

  Examples of germanium compounds include organic germanium compounds, inorganic germanium compounds, germanium oxide, and the like.

  Examples of the indium compound include indium oxide and indium chloride.

  However, from the viewpoint that a high-performance barrier layer (silicon-containing film) can be more efficiently formed, the additive element compound is preferably an alkoxide of the additive element. Here, the “addition element alkoxide” refers to a compound having at least one alkoxy group bonded to the addition element. In addition, you may use an additive element compound individually or in mixture of 2 or more types. As the additive element compound, a commercially available product or a synthetic product may be used.

  Examples of the alkoxide of the additive element include, for example, beryllium acetylacetonate, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert-butyl borate, Magnesium ethoxide, magnesium ethoxyethoxide, magnesium methoxyethoxide, magnesium acetylacetonate, aluminum trimethoxide, aluminum triethoxide, aluminum tri n-propoxide, aluminum triisopropoxide, aluminum tri n-butoxide, aluminum tri sec-butoxide, aluminum tri-tert-butoxide, aluminum acetylacetonate, acetoalkoxy aluminum diisopropylate, aluminum ethyl acetate Acetate diisopropylate, aluminum ethyl acetoacetate di n-butyrate, aluminum diethyl acetoacetate mono n-butyrate, aluminum diisopropylate mono sec-butylate, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, bis (ethylacetoacetate ) (2,4-pentanedionato) aluminum, aluminum alkyl acetoacetate diisopropylate, aluminum oxide isopropoxide trimer, aluminum oxide octylate trimer, calcium methoxide, calcium ethoxide, calcium isopropoxide, calcium acetylacetonate , Strontium acetylacetonate, gallium methoxide, galiu Ethoxide, gallium isopropoxide, gallium acetylacetonate, germanium methoxide, germanium ethoxide, germanium isopropoxide, germanium n-butoxide, germanium tert-butoxide, ethyltriethoxygermanium, strontium isopropoxide, tris (2,4 -Pentandionato) indium, indium isopropoxide, indium isopropoxide, indium n-butoxide, indium methoxyethoxide, tin n-butoxide, tin tert-butoxide, tin acetylacetonate, barium diisopropoxide, barium tert -Butoxide, barium acetylacetonate, thallium ethoxide, thallium acetylacetonate, lead acetylacetonate, etc. Can be mentioned. Among these additive alkoxides, triisopropyl borate, magnesium ethoxide, aluminum trisec-butoxide, aluminum ethyl acetoacetate diisopropylate, calcium isopropoxide, gallium isopropoxide, aluminum diisopropylate monosec-butyrate Aluminum ethyl acetoacetate di n-butyrate and aluminum diethyl acetoacetate mono n-butyrate are preferred.

  The formation method of the barrier layer formed by applying a solution containing a polysilazane compound is not particularly limited, and a known method can be applied, but a polysilazane compound, a compound containing an additive element in a solvent, and as necessary A method of applying a solution containing a polysilazane compound containing a catalyst by a known wet coating method, removing the solvent by evaporation, and then performing a reforming treatment is preferable.

(Solution containing polysilazane compound)
The solvent for preparing the solution containing the polysilazane compound is not particularly limited as long as it can dissolve the polysilazane compound and the additive element compound, but water and reactive groups that easily react with the polysilazane compound (for example, An organic solvent that does not contain a hydroxyl group or an amine group and is inert to the polysilazane compound is preferred, and an aprotic organic solvent is more preferred. Specifically, the solvent includes an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben. Hydrogen solvents; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. The solvent is selected in accordance with purposes such as the solubility of the polysilazane compound and the additive element compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of the polysilazane compound in the solution containing the polysilazane compound is not particularly limited and varies depending on the film thickness of the layer and the pot life of the solution, but is preferably 0.1 to 30% by weight, more preferably 0.5 to 20%. % By weight, more preferably 1 to 15% by weight.

  In addition, the concentration of the additive element compound in the solution containing the polysilazane compound is not particularly limited, and is preferably 0.01 to 20% by weight, more preferably 0.8%, although it varies depending on the layer thickness and the pot life of the solution. 1 to 10% by weight, more preferably 0.2 to 5% by weight.

  Furthermore, the weight ratio of the polysilazane compound to the additive element compound in the solution containing the polysilazane compound is preferably the solid content weight of the polysilazane compound: additive element compound = 1: 0.01 to 1:10, and 1: 0.06. ˜1: 6 is more preferred. Within this range, a high-performance barrier layer (silicon-containing film) can be obtained more efficiently.

  An amine or a metal catalyst may be added to the solution containing the polysilazane compound in order to promote the modification. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials. The amount of the catalyst added at this time is preferably adjusted to 2% by mass or less with respect to the polysilazane compound in order to avoid excessive silanol formation by the catalyst, reduction in film density, increase in film defects, and the like.

  In addition to the polysilazane compound, the solution containing the polysilazane compound can contain an inorganic precursor compound. The inorganic precursor compound other than the polysilazane compound is not particularly limited as long as a solution can be prepared.

  Specifically, for example, as a compound containing silicon, polysiloxane, polysilsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, Methyltriethoxysilane, tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, Dimethyldivinylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-tri Fluoropropyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltri Acetoxysilane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane, diaryldimethoxysilane, butyl Dimethoxyvinylsilane, trimethyl-3-vinylthiopropylsilane, phenyltrimethyl Lan, dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycid Xylpropyltrimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3 -Methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane , Dibutoxydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane Diacetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxypropyl Methylsilane, octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenylsilane, diphenyl Tilvinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1,3,3 -Tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) tetramethyl Disiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclo Trisiloxane, octamethylcyclotetrasiloxane, 1, , It may be mentioned 5,7-tetraethoxy-1,3,5,7-tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.

  As polysiloxane, what has highly reactive Si-H is preferable, and methyl hydrogen polysiloxane is preferable. Examples of the methyl hydrogen polysiloxane include TSF484 manufactured by Momentive.

  As the polysilsesquioxane, a cage, ladder, or random structure can be preferably used. The polysilsesquioxane considered to be a mixture of cage-like, ladder-like, and random structures is a polyphenylsilsesquioxane manufactured by Konishi Chemical Co., Ltd., SR-20, SR-21, SR- 23, SR-13 which is polymethylsilsesquioxane, SR-33 which is polymethyl phenylsilsesquioxane. Further, the Fox series manufactured by Toray Dow Corning, which is a polyhydrogensilsesquioxane solution commercially available as a spin-on-glass material, can also be preferably used.

  Among the compounds shown above, inorganic silicon compounds that are solid at room temperature are preferable, and hydrogenated silsesquioxane is more preferably used.

  Additives listed below can be used in the solution containing the polysilazane compound, if necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

(Method of applying a solution containing a polysilazane compound)
As a method of applying a solution containing a polysilazane compound, a conventionally known appropriate wet coating method can be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

  The coating thickness can be appropriately set according to the purpose. For example, the coating thickness is preferably 0.01 to 1 μm after drying, more preferably 0.02 to 0.6 μm, and further preferably 0.04 to 0.4 μm. preferable. If the film thickness is 0.01 μm or more, sufficient barrier properties can be obtained, and if it is 1 μm or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized. Moreover, if it is 1 micrometer or less, sufficient flexibility will be acquired and the crack of a film | membrane will not generate | occur | produce easily.

  After coating the solution containing the polysilazane compound, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable barrier layer can be obtained. The remaining solvent can be removed later.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 50-200 degreeC. For example, when a polyethylene terephthalate base material having a glass transition temperature (Tg) of 70 ° C. is used as the base material, the drying temperature is preferably set to 150 ° C. or lower in consideration of deformation of the base material due to heat. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

(Modification process)
In the present invention, the barrier layer formed by applying a solution containing a polysilazane compound is preferably modified. The modification treatment in the present invention refers to a reaction in which part or all of the polysilazane compound is converted into silicon oxide or silicon oxynitride.

Thereby, an inorganic thin film of a level that can contribute to the development of the gas barrier property (water vapor permeability of 1 × 10 ⁻³ g / m ² · day or less) as a whole of the gas barrier film of the present invention can be formed.

  Specifically, heat treatment, plasma treatment, active energy ray irradiation treatment, and the like can be given. Among these, from the viewpoint that it can be modified at a low temperature and has a high degree of freedom in selecting a base material species, a treatment with active energy ray irradiation is preferable.

(Heat treatment)
As a heat treatment method, for example, a method of heating a coating film by heat conduction by bringing a substrate into contact with a heating element such as a heat block, a method of heating an environment in which the coating film is placed by an external heater such as a resistance wire, Although the method using the light of infrared region, such as IR heater, is mentioned, It is not limited to these. What is necessary is just to select suitably the method which can maintain the smoothness of a coating film, when performing heat processing.

  As temperature which heats a coating film, the range of 40-250 degreeC is preferable, and the range of 60-150 degreeC is more preferable. The heating time is preferably in the range of 10 seconds to 100 hours, and more preferably in the range of 30 seconds to 5 minutes.

(Plasma treatment)
In the present invention, a known method can be used as the plasma treatment that can be used as the modification treatment, and an atmospheric pressure plasma treatment or the like can be preferably used. The atmospheric pressure plasma CVD method, which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum. The film speed is high, and further, under a high pressure condition of atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free path is very short, so that a very homogeneous film can be obtained.

  In the case of atmospheric pressure plasma treatment, nitrogen gas or a group 18 atom in the long-period periodic table, specifically helium, neon, argon, krypton, xenon, radon, or the like is used as the discharge gas. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

(Active energy ray irradiation treatment)
As the active energy rays, for example, infrared rays, visible rays, ultraviolet rays, X rays, electron rays, α rays, β rays, γ rays and the like can be used, but electron rays or ultraviolet rays are preferable, and ultraviolet rays are more preferable. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form a barrier layer having high density and insulating properties at low temperatures.

  In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.

  In the method for producing a gas barrier film in the present invention, the coating film containing the polysilazane compound from which moisture has been removed is modified by treatment with ultraviolet light irradiation. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperatures. It is.

This ultraviolet light irradiation excites and activates O ₂ and H ₂ O, UV absorbers, and polysilazane itself that contribute to ceramics. And the ceramicization of the excited polysilazane is promoted, and the resulting ceramic film becomes dense. Irradiation with ultraviolet light is effective at any time after the formation of the coating film.

  Any commonly used ultraviolet ray generator can be used for the vacuum ultraviolet ray irradiation treatment in the present invention. The ultraviolet light referred to in the present invention generally refers to ultraviolet light including electromagnetic waves having a wavelength of 10 to 200 nm called vacuum ultraviolet light.

  In the irradiation with vacuum ultraviolet light, it is preferable to set the irradiation intensity and the irradiation time within a range in which the substrate carrying the coating containing the polysilazane compound before modification is not damaged.

For example, when a plastic film is used as the substrate, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the substrate and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation for 0.1 second to 10 minutes can be performed.

  In general, when the temperature of the substrate during the ultraviolet irradiation treatment is 150 ° C. or higher, the properties of the substrate are impaired in the case of a plastic film or the like, for example, the substrate is deformed or its strength is deteriorated. . However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generating means include, but are not limited to, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp, and a UV light laser. In addition, when the polysilazane layer before modification is irradiated with the generated ultraviolet light, the polysilazane before modification is reflected after reflecting the ultraviolet light from the generation source with a reflector from the viewpoint of improving efficiency and uniform irradiation. It is desirable to hit the layer.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. When the substrate having a coating film formed by applying a solution containing a polysilazane compound is in the form of a long film, it is continuously conveyed in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. Ceramics can be formed by irradiating ultraviolet rays. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although depending on the composition and concentration of the coating film containing the base material and polysilazane compound to be used.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment).

  A dry inert gas is preferably used as a gas other than oxygen at the time of vacuum ultraviolet light (VUV) irradiation, and dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

  Specifically, the modification treatment method for a coating film containing a polysilazane compound before modification in the present invention is treatment by irradiation with vacuum ultraviolet light. The treatment by vacuum ultraviolet light irradiation uses light energy of 100 to 200 nm, preferably light energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and the bonding of atoms is called a photon process called a photon process. This is a method in which a silicon oxide film is formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by only the action. As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

Note that rare gas atoms such as Xe, Kr, Ar, and Ne are called inert gases because they are chemically bonded and do not form molecules. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. When the rare gas is xenon,
e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light (vacuum ultraviolet light) of 172 nm is emitted.

  A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

In the vacuum ultraviolet ray irradiation step of the present invention, the illuminance of the vacuum ultraviolet ray on the coating surface received by the coating film containing the polysilazane compound is preferably 1 mW / cm ^{2 to} 10 W / cm ² , and preferably 30 mW / cm ^{2 to} 200 mW / cm. more preferably ^2, further preferably at ^{50mW / cm 2 ~160mW / cm 2} . If it is 1 mW / cm ² or more, sufficient reforming efficiency can be obtained. Moreover, if it is 10 W / cm < ² > or less, it is hard to produce the ablation of a coating film and it is hard to damage a base material.

Irradiation energy amount of the VUV in coated surface containing the polysilazane compound is preferably 10 to 10000 mJ / cm ^2, more preferable to be 100~8000mJ / cm ^2, further preferable to be 200~6000mJ / cm ^2, 500 It is especially preferable that it is -6000mJ / cm < ² >. If 10 mJ / cm ² or more sufficient reforming efficiency is obtained, 10000 mJ / cm ² or less value, if difficult to thermal deformation of the cracks or the substrate occurs.

Moreover, it is preferable that oxygen concentration at the time of irradiating with vacuum ultraviolet light (VUV) is 300 ppm to 10000 ppm (1%), and more preferably 500 ppm to 5000 ppm. By adjusting to such an oxygen concentration range, it is possible to prevent the formation of an excessive oxygen barrier layer and to prevent the deterioration of the barrier property.

The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. The high energy possessed by the active oxygen, ozone and ultraviolet radiation can realize the modification of the coating film formed by applying the solution containing the polysilazane compound in a short time. Therefore, compared to low-pressure mercury lamps with a wavelength of 185 nm and 254 nm and plasma cleaning, the process time is shortened due to high throughput, the equipment area is reduced, and organic materials, plastic substrates, resin films, etc. that are easily damaged by heat are irradiated. It is possible.

The barrier layer formed by application of the solution containing the polysilazane compound described above is such that at least part of the polysilazane is modified in the step of irradiating the coating film formed by applying the solution containing the polysilazane compound with vacuum ultraviolet rays. Thus, a barrier layer containing silicon oxynitride having a composition of SiO _x N _y M _z as a whole layer is formed.

  The film composition can be measured by measuring the atomic composition ratio using an XPS surface analyzer. It can also be measured by cutting the barrier layer and measuring the cut surface with an XPS surface analyzer.

Further, the film density can be appropriately set according to the purpose. For example, the film density of the barrier layer is preferably in the range of 1.5 to 2.6 g / cm ³ . Within this range, the density of the film can be improved and deterioration of gas barrier properties and film deterioration under high temperature and high humidity conditions can be prevented.

(Post-processing)
The barrier layer formed by applying a solution containing a polysilazane compound is preferably subjected to post-treatment after application or after modification, particularly after modification. The post-treatment described here includes temperature treatment (heat treatment) at a temperature of 10 ° C. to less than 800 ° C., humidity: 0% to 100%, or humidity treatment immersed in a water bath, and the treatment time is 5 seconds. It is defined as a range selected from the range of 48 days. Both temperature and humidity treatments may be performed, or only one of them may be performed.

  When the temperature treatment is performed, any method such as a contact method such as placing on a hot plate or a non-contact method where the sample is left standing in an oven may be used in combination or a single method.

  Considering productivity, load on the apparatus, and resistance of the resin support when using the resin support, preferable conditions are a temperature of 40 to 120 ° C., a humidity of 30% to 85%, and a treatment time of 30 seconds to 100 hours. It is.

  In addition, the barrier layer (silicon-containing film) formed by applying a solution containing a polysilazane compound and a specific additive element may form only one layer or two or more layers. Moreover, although it forms by apply | coating the solution containing a polysilazane compound, you may use it in combination with the barrier layer which does not contain an additional element. A barrier layer that does not contain an additive element is formed by applying a solution containing the above polysilazane compound except that the additive element compound is not used. The barrier layer can be formed by the same method. Thus, by providing a plurality of barrier layers, the gas barrier property can be further improved. Preferably, a barrier layer formed by vapor deposition of an inorganic compound is formed on a substrate, and then formed by applying a solution containing a polysilazane compound, but does not contain an additive element and A barrier layer formed by applying a solution containing the above additive element and containing a polysilazane compound is sequentially formed.

(Middle layer)
In the present invention, as a method of forming an intermediate layer between the barrier layers, a method of forming a polysiloxane modified layer can be applied. In this method, a coating solution containing polysiloxane is applied onto the barrier layer by a wet coating method and dried, and then the dried coating film is irradiated with vacuum ultraviolet light to form a polysiloxane modified layer. It is a method of forming.

  The coating liquid used for forming the intermediate layer in the present invention mainly contains polysiloxane and an organic solvent.

  The intermediate layer covers the barrier layer and has a function of preventing the barrier layer in the gas barrier film from being damaged, but the barrier layer can also be prevented from being damaged during the manufacturing process of the gas barrier film.

(Protective layer)
The gas barrier film according to the present invention may be provided by providing a protective layer containing an organic compound on a barrier layer formed by coating or a barrier layer formed by vapor deposition of an inorganic compound (dry barrier layer). Good. As the organic compound used in the protective layer, an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used. Can do.

  The protective layer is blended with the organic resin or inorganic material and other components as necessary, and prepared as a coating solution by using a diluting solvent as necessary, and the coating solution is conventionally known on the substrate surface. It is preferable to form the film by applying it with an application method and then curing it by irradiation 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 barrier layer and the protective layer are applied and formed on the same line, the protective layer is preferably cured by irradiation with an excimer lamp.

  In addition, before modifying the barrier layer formed by applying a solution containing a polysilazane compound, an alkoxy-modified polysiloxane coating film is formed on the coating film and then irradiated with vacuum ultraviolet light The alkoxy-modified polysiloxane coating film becomes a protective layer, and can further modify the coating film obtained by applying a solution containing a polysilazane compound as a lower layer, and has an excellent barrier due to storage stability under high temperature and high humidity. A layer can be obtained.

  As the protective layer, a method of forming the intermediate polysiloxane modified layer can be applied.

[Desicant layer]
The gas barrier film of the present invention may have a desiccant layer (moisture adsorption layer). Examples of the material used for the desiccant layer include calcium oxide and organometallic oxide. As calcium oxide, what was disperse | distributed to binder resin etc. is preferable, and, as a commercial item, the AqvaDry series of SAESGETTER, etc. can be used preferably, for example. In addition, as the organic metal oxide, OleDry (registered trademark) series manufactured by Futaba Electronics Co., Ltd. or the like can be used.

[Smooth layer (underlayer, primer layer)]
The gas barrier film of the present invention may have a smooth layer (underlayer, primer layer) between the surface of the substrate having the barrier layer, preferably between the substrate and the first barrier layer. The smooth layer is provided in order to flatten the rough surface of the substrate on which the protrusions and the like exist, or to fill the unevenness and pinholes generated in the barrier layer with the protrusions on the substrate and to flatten the surface. Such a smooth layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, it is preferable that the gas barrier film of the present invention further has a smooth layer containing a carbon-containing polymer between the base material and the first barrier layer.

  The smooth layer also contains a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material or the like with an active energy ray such as an ultraviolet ray to be cured is heated. And thermosetting resins obtained by curing. These curable resins may be used alone or in combination of two or more.

  Examples of the active energy ray-curable material used for forming the smooth layer include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, and polyester. Examples include compositions containing polyfunctional acrylate monomers such as acrylates, polyether acrylates, polyethylene glycol acrylates, and glycerol methacrylates. Specifically, an organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series (compound formed by bonding an organic compound having a polymerizable unsaturated group to silica fine particles), which is an ultraviolet curable material manufactured by JSR Corporation. Can be used. It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no restriction in particular.

  Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene Oxide modified pentaerythritol triacrylate, propylene oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

  It is preferable that the composition containing an active energy ray-curable material contains a photopolymerization initiator.

  Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoy Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoin peroxide And combinations of photoreducing dyes such as eosin and methylene blue and reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more. .

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nitto Boseki Co., Ltd. Inorganic / organic nanocomposite material SSG coating, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicon resin, polyamidoamine-epichlorohydrin resin And the like.

  The method for forming the smooth layer is not particularly limited, but a coating solution containing a curable material is applied to a dry coating method such as a spin coating method, a spray method, a blade coating method, a dipping method, a gravure printing method, or a vapor deposition method. After applying the coating method to form a coating film, irradiation with active energy rays such as visible light, infrared rays, ultraviolet rays, X-rays, α rays, β rays, γ rays, electron beams, and / or heating, the coating films are formed. A method of forming by curing is preferred. As a method of irradiating active energy rays, for example, 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 is preferably used to irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm Alternatively, a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator can be used.

  Solvents used when forming a smooth layer using a coating solution in which a curable material is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol. Terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carb Acetic esters such as tall acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate , Diethylene glycol dialkyl ether, dipropylene Glycol dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smooth layer can contain additives such as a thermoplastic resin, an antioxidant, an ultraviolet absorber, and a plasticizer, if necessary, in addition to the above-described materials. In addition, an appropriate resin or additive may be used for improving the film formability and preventing the occurrence of pinholes in the film. Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof and the like. Examples include resins, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, and polycarbonate resins.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less.

  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.

  Although it does not restrict | limit especially as a film thickness of a smooth layer, The range of 0.1-10 micrometers is preferable.

[Anchor coat layer]
In the gas barrier film according to the present invention, an anchor coat layer may be formed as an easy-adhesion layer on the surface of the substrate for the purpose of improving adhesiveness (adhesion). Examples of the anchor coat 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. Can be used alone or in combination of two or more. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” 3% isopropyl alcohol solution) can be used.

(Bleed-out prevention layer)
The gas barrier film of the present invention may have a bleed-out prevention layer on the base material surface opposite to the surface on which the barrier layer is provided.

  The bleed-out prevention layer is provided for the purpose of suppressing a phenomenon that, when the film is heated, unreacted oligomers and the like are transferred from the film to the surface and contaminate the contact surface. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

The unsaturated organic compound having a polymerizable unsaturated group that can be contained as a hard coat agent in the bleed-out prevention layer is a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule. Alternatively, a monounsaturated organic compound having one polymerizable unsaturated group in the molecule can be exemplified.

The thickness of the bleed-out prevention layer is in the range of 1.0 to 10 μm from the viewpoint of improving the heat resistance of the film, facilitating the balance adjustment of the optical properties of the film, and adjusting the curl of the gas barrier film. More preferably, it is preferable to be in the range of 2 μm to 7 μm.

<< Packing 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 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 for preventing scratches on the surface of the barrier layer 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.

<< Water vapor permeability of gas barrier film >>
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.

  In the present invention, the water vapor permeability was measured by the following Ca method.

<Ca method 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)
Preparation of cell for evaluating water vapor barrier property Using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400) on the barrier layer surface of the barrier film sample, a portion (12 mm) to be deposited on the barrier film sample before attaching the transparent conductive film Other than 9 x 12 mm masks, metal calcium was vapor-deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays. Further, as shown in the examples described later, in order to confirm the change in gas barrier properties before and after bending, the same water vapor is applied to the gas barrier film subjected to the bending treatment and the gas barrier film not subjected to the bending treatment. A cell for evaluating barrier properties was produced.

  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 barrier film surface, instead of the barrier film sample as a comparative sample, a sample in which metallic calcium was deposited using a quartz glass plate having a thickness of 0.2 mm, The same 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.

<Electronic device>
The gas barrier film of the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. Examples of the device include electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device.

  The gas barrier film of the present invention can also be used for device film sealing. That is, it is a method of providing the gas barrier film of the present invention on the surface of the device itself as a support. The device may be covered with a protective layer before providing the gas barrier film.

  The gas barrier film of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.

(Organic EL device)
An example of an organic EL element using a gas barrier film is described in detail in Japanese Patent Application Laid-Open No. 2007-30387.

(Liquid crystal display element)
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has the structure which consists of a film | membrane. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The type of the liquid crystal cell is not particularly limited, but more preferably a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment), an EC type, a B type. OCB type (Optically Compensated Bend), IPS type (In-Plane Switching), and CPA type (Continuous Pinwheel Alignment) are preferable.

(Solar cell)
The gas barrier film of the present invention can also be used as a sealing film for solar cell elements. Here, the gas barrier film of the present invention is preferably sealed so that the barrier layer is closer to the solar cell element. The solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. Amorphous silicon-based solar cell elements, III-V compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I / III- such as copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur system (so-called CIGS system) Group VI compound semiconductor solar cell element, dye-sensitized solar cell element, organic solar cell element, etc. And the like. In particular, in the present invention, the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur. It is preferable that it is an I-III-VI group compound semiconductor solar cell element, such as a system (so-called CIGSS system).

(Other)
As other application examples, the thin film transistor described in JP-A-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., described in JP-A-2000-98326. Electronic paper and the like.

<Optical member>
The gas barrier film of the present invention can also be used as an optical member. Examples of the optical member include a circularly polarizing plate.

(Circularly polarizing plate)
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate is 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, the one described in JP-A-2002-86554 can be suitably used. .

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Further, in the examples, the display of “part” or “%” is used, but “part by weight” or “% by weight” is expressed unless otherwise specified. Moreover, in the following operation, unless otherwise specified, the measurement of the operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

<Manufacture of gas barrier film>
(Comparative Example 1-1)
[Formation of the first layer (dry process film formation)]
Transparent resin with a hard coat layer (intermediate layer) by an atmospheric pressure plasma method using an atmospheric pressure plasma film forming apparatus (described in FIG. 3 of JP-A-2008-56967, roll-to-roll atmospheric pressure plasma CVD apparatus) Base material (polyethylene terephthalate (PET) film with clear hard coat layer (CHC) manufactured by Kimoto Co., Ltd., hard coat layer is composed of UV curable resin mainly composed of acrylic resin, PET thickness 125 μm, CHC thickness 6 μm) A silicon oxide first layer (100 nm) was formed thereon under the following thin film formation conditions.

(Mixed gas composition)
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: Tetraethoxysilane 0.1% by volume
Additive gas: Oxygen gas 5.0% by volume
(Deposition conditions)
<First electrode side>
Power supply type: HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency: 100kHz
Output density: 10 W / cm ²
Electrode temperature: 120 ° C
<Second electrode side>
Power supply type: Pearl Industry 13.56MHz CF-5000-13M
Frequency: 13.56MHz
Output density: 10 W / cm ²
Electrode temperature: 90 ° C
The first layer formed according to the above method was composed of silicon oxycarbide (SiOC), the film thickness was 100 nm, and the elastic modulus E1 was 30 GPa uniformly in the film thickness direction.

[Formation of second layer (application of solution containing polysilazane compound)]
(Preparation of solution containing polysilazane compound)
A dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane containing amine catalyst (AZ Electronic Materials ( Co., Ltd., NAX120-20) was mixed at a ratio of 4: 1, and further diluted with a dibutyl ether solvent so that the solid content of the solution was 5% by mass.

(Film formation)
A film having a thickness of 150 nm was formed on the substrate with a spin coater and allowed to stand for 2 minutes, and then subjected to additional heat treatment for 1 minute on a hot plate at 80 ° C. to form a polysilazane coating film.

After forming the polysilazane coating film, according to the following method, vacuum ultraviolet light (M.D.M. excimer irradiation device MODEL: MECL-M-1-200, wavelength 172 nm, stage temperature 100 ° C., integrated light quantity 3000 mJ / cm ² The gas barrier film was produced by irradiation with an oxygen concentration of 0.1%.

<Measurement of vacuum ultraviolet irradiation conditions and irradiation energy>
The vacuum ultraviolet irradiation was performed using the apparatus shown in the schematic cross-sectional view of FIG.

  In FIG. 3, reference numeral 21 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber. The oxygen concentration can be maintained at a predetermined concentration. Reference numeral 22 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, and reference numeral 23 denotes an excimer lamp holder that also serves as an external electrode. Reference numeral 24 denotes a sample stage. The sample stage 24 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 21 by a moving means (not shown). The sample stage 24 can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 25 denotes a sample on which a coating film obtained by applying a solution containing a polysilazane compound is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the sample coating surface and the excimer lamp tube surface is 3 mm. Reference numeral 26 denotes a light shielding plate, which prevents the vacuum ultraviolet light from being applied to the coating film of the sample during the aging of the Xe excimer lamp 22.

  The energy irradiated on the coating film surface of the sample in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using an ultraviolet integrated light meter: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics. In the measurement, the sensor head is installed in the center of the sample stage 24 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 21 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 24 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 22, 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.

Based on the irradiation energy obtained by this measurement, the moving speed of the sample stage was adjusted to adjust the irradiation energy to 3000 mJ / cm ² . The vacuum ultraviolet irradiation was performed after aging for 10 minutes as in the case of irradiation energy measurement.

  The gas barrier film produced above was evaluated as sample 1-1 below.

<< Method for measuring characteristic values of gas barrier film >>
<Evaluation of adhesion>
About the gas barrier film produced above, a sample was prepared that was exposed to high temperature and high humidity of 85 ° C. and 85% RH for 100 hours.

  The 100 mass test of the crosscut method JIS 5400 was conducted.

  The number of squares without peeling in 100 squares was measured. The larger the number of cells without peeling, the better the adhesion.

  This evaluation was carried out for both a sample before being exposed to a high temperature and high humidity of 85 ° C. and 85% RH (immediately) and a sample after being exposed to a high temperature and high humidity of 85 ° C. and 85% RH (100 hours after DH). did.

《Bending resistance evaluation》
The gas barrier film produced above was bent 100 times at an angle of 180 degrees so that the radius was 5 mm, and then the water vapor transmission rate was measured by the same method as above, before and after the bending treatment. From the change in water vapor transmission rate, the degree of deterioration resistance was measured according to the following formula, and the bending resistance was evaluated according to the following criteria.

Deterioration resistance = (water vapor permeability after bending test / water vapor permeability before bending test) × 100 (%)
The deterioration resistance was classified into the following five grades and evaluated.

5: Deterioration resistance is 95% or more 4: Deterioration resistance is 85% or more and less than 95% 3: Deterioration resistance is 50% or more and less than 85% 2: Deterioration resistance is 10% or more and less than 50% 1: Deterioration resistance is less than 10%.

  This evaluation was carried out for both a sample before being exposed to a high temperature and high humidity of 85 ° C. and 85% RH (immediately) and a sample after being exposed to a high temperature and high humidity of 85 ° C. and 85% RH (100 hours after DH). did.

<Evaluation of barrier test>
About the gas barrier film produced above, a sample (DH after 100 hours) exposed to high temperature and high humidity of 85 ° C. and 85% RH was prepared.

  The barrier property test was performed by depositing metallic calcium having a thickness of 80 nm on a gas barrier film, and evaluating the time for 50% of the area as the degradation time. Evaluation of 50% area time of sample (immediate) before exposure to high temperature and high humidity of 85 ° C and 85% RH for 100 hours and sample after exposure to high temperature and high humidity of 85 ° C and 85% RH (after 100 hours of DH) Then, 50% area time (after DH 100 hours) / (immediately) 50% area time was calculated as the retention rate (%) and is also shown in Table 1. As an index of retention rate, 70% or more was considered acceptable, and less than 70% was judged as nonconforming.

(Metal calcium film forming equipment)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation sample)
Using a vacuum deposition apparatus (vacuum deposition apparatus JEE-400 manufactured by JEOL Ltd.), metallic calcium was deposited on the barrier layer surface of the produced gas barrier film in a size of 12 mm × 12 mm through a mask. 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, quickly transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum deposition surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX). A water vapor barrier property evaluation sample was produced by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.

  The obtained sample was stored at a high temperature and high humidity of 85 ° C. and 85% RH, and the state in which the metal calcium was corroded with respect to the storage time was observed. Observation is a sample before and after exposure to high temperature and high humidity of 85 ° C and 85% RH at a temperature of 85 ° C and 85% RH by linearly interpolating from the observation results the time that the area where metal calcium corrodes relative to the 12 mm x 12 mm metal calcium deposition area is 50%. The results are shown in Table 1.

<< Production of organic thin film electronic devices >>
Using the gas barrier film produced above, an organic EL device was produced by the following method.

[Production of organic EL elements]
(Formation of first electrode layer)
On the barrier layer of the gas barrier film produced in each example and comparative example, ITO (indium tin oxide) having a thickness of 150 nm was formed by sputtering. Next, patterning was performed by a photolithography method to form a first electrode layer. Patterning was performed so that the light emitting area was 50 mm square.

(Formation of hole transport layer)
On the first electrode layer of each gas barrier film on which the first electrode layer is formed, the hole transport layer forming coating liquid shown below is applied by an extrusion coater and then dried to form a hole transport layer. did. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

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

<Application conditions>
The coating process was performed in an atmosphere of 25 ° C. and a relative humidity (RH) of 50%.

<Preparation of hole transport layer forming coating solution>
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 an apparatus to form a hole transport layer.

(Formation of light emitting layer)
Subsequently, a white light emitting layer forming coating solution shown below was applied onto the hole transport layer by an extrusion coater and then dried to form a light emitting layer. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

<White luminescent 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 100 g of toluene. And was prepared as a white light emitting layer forming 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 the white light emitting layer forming coating solution was applied, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. Next, heat treatment was performed at a temperature of 130 ° C. to form a light emitting layer.

(Formation of electron transport layer)
Next, the following coating liquid for forming an electron transport layer was applied by an extrusion coater and then dried to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

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

<Coating liquid for electron transport layer formation>
The electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating liquid for forming an electron transport layer.

<Drying and heat treatment conditions>
After applying the electron transport layer forming coating solution, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 60 ° C. Next, in the heat treatment section, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
Next, an electron injection layer was formed on the formed electron transport layer. First, the substrate was put into a decompression chamber and decompressed to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of second electrode)
Except for the part that becomes the extraction electrode on the first electrode, aluminum is used as the second electrode forming material on the formed electron injection layer under a vacuum of 5 × 10 ⁻⁴ Pa so as to have the extraction electrode Then, a mask pattern was formed by vapor deposition so that the light emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.

(Cutting)
Each gas barrier film formed up to the second electrode was moved again to a nitrogen atmosphere and cut to a prescribed size using an ultraviolet laser to produce an organic EL device.

(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 circuit 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 to produce an organic EL element.

  In addition, as a sealing member, a polyethylene terephthalate (PET) film (PET) film (on Toyo Aluminum Co., Ltd.) on a 30 μm-thick aluminum foil using a dry lamination adhesive (two-component reaction type urethane adhesive). 12 μm thick) (adhesive layer thickness 1.5 μm) was used.

  Using a dispenser, a thermosetting adhesive was uniformly applied to the aluminum surface with a thickness of 20 μm along the adhesive surface (shiny surface) of the aluminum foil.

  The following epoxy adhesives were used as the thermosetting adhesive.

Bisphenol A diglycidyl ether (DGEBA)
Dicyandiamide (DICY)
Epoxy adduct-based curing accelerator After that, the sealing substrate is closely attached and arranged so as to cover the joint between the take-out electrode and the electrode lead, and pressure bonding conditions using the pressure roll: pressure roll temperature 120 ° C., pressure 0. Close sealing was performed at 5 MPa and an apparatus speed of 0.3 m / min.

<< Evaluation of organic EL elements >>
About the produced organic EL element, durability was evaluated in accordance with the following method.

[Evaluation of durability]
(Accelerated deterioration processing)
Each of the produced organic EL elements was subjected to an accelerated deterioration treatment for 500 hours in an environment of 85 ° C. and 85% RH, and then evaluated for the following black spots together with the organic EL elements not subjected to the accelerated deterioration treatment. .

(Evaluation of sunspots)
A current of 1 mA / cm ² was applied to the organic EL element 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 magnified with a Moritex MS-804 and a lens MP-ZE25-200) and photographed. 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 ◎, it was determined to be a practically preferable characteristic.

Element deterioration tolerance rate = (area of black spots generated in elements not subjected to accelerated deterioration processing / area of black spots generated in elements subjected to accelerated deterioration processing) × 100 (%)
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%.

  This evaluation was performed for both a sample before being exposed to a high temperature and high humidity of 85 ° C. and 85% RH (immediately) and a sample after being exposed to a high temperature and high humidity of 85 ° C. and 85% RH for 100 hours (after 100 hours of DH). .

  The evaluation results are shown in Table 1 below.

  Furthermore, the following comparative samples were prepared and subjected to the same evaluation.

(Comparative Example 1-2: Preparation of Sample 1-2)
Sample 1-2 was produced in the same manner as Comparative Example 1-1 except that the modification treatment of the second layer of Comparative Example 1-1 was not performed.

(Comparative Example 1-3: Production of Sample 1-3)
Sample 1-3 was produced in the same manner as Comparative Example 1-1 except that after the modification treatment of the second layer of Comparative Example 1-1, the post-treatment was performed at 80 ° C. for 24 hours.

(Comparative Example 1-4: Preparation of Sample 1-4)
A sample 1-4 was produced in the same manner as in the comparative example 1-1 except that the first layer and the second layer of the sample 1-1 were replaced.

(Comparative Example 1-5: Production of Sample 1-5)
Sample 1-5 was produced in the same manner as Comparative Example 1-2 except that the first layer and the second layer of Sample 1-2 were replaced.

(Comparative Example 1-6: Production of Sample 1-6)
Sample 1-6 was produced in the same manner as Comparative Example 1-3 except that the first layer and the second layer of Sample 1-3 were replaced.

(Comparative Example 1-7: Production of Sample 1-7)
Comparative Example 1-1, except that a layer modified in the same manner as the second layer of Sample 1-1 was provided as the third layer on the second layer of Sample 1-1. Sample 1-7 was produced in the same manner as described above.

(Comparative Example 1-8: Production of Sample 1-8)
Sample 1-8 was produced in the same manner as in Comparative Example 1-7, except that the third layer of Sample 1-7 was post-treated at 80 ° C. for 24 hours.

(Comparative Example 1-9: Production of Sample 1-9)
Comparative Example 1-4 with the exception that a layer similar to the second layer of Sample 1-1 and similarly modified was provided as the third layer on the second layer of Sample 1-4. Similarly, Sample 1-9 was produced.

  The sample of this invention was produced below and the same evaluation was implemented.

(Example 1-10: Production of sample 1-10)
On the first layer of Sample 1-1, a solution containing the following second polysilazane compound was prepared, formed on a substrate with a spin coater to a thickness of 150 nm, and allowed to stand for 2 minutes. An additional heat treatment was performed for 1 minute on an 80 ° C. hot plate to form a coating film. After forming the coating film, the same modification treatment as that of Sample 1-1 was performed to prepare Sample 1-10.

Solution containing second polysilazane compound Dibutyl ether solution containing 20% by mass of perhydropolysilazane (Aquamica (registered trademark) NN120-20: manufactured by AZ Electronic Materials Co., Ltd.), 1% by mass of amine catalyst and 19% by mass % Of perhydropolysilazane (Aquamica NAX120-20: manufactured by AZ Electronic Materials Co., Ltd.) was mixed at a ratio of 4 g: 1 g, 3.74 g was collected, and ALCH (manufactured by Kawaken Fine Chemical Co., Ltd.) In addition, 19.2 g of dibutyl ether was added to 0.46 g of aluminum ethyl acetoacetate / diisopropylate to prepare a solution.

(Example 1-11: Production of sample 1-11)
Sample 1-11 was produced in the same manner as in Example 1-10 except that the second layer of Sample 1-10 was not modified.

(Example 1-12: Production of sample 1-12)
Sample 1-12 was produced in the same manner as in Example 1-10, except that after the second layer modification treatment of Sample 1-10, post-treatment was performed at 80 ° C. for 24 hours.

(Example 1-13: Production of sample 1-13)
Sample 1-13 was produced in the same manner as in Example 1-10, except that the second layer of sample 1-10 was replaced with the first layer and the first layer was replaced with the second layer.

(Example 1-14: Production of sample 1-14)
Sample 1-14 was produced in the same manner as in Example 1-13, except that the first layer of Sample 1-13 was not modified.

(Example 1-15: Production of sample 1-15)
Sample 1-15 was produced in the same manner as in Example 1-13, except that the post-treatment at 80 ° C. was performed for 24 hours after the modification treatment of the second layer of Sample 1-13.

(Example 1-16: Production of sample 1-16)
Sample 1-16 was produced in the same manner as in Comparative Example 1-7, except that the third layer of Sample 1-7 was the second layer of Sample 1-10.

(Example 1-17: Production of sample 1-17)
Sample 1-17 was produced in the same manner as in Example 1-16, except that after the third layer modification treatment of Sample 1-16, post-treatment was performed at 80 ° C. for 24 hours.

(Example 1-18: Production of sample 1-18)
A sample 1-18 was produced in the same manner as in Example 1-10 except that the second layer of the sample 1-10 was further laminated as a third layer on the sample 1-10.

(Example 1-19: Production of sample 1-19)
Sample 1-19 was produced in the same manner as in Example 1-18, except that after the third layer modification treatment of Sample 1-18, post-treatment was performed at 80 ° C. for 24 hours.

(Example 1-20: Production of sample 1-20)
Sample 1-20 was produced in the same manner as in Example 1-19 except that the following modification treatment was performed after forming the first layer of sample 1-19.

Modification Treatment The integrated light quantity of the modification treatment of the second layer of Sample 1-1 was changed to 0.5 J / cm ² and the oxygen concentration was changed to 1.0%.

(Example 1-21: Production of sample 1-21)
The same procedure as in Example 1-16 except that the ALCH of the solution for preparing the third layer of Sample 1-16 was changed to 0.46 g of gallium (III) isopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.). Then, a film having a similar thickness of 150 nm was formed to prepare Sample 1-21.

(Example 1-22: Preparation of sample 1-22)
The same procedure as in Example 1-16 except that the ALCH of the solution for preparing the third layer of Sample 1-16 was changed to 0.46 g of indium (III) isopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.). A film having a similar thickness of 150 nm was formed to prepare Sample 1-22.

(Example 1-23: Production of sample 1-23)
The same thickness as in Example 1-16, except that ALCH of the solution at the time of preparing the third layer of Sample 1-16 was changed to 0.46 g of magnesium ethoxide (manufactured by Wako Pure Chemical Industries, Ltd.) A film was formed to 150 nm to prepare Sample 1-23.

(Example 1-24: Production of sample 1-24)
The same procedure as in Example 1-16 except that ALCH of the solution at the time of preparing the third layer of Sample 1-16 was changed to 0.46 g of calcium isopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.). A film was formed to a thickness of 150 nm to prepare Sample 1-24.

(Example 1-25: Production of sample 1-25)
The same procedure as in Example 1-16, except that the ALCH of the solution for preparing the third layer of Sample 1-16 was changed to 0.46 g of triisopropyl borate (manufactured by Wako Pure Chemical Industries, Ltd.). A film was formed to a thickness of 150 nm to prepare Sample 1-25.

(Example 1-26: Production of sample 1-26)
Sample 1-26 was produced in the same manner as Comparative Example 1-9 except that the third layer of Sample 1-9 was the second layer of Sample 1-10.

  Moreover, the following comparative samples were produced and the same evaluation was performed.

(Comparative Example 1-27: Production of Sample 1-27)
Tris (dibutyl sulfide) rhodium chloride (Tris (dibutylsulfide) RhCl ₃ , Gelest, Inc.) in the same amount as the ALCH of the solution used for the third layer preparation of Sample 1-21. Sample 1-27 was produced in the same procedure as in Example 1-21, except that the product was changed to “made”, and formed into the same thickness of 150 nm.

(Comparative Example 1-28: Production of Sample 1-28)
Sample 1-28 was produced in the same procedure as Comparative Example 1-1 except that the first layer of sample 1-1 was changed to the following deposited film.

  A barrier layer was formed on the smooth layer surface of the target substrate using the vacuum plasma CVD apparatus described in FIG. At this time, the high frequency power source used was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm.

  As source gases, silane gas was introduced into the vacuum chamber under conditions of 7.5 sccm, ammonia gas as flow rate of 50 sccm, and hydrogen gas as flow rate of 200 sccm. At the start of film formation, the temperature of the target substrate was set to 100 ° C., the gas pressure during film formation was set to 4 Pa, and an inorganic film mainly composed of silicon nitride was formed to a thickness of 30 nm. While maintaining the material temperature, the gas pressure was changed to 30 Pa, and an inorganic film containing silicon nitride as a main component was continuously formed with a film thickness of 30 nm to form a first layer having a total film thickness of 60 nm.

(Comparative Example 1-29: Production of Sample 1-29)
Sample 1-29 was produced in the same procedure as Comparative Example 1-28, except that after the second layer of sample 1-28 was formed, post-treatment was performed at 80 ° C for 24 hours.

(Comparative Example 1-30: Production of Sample 1-30)
Sample 1-30 was produced in the same procedure as Comparative Example 1-28, except that a layer similar to the second layer of Sample 1-28 was provided as the third layer after forming the second layer of Sample 1-28.

(Comparative Example 1-31: Production of Sample 1-31)
Sample 1-31 was produced in the same procedure as Comparative Example 1-30, except that after the third layer formation of Sample 1-30, post-treatment was performed at 80 ° C. for 24 hours.

  Example samples were prepared below and evaluated in the same manner.

(Example 1-32: Production of sample 1-32)
Sample 1-32 was produced in the same procedure as Comparative Example 1-28, except that the second layer of Sample 1-10 was provided instead of the second layer of Sample 1-28.

(Example 1-33: Production of sample 1-33)
Sample 1-33 was produced in the same procedure as Comparative Example 1-32, except that post-treatment was performed at 80 ° C. for 24 hours after the formation of the second layer of Sample 1-32.

(Example 1-34: Production of sample 1-34)
Sample 1-34 was produced in the same procedure as in Example 1-16, except that the first layer of Sample 1-16 was the first layer of Sample 1-32.

(Example 1-35: Production of sample 1-35)
Sample 1-35 was produced in the same procedure as Example 1-34, except that after the third layer formation of sample 1-34, post-treatment was performed at 80 ° C. for 24 hours.

(Example 1-36: Production of sample 1-36)
Sample 1-36 was produced in the same procedure as in Example 1-35, except that the same treatment as the modification treatment of Sample 1-20 was performed after the formation of the first layer of Sample 1-35.

(Example 1-37: Production of sample 1-37)
Magnesium ethoxide (manufactured by Wako Pure Chemical Industries, Ltd.) in the same amount as ALCH of the solution at the time of preparing the third layer of Sample 1-35 was added, and the same thickness as in Example 1-35 except that the thickness was 150 nm. Sample 1-37 was produced.

  For comparison, the following samples were prepared and subjected to the same evaluation.

(Comparative Example 1-38: Production of Sample 1-38)
The same amount of tris (dibutylsulfide) rhodium chloride [Tris (dibutylsulfide) RhCl ₃ , Gelest, Inc. Sample 1-38 was produced in the same procedure as in Example 1-34 except that the thickness was changed to 150 nm, and the thickness was changed to 150 nm.

(Comparative Example 1-39: Production of Sample 1-39)
A sample 1-39 was prepared in the same procedure as in Example 1-1 except that the first layer of the sample 1-1 was changed to the following deposited film.

[Vapor deposition film forming method]
Using the plasma discharge processing unit (for example, the roll-to-roll atmospheric pressure plasma discharge processing apparatus described in FIG. 3 of JP-A-2008-56967), the bleed-out prevention layer and the smooth layer are formed by the atmospheric pressure plasma method. A three-layered vapor deposition layer was formed on the smooth layer surface of the base material “B0” on which was formed under the following conditions.

  The first to third vapor deposition layers each contained a metal oxide (silicon oxide), and the thicknesses of the first to third vapor deposition layers were 160 nm, 30 nm, and 30 nm, respectively, for a total of 160 nm.

First vapor deposition layer Discharge gas: N ₂ gas Reaction gas 1: 1% of hydrogen gas with respect to the total gas
Reaction gas 2: 0.5% TEOS (tetraethoxysilane) with respect to the total gas
Film formation conditions;
・ First electrode side Power supply type Applied Electronics 80kHz
Frequency 80kHz
Output density 8W / cm ²
Electrode temperature 115 ° C
・ Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 95 ° C
Second vapor deposition layer Discharge gas: N ₂ gas Reaction gas 1: Oxygen gas 5% of the total gas
Reaction gas 2: TEOS is 0.1% of the total gas
Film formation conditions;
-1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10W / cm ²
Electrode temperature 120 ° C
・ Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 95 ° C
Third vapor deposition layer Discharge gas: N ₂ gas Reaction gas 1: 1% of hydrogen gas with respect to the total gas
Reaction gas 2: 0.5% of TEOS with respect to the total gas
Film formation conditions;
・ First electrode side Power supply type Applied Electronics 80kHz
Frequency 80kHz
Output density 8W / cm ²
Electrode temperature 120 ° C
・ Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 100 ° C.

(Comparative Example 1-40: Production of Sample 1-40)
Sample 1-40 was produced in the same procedure as Comparative Example 1-39, except that after the second layer formation of Sample 1-39, post-treatment was performed at 80 ° C. for 24 hours.

(Comparative Example 1-41: Production of Sample 1-41)
Sample 1-41 was produced in the same manner except that the first layer of Sample 1-7 was changed to the first layer of Sample 1-39.

(Comparative Example 1-42: Production of Sample 1-42)
Sample 1-42 was produced in the same procedure as Comparative Example 1-41 except that post-treatment was performed at 80 ° C. for 24 hours after the formation of the third layer of Sample 1-41.

  Example samples were prepared below and evaluated in the same manner.

(Example 1-43: Production of sample 1-43)
Sample 1-43 was produced in the same procedure except that the second layer of sample 1-39 was changed to the second layer of sample 1-10.

(Example 1-44: Production of sample 1-44)
Sample 1-43 was produced in the same procedure as in Example 1-43, except that after the second layer formation of sample 1-43, post-treatment was performed at 80 ° C. for 24 hours.

(Example 1-45: Production of sample 1-45)
Sample 1-45 was produced in the same procedure as Comparative Example 1-41 except that the third layer of Sample 1-41 was changed to the third layer of Sample 1-16.

(Example 1-46: Production of sample 1-46)
Sample 1-46 was produced in the same procedure as in Example 1-45, except that after the third layer formation of sample 1-45, post-treatment was performed at 80 ° C for 24 hours.

(Example 1-47: Production of sample 1-47)
Sample 1-47 was prepared in the same procedure as in Example 1-46, except that double the amount of ALCH of the solution at the time of preparing the third layer of sample 1-46 was added to give a similar thickness of 150 nm.

(Example 1-48: Production of sample 1-48)
Sample 1-45 was produced in the same procedure as Example 1-45 except that after the third layer formation of sample 1-45, post-treatment was performed at 80 ° C., 80% humidity, and 24 hours.

(Example 1-49: Production of sample 1-49)
Except for changing the modification treatment energy of the third layer of Sample 1-46 from 3000 mJ / cm ² to 6000 J / cm ² was produced samples 1-49 in the same manner as in Example 1-46.

(Example 1-50: Production of sample 1-50)
Sample 1-50 was produced in the same procedure as in Example 1-49, except that the modification treatment similar to that after the first formation of sample 1-36 was performed after the formation of the first layer of sample 1-49.

(Example 1-51: Production of sample 1-51)
Sample 1-51 was produced in the same procedure as in Example 1-47, except that the third layer of sample 1-47 was changed to the third layer of sample 1-37.

  In addition, the following comparative samples were prepared and subjected to the same evaluation.

(Comparative Example 1-52: Preparation of Sample 1-52)
Tris (dibutylsulfide) rhodium chloride (Tris (dibutylsulfide) RhCl ₃ , Gelest, Inc.) in the same amount as ALCH in the third layer of sample 1-45. Sample 1-52 was produced in the same procedure as in Example 1-45, except that the thickness was changed to 150 nm.

  The following samples of the present invention were prepared and subjected to the same evaluation.

(Example 1-53: Production of sample 1-53)
Example 1-45 except that the ALCH of the solution in the third layer preparation of Sample 1-45 was changed to 150 nm except that the same amount of germanium oxide (Mitsubishi Materials Electronics Co., Ltd.) was added and changed. Sample 1-53 was produced in the same procedure.

  The evaluation results of the gas barrier films produced in each example and comparative example are shown in Table 1 below.

  As is clear from Table 1 above, it was found that the gas barrier film of the present invention has excellent adhesion, bending resistance and barrier properties even before and after high temperature and high humidity.

  For example, when Comparative Examples 1-1 to 1-3 and Examples 1-10 to 1-12 are compared, in a comparison between gas barrier films having the same layer structure, a solution containing a polysilazane compound is applied. In Examples 1-10 to 1-12 in which the barrier layer formed in this manner contains a predetermined metal element, not only the gas barrier property is remarkably improved, but also the retention rate is greatly improved, and the adhesion and bending resistance are also high. . And the organic EL element using these gas-barrier films is hard to produce a black spot even after storing in a high temperature and high humidity environment. Similarly, comparison between Comparative Examples 1-4 to 1-6 and Examples 1-13 to 1-15; comparison between Comparative Examples 1-7 and 1-8 and Examples 1-16 and 1-17 From the comparison between Comparative Example 1-9 and Example 1-26, it can be seen that the element of the present invention exhibits excellent gas barrier properties and durability with the same layer structure.

  Further, from comparison of the results of Examples 1-10, 1-11, and 1-12, a barrier layer formed by vapor deposition of an inorganic compound or a barrier formed by applying a solution containing a polysilazane compound In Examples 1-10 and 1-12, in which at least one of the layers is modified, the adhesion, bending resistance, gas barrier property, and organic EL element of Example 1-11 that is not modified are improved. In the evaluation of the sunspots, all of them showed good performance, and Example 1-12 in which post-treatment was performed in addition to the reforming treatment showed better performance.

  Further, as in Examples 1-10, 1-11, and 1-12, formed by applying a base material, a barrier layer formed by vapor deposition of an inorganic compound, and a solution containing a polysilazane compound The gas barrier film having the barrier layers in this order was laminated in the order of the base material, the barrier layer formed by applying a solution containing a polysilazane compound, and the barrier layer formed by vapor deposition of an inorganic compound. Compared to Examples 1-13, 1-14, and 1-15, it was found that higher performance was exhibited when the conditions of the reforming treatment and the post-treatment were the same.

  As shown in Examples 1-18 and 1-21 to 1-25, the metal elements contained in the barrier layer formed by applying a solution containing a polysilazane compound are Al, Ga, In, Mg, and Ca. If it is a predetermined element such as B, the gas barrier property and the retention rate are much higher than those of Comparative Example 1-7 containing no metal element, the adhesion and the bendability are improved, and the black spot of the organic EL element is also improved. Although improved, among others, Examples 1-18 containing aluminum have particularly high performance. However, it was found that in Comparative Example 1-27 containing a metal element other than the predetermined metal element of the present invention, sufficient improvement in gas barrier properties cannot be obtained.

The same tendency was confirmed when the barrier layer formed by vapor deposition of an inorganic compound was Si ₃ N ₄ or SiO ₂ in addition to SiOC.

  For example, when Comparative Examples 1-28 to 1-31 and 1-38 were compared with Examples 1-32 to 1-37, the same layer structure was formed by applying a solution containing a polysilazane compound. Examples 1-32 to 1-37 containing a predetermined metal element in the barrier layer have better performance. At this time, Example 1-35 subjected to post-processing exhibits higher performance than Example 1-34 not subjected to post-processing with the same layer configuration. In addition, Example 1-36 in which the barrier layer formed by vapor deposition of the inorganic compound was also subjected to the modification treatment was superior to Example 1-35 in which the modification treatment was not performed with the same layer configuration. Show performance.

  Further, when Comparative Examples 1-39 to 1-42 and 1-52 are compared with Examples 1-43 to 1-51 and 1-53, a solution containing a polysilazane compound is applied if the same layer structure is applied. Examples 1-43 to 1-51 and 1-53, which include a predetermined metal element in the formed barrier layer, have more excellent performance. At this time, Example 1-44 which performed post-processing shows higher performance than Example 1-43 which is not post-processed by the same layer structure. In addition, Example 1-50 in which the barrier layer formed by vapor deposition of the inorganic compound was also subjected to the modification treatment was superior to Example 1-49 in which the modification treatment was not performed with the same layer configuration. Show performance.

In addition, in the gas barrier film of the present invention, when the barrier layer formed by vapor deposition of an inorganic compound contains nitrogen atoms, the adhesion, bending resistance, and gas barrier are lower than when no nitrogen atoms are contained. It was confirmed that the effect of suppressing the black spot of the organic EL element was further enhanced. For example, Example 1-35 in which the barrier layer formed by vapor deposition of an inorganic compound contains nitrogen atoms (is Si ₃ N ₄ ) has the same layer structure and is formed by vapor deposition of an inorganic compound. Compared with Example 1-17 or Example 1-46 in which the formed barrier layer does not have nitrogen atoms, superior performance is exhibited.

  In addition, this application is based on the JP Patent application 2013-017831 for which it applied on January 31, 2013, The content of an indication is referred as a whole by reference.

Claims (10)

A barrier layer formed by vapor deposition of an inorganic compound on at least one surface of the substrate, and a barrier layer formed by vapor deposition of at least the inorganic compound on the substrate; In a gas barrier film comprising a barrier layer formed by applying a solution containing a polysilazane compound, formed on the same side surface as formed,
The barrier layer formed by applying the solution containing the polysilazane compound is at least one selected from the group consisting of elements of Group 2, Group 13, and Group 14 of the long-period periodic table (provided that , A gas barrier film containing the elements of (except for silicon and carbon).   The element is at least one selected from the group consisting of aluminum (Al), indium (In), gallium (Ga), magnesium (Mg), calcium (Ca), germanium (Ge), and boron (B). The gas barrier film according to claim 1, wherein   At least one of a barrier layer formed by vapor deposition of the inorganic compound or a barrier layer formed by applying a solution containing the polysilazane compound is formed by a modification treatment by vacuum ultraviolet irradiation. The gas barrier film according to claim 1 or 2.   The gas barrier film according to any one of claims 1 to 3, wherein the barrier layer formed by vapor deposition of the inorganic compound is a vapor deposition layer containing nitrogen atoms.   The gas barrier film according to claim 1, wherein the gas barrier film is formed by post-treatment.   The base material, a barrier layer formed by vapor deposition of the inorganic compound, and a barrier layer formed by applying a solution containing the polysilazane compound in this order. The gas barrier film according to any one of the above. Forming a layer by vapor deposition of an inorganic compound on a substrate; and
At least one selected from the group consisting of polysilazane compounds and elements of Group 2, Group 13, and Group 14 of the long-period periodic table on the layer formed by vapor-depositing an inorganic compound Applying a solution containing a compound containing an element (excluding silicon and carbon) to form a coating film;
A step of modifying the coating film by irradiating with vacuum ultraviolet rays; and
A method for producing a gas barrier film, comprising:   The manufacturing method according to claim 7, further comprising a step of performing a modification treatment by irradiating the layer with vacuum ultraviolet rays after the step of forming a layer by vapor-depositing the inorganic compound.   The manufacturing method according to claim 7, further comprising a step of post-treating the coating film after the modification treatment.   The electronic device which has a gas barrier film of any one of Claims 1-6.