JP2018118381A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having excellent durability in a high-temperature, high-humidity environment.SOLUTION: A gas barrier film has a resin substrate 11 and a silicon-containing layer 12, the silicon-containing layer 12 having a region (A)13 that satisfies a relational expression (1) when the composition is indicated by SiMxNyOz in an atomic composition distribution profile obtained when performing an XPS composition analysis in a thickness direction, and the region (A) being formed by an ion implantation method or an ion plating method.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film.

  Gas barrier films are used as substrate films and sealing films in flexible electronic devices, particularly flexible organic EL devices. High barrier properties are required for gas barrier films used in these.

  In general, a gas barrier film is produced by forming an inorganic barrier layer on a base film by a vapor deposition method such as vapor deposition, sputtering, or CVD. In recent years, a manufacturing method for forming a gas barrier layer by applying energy to a precursor layer formed by applying a solution on a substrate has been studied. In particular, studies using a polysilazane compound as a precursor have been widely conducted, and studies are being conducted as a technique for achieving both high productivity and barrier properties by coating. In particular, the modification of the polysilazane layer using excimer light having a wavelength of 172 nm has attracted attention.

  Here, Patent Document 1 discloses a molded body having a layer obtained by implanting hydrocarbon compound ions into a layer containing a polysilazane compound. In Patent Document 2, after applying a solution containing polysilazane and a catalyst onto a substrate, then removing the solvent to form a polysilazane layer, the above polysilazane layer is less than 230 nm in an atmosphere containing water vapor. Disclosed is a method for forming a gas barrier layer on a substrate by irradiation with VUV radiation containing a wavelength component and UV radiation containing a wavelength component of 230-300 nm. Further, Patent Document 3 discloses a first step in which a polysilazane is applied on a resin base material to form a polymer film having a thickness of 250 nm or less, and a second step in which the formed polymer film is irradiated with vacuum ultraviolet light. And a third step in which the first step and the second step are repeated on the film formed in the second step to form a film, and a method for producing a flexible gas barrier film is disclosed. .

International Publication No. 2011-122547 Special table 2009-503157 JP 2009-255040 A

  However, an inorganic barrier layer or a gas barrier layer formed by excimer photo-modification of polysilazane by a vapor deposition method such as a sputtering method or a CVD method is used in a very severe environment of high temperature and high humidity such as 80 ° C. and 85% RH. Then, it turned out that gas-barrier property falls with time.

  Thus, there has been a demand for a gas barrier film that can be used as an electronic device by suppressing the performance deterioration of the gas barrier layer obtained by modifying polysilazane under high temperature and high humidity conditions.

  Then, an object of this invention is to provide the gas barrier film excellent in durability in a high temperature, high humidity environment.

  The present invention relates to a gas barrier film having a resin base material and a silicon-containing layer, and the composition is SiMxNyOz in the atomic composition distribution profile obtained when the silicon-containing layer is subjected to XPS composition analysis in the thickness direction. It is a gas barrier film that has a region (A) that satisfies the following relational expression (1) when it is shown, and that the region (A) is formed by an ion implantation method or an ion plating method.

  ADVANTAGE OF THE INVENTION According to this invention, the gas-barrier film excellent in durability in a high temperature / humidity environment can be provided.

FIG. 1 is a schematic cross-sectional view showing a gas barrier film according to an embodiment of the present invention. It is a schematic diagram which shows an example of the plasma CVD apparatus which has a counter roll electrode. It is a conceptual diagram of a hollow cathode type ion plating apparatus.

  The present invention relates to a gas barrier film having a resin base material and a silicon-containing layer, and the composition is SiMxNyOz in the atomic composition distribution profile obtained when the silicon-containing layer is subjected to XPS composition analysis in the thickness direction. It is a gas barrier film that has a region (A) that satisfies the following relational expression (1) when it is shown, and that the region (A) is formed by an ion implantation method or an ion plating method.

  As described above, an inorganic barrier layer or a gas barrier layer formed by excimer photo-modification of polysilazane by a vapor deposition method such as sputtering or CVD is very harsh at a high temperature and high humidity of 80 ° C. and 85% RH. Under such circumstances, the gas barrier property may deteriorate with time.

  On the other hand, the gas barrier film of the present invention has a region (A) in the silicon-containing layer. Due to the presence of such a region (A), the durability under a high temperature and high humidity environment is remarkably improved.

Although the detailed mechanism by which the durability in a high-temperature and high-humidity environment is improved due to the presence of the region (A) is unknown, it is presumed as follows.

  Due to the presence of the transition metal and oxygen in the region (A), the region (A) is easily oxidized prior to the silicon-containing layer. Further, the left side (4 + Σax) − (3y + 2z) of the above formula (1) (hereinafter also simply referred to as the left side of the formula (1)) is the sum of O and N with respect to the combined number of Si and M. This means that the number of couplings made is small. In other words, when the left side of Formula (1) is 0, it is the same as the theoretical number of bonds, whereas when it is greater than 0, the silicon and transition metal bonds are considered to be in a slightly surplus state. For this reason, the region (A) is a region where there is room for further oxidation. In such a region (A), the bonding distance between silicon and the transition element is short, and as a result, the region has a high film density. For this reason, it is considered that oxygen molecules and water molecules do not easily permeate even under high temperature and high humidity, and are excellent in durability in high temperature and high humidity environments.

  Hereinafter, preferred embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

  In this specification, unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

  FIG. 1 is a schematic cross-sectional view showing a gas barrier film according to an embodiment of the present invention. In the gas barrier film 10 of FIG. 1, a resin base material 11, a silicon-containing layer 12, and a layer (not including silicon) 13 containing a transition metal compound are arranged in this order. Then, the region (A) is formed in the silicon-containing layer near the interface between the silicon-containing layer 12 and the layer 13 containing the transition metal compound.

[Silicon-containing layer]
The silicon-containing layer means a layer containing silicon. Preferably, the silicon-containing layer preferably includes any one selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, silicon oxynitride and silicon oxycarbide, and silicon oxide, silicon oxycarbide and oxynitride More preferably, any one selected from the group consisting of silicon is included.

  From the viewpoint of gas barrier performance, the thickness of the silicon-containing layer (when it is a laminated structure of two or more layers) is preferably 10 to 1000 nm, more preferably 50 to 600 nm, and 50 to More preferably, it is 300 nm. If it is this range, the balance of gas barrier property and durability becomes favorable and is preferable.

  The silicon-containing layer may be a single layer or a laminated structure of two or more layers.

  As a method for forming the silicon-containing layer, any method can be used as long as the target thin film can be formed. The silicon-containing layer is preferably obtained by forming a silicon-containing precursor layer and then applying an ion implantation method or an ion plating method which is a means for forming the region (A).

  The silicon-containing precursor layer means a layer containing silicon. Preferably, the silicon-containing precursor layer preferably contains any one selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, silicon oxynitride and silicon oxycarbide, and includes silicon oxide, silicon oxycarbide and More preferably, any one selected from the group consisting of silicon oxynitride is included.

The silicon-containing precursor layer is preferably a vapor-deposited layer obtained by a vapor deposition method, or a polysilazane-derived layer obtained by applying and drying a coating solution containing polysilazane, under a high-temperature and high-humidity environment. Since the durability at is particularly good, a polysilazane-derived layer obtained by applying and drying a coating liquid containing polysilazane is more preferable. Here, “obtained by applying and drying a coating liquid containing polysilazane” means that the silicon precursor layer and the silicon-containing layer obtained thereafter apply and dry the coating liquid containing polysilazane. Means having it at any of the manufacturing stages. That is, the silicon-containing layer is preferably obtained by applying and drying a coating liquid containing polysilazane. Furthermore, the silicon-containing layer is more preferably obtained by irradiating a coating film obtained by applying and drying a coating liquid containing polysilazane with vacuum ultraviolet rays.

  When the silicon-containing precursor layer is a polysilazane-derived layer, the detailed mechanism that the durability under a high-temperature and high-humidity environment is particularly good is unknown, but the transition metal atom and the silicon atom in the region (A) This is considered to be because it is easy to form a direct bond. Since the interatomic distance between the silicon element and the transition metal atom is shorter than the bond between the silicon atom and the oxygen atom, the film becomes dense due to the direct bond between the transition metal atom and the silicon atom, resulting in high temperature and high humidity conditions. It is thought that the barrier performance below is improved.

  The vapor deposition method for forming the silicon-containing precursor layer is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, and ion plating, plasma CVD (chemical), and the like. Examples thereof include chemical vapor deposition methods such as vapor deposition method and ALD (Atomic Layer Deposition). Considering productivity and the like, it is preferable to use the sputtering method or the plasma CVD method among the vapor phase film forming methods.

  For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used. In addition, a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used. By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable. When performing DC sputtering or DMS sputtering, a silicon oxide thin film can be formed by using silicon as a target and introducing oxygen into the process gas. In the case of film formation by RF (high frequency) sputtering, a silicon oxide target can be used. As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Furthermore, by introducing a reaction gas such as oxygen, nitrogen, carbon dioxide, carbon monoxide or the like into the process gas, a silicon compound thin film such as silicon oxide, nitride, nitride oxide or carbonate can be produced. . Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, film material, film thickness, and the like.

  On the other hand, in chemical vapor deposition (Chemical Vapor Deposition), a raw material gas containing a target thin film component is supplied onto a substrate, and a film is deposited by a chemical reaction in the substrate surface or in the gas phase. Is the method. 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. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of the film formation speed and the processing area.

  Although it does not specifically limit as a plasma CVD method, The plasma CVD method using the plasma CVD method of the atmospheric pressure or the atmospheric pressure described in the international publication 2006/033233, and the plasma CVD apparatus with a counter roll electrode is mentioned. . Especially, since productivity is high, it is preferable to form a silicon-containing precursor layer by a plasma CVD method using a plasma CVD apparatus having a counter roll electrode. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

  A method for producing a silicon-containing layer by a plasma CVD method using such a plasma CVD apparatus having a counter roll electrode is known, and is described in, for example, Japanese Patent Application Laid-Open No. 2014-1000080.

  FIG. 2 is a schematic diagram showing an example of a plasma CVD apparatus having a counter roll electrode. As the configuration of the plasma CVD apparatus 31 having the counter roll electrode shown in FIG. 2, the feed roller 32, the transport rollers 33, 34, 35, and 36, a pair of film forming rollers 39 and 40, a gas supply port 41, A plasma generating power source 42, magnetic field generators 43 and 44 installed inside the film forming rollers 39 and 40, and a winding roller 45 are provided. Further, in such a manufacturing apparatus 31, at least the film forming rollers 39, 40, the gas supply port 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43, 44 made of permanent magnets are not shown. Located in the chamber. 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 such a vacuum pump. In such a manufacturing apparatus 31, each film-forming roller is for plasma generation so that a pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. Connected to a power source 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge to the facing space (discharge region) between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. In this way, plasma can be generated in the facing space between the film forming roller 39 and the film forming roller 40. 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. Further, inside the film forming roller 39 and the film forming roller 40, magnetic field generators 43 and 44 are provided, which are fixed so as not to rotate even if these film forming rollers rotate.

As a film forming gas (a raw material gas or the like) used in a plasma CVD method using a plasma CVD apparatus having a counter roll electrode, a raw material gas, a reactive gas, a carrier gas, or a discharge gas is used alone or in combination. The source gas in the film forming gas used for forming the silicon-containing precursor layer can be appropriately selected and used according to the material of the barrier layer to be formed. As such a source gas, for example, an organosilicon compound containing silicon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), 1.1.3.3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, silane, methylsilane, and dimethylsilane. And trimethylsilane, tetramethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), and the like. Among these organosilicon compounds, hexamethyldisiloxane and 1.1.3.3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting silicon-containing layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types. As these organosilicon compound gases, appropriate source gases are selected according to the type of the barrier layer. 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, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as a 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, etc .; hydrogen can be used.

  When such a film forming gas contains a raw material gas and a reactive gas, the ratio of the raw material gas and the reactive gas is the reaction gas that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable that the ratio of the reaction gas is not excessively increased rather than the ratio of the amount.

The polysilazane used in forming a polysilazane-derived layer obtained by applying and drying a coating liquid containing polysilazane is a polymer having a silicon-nitrogen bond, and Si-N, Si-H, It is a ceramic precursor inorganic polymer such as SiO ₂ having a bond such as N—H, Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y .

  Specifically, the polysilazane preferably has the following structure.

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.

  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. Is preferred.

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 ′} are each independently 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. 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.

Among the polysilazanes of the above 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' , R _{4 '} each represents a methyl group, and R _5' represents a vinyl group; R _{1 '} , R _3' , 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.

In the general formula (III), n ″, p ″ and q are integers, and the polysilazane having the 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 above 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 coating liquid for forming a polysilazane-derived layer. As a commercially available product of polysilazane solution, NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, etc. manufactured by AZ Electronic Materials Co., Ltd. Is mentioned. These polysilazane solutions can be used alone or in combination of two or more.

  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.

  When polysilazane is used, the content of polysilazane in the polysilazane coating film before irradiation with vacuum ultraviolet rays can be 100% by mass when the total mass of the polysilazane coating film is 100% by mass. When the polysilazane coating film before irradiation with vacuum ultraviolet rays contains a material other than polysilazane, the content of polysilazane in the film is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass. % Or less, more preferably 70% by mass or more and 95% by mass or less.

(Coating liquid for polysilazane-derived layer formation)
The solvent for preparing the coating liquid for forming the polysilazane-derived layer is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups (for example, hydroxyl group or amine) that easily react with polysilazane. An organic solvent inert to polysilazane, and more preferably an aprotic organic solvent. Specifically, the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc. 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 according to purposes such as the solubility of polysilazane 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 polysilazane in the polysilazane-derived layer forming coating solution is not particularly limited, and varies depending on the film thickness of the layer and the pot life of the coating solution, but preferably 1 to 80% by mass, more preferably 5 to 50% by mass, More preferably, it is 10-40 mass%.

In the case of modifying the polysilazane-derived layer, the polysilazane-derived layer forming coating solution preferably contains a catalyst in order to promote the modification. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ', N'-tetramethyl-1,3-diaminopropane, amine catalysts such as N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on polysilazane. By making the amount of catalyst added within this range, excessive silanol formation due to rapid progress of the reaction,
In addition, a decrease in film density and an increase in film defects can be avoided.

  The following additives can be used in the polysilazane-derived layer forming coating solution as 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, particularly urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyester resins or modified polyester resins, epoxy resins, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

(Method of applying a coating liquid for forming a polysilazane-derived layer)
As a method of applying the polysilazane-derived layer forming coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method and the like. It is done.

  The coating thickness can be appropriately set according to the preferred thickness and purpose.

  After coating the coating solution, the coating film is dried. 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 silicon-containing precursor 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.

  The coating film obtained by applying the polysilazane-derived layer forming coating solution may include a step of removing moisture before irradiation with vacuum ultraviolet rays or during irradiation with vacuum ultraviolet rays. As a method for removing moisture, a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. The preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), the more preferable dew point temperature is −5 ° C. or lower (temperature 25 ° C./humidity 10%), and the time to be maintained is the film thickness of the silicon-containing layer. It is preferable to set appropriately. Specifically, it is preferable that the dew point temperature is −5 ° C. or lower and the maintained time is 1 minute or longer. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher and preferably −40 ° C. or higher. From the viewpoint of promoting the dehydration reaction of the silicon-containing layer converted to silanol by removing moisture before or during the modification treatment.

Even if the coating film containing polysilazane formed as described above is used as a silicon-containing precursor layer as it is, silicon is obtained by irradiating the obtained coating film with vacuum ultraviolet rays and performing a conversion reaction to silicon oxynitride or the like. It is good also as a containing precursor layer. In the case of irradiation with vacuum ultraviolet rays, it is preferable that the amount of light is low because the thickness of the region (A) is thick. When the amount of vacuum ultraviolet light is low or when no vacuum ultraviolet light is irradiated, the outermost surface of the silicon-containing precursor layer exists in a metastable state. For example, as described later, a transition metal compound is formed on the silicon precursor layer. When forming a film, it is preferable because the bonds can be easily recombined and the ratio of the transition metal and silicon element to be bonded becomes high. Here, “the amount of vacuum ultraviolet light is low or vacuum ultraviolet light is not irradiated” is preferably a vacuum ultraviolet light irradiation energy amount (irradiation amount) of 0 to 5.0 J / cm ² , and 0 to 3 J / cm ^2. more preferably cm ^2.

<Vacuum UV irradiation>
The coating film containing polysilazane formed as described above can be used as a silicon-containing precursor layer as it is. However, the obtained coating film is irradiated with vacuum ultraviolet rays to perform a conversion reaction to silicon oxynitride or the like. It is good also as a silicon-containing precursor layer by performing.

  The vacuum ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the resin substrate used. For example, in the case of batch processing, it can be processed in an ultraviolet baking furnace equipped with an ultraviolet ray generation source. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. Further, when the object is a long film, it can be converted to ceramics by continuously irradiating ultraviolet rays in a drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate and silicon-containing layer to be used.

  The modification by vacuum ultraviolet irradiation uses a light energy of 100 to 200 nm, preferably a light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane, and bonds the atoms with only photons called photon processes. In this method, a film containing silicon oxynitride is formed at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together.

  The vacuum ultraviolet ray source in the present invention may be any source that generates light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator (for example, Xe excimer lamp) having a maximum emission at about 172 nm, and an emission line at about 185 nm. Low pressure mercury vapor lamps with medium pressure and medium and high pressure mercury vapor lamps with wavelength components of 230 nm or less, and excimer lamps with maximum emission at about 222 nm.

  Among these, 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.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. The coating film can be modified in a short time by the high energy of the active oxygen, ozone and ultraviolet radiation.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

Oxygen is required for the reaction at the time of vacuum ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. In addition, it is preferably performed in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). More preferably. Also, the water vapor concentration during the conversion process is preferably in the range of 1,000 to 4,000 volume ppm.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a 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.

In vacuum ultraviolet irradiation step, preferably the intensity of the vacuum ultraviolet rays in the coated surface of the coating film is subjected is a ^{1mW / cm 2 ~10W / cm 2} , more preferably 30mW / cm ² ~200mW / cm 2 and further preferably ^{50mW / cm 2 ~160mW / cm 2} . If it is 1 mW / cm ² or more, the reforming efficiency is improved, and if it is 10 W / cm ² or less, ablation that can occur in the coating film and damage to the substrate can be reduced.

Irradiation energy amount of the VUV at the surface of the coating film in the case of reforming (dose) is preferably 0.1~10J / cm ^2, more preferably 0.1~7J / cm ² . If it is this range, generation | occurrence | production of the crack by excessive modification | reformation and the thermal deformation of a resin base material can be suppressed, and productivity will improve.

The vacuum ultraviolet ray used may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.

  In the vacuum ultraviolet irradiation process, it is preferable to use heat treatment in combination. As the heat treatment, for example, a method of heating a coating film by contacting a substrate with a heating element such as a heat block, a method of heating an atmosphere by an external heater such as a resistance wire, an infrared region such as an IR heater, etc. Although the method using light etc. are mentioned, it does not specifically limit. As heating temperature, it is preferable to adjust suitably in the range of 50 to 250 degreeC.

[Area (A)]
The region (A) is a region that satisfies the formula (1). In the region (A), a co-oxynitride layer of Si and M is formed, and this co-oxynitride layer of Si and M is considered to exhibit high wet heat resistance. Further, the region (A) is a region where there is room for further oxidation, and it is considered that the deterioration of the silicon-containing layer accompanying oxygen intrusion is suppressed, and the durability under high temperature and high humidity conditions is further improved.

  The location of the region (A) in the silicon-containing layer is not particularly limited, but it is preferably present in the surface layer facing the substrate of the silicon-containing layer. The presence of the region (A) at such a position further suppresses deterioration of the silicon-containing layer accompanying oxygen intrusion from the surface layer, and further improves durability under high temperature and high humidity conditions.

In the formula (4 + Σax) − (3y + 2z), M is a transition metal, a is the stoichiometric valence of the transition metal M, x is the existing atomic ratio of the transition metal M to the silicon atom, y is the existing atomic ratio of nitrogen to silicon atoms, and z is the existing atomic ratio of oxygen to silicon atoms. x is 0 <x, and preferably 0 <x <10. y is 0 ≦ y, and preferably 0 ≦ y <10. z is 0 <z, and preferably 0 <z <100.

  In the formula, Σax means the sum of products of the stoichiometric maximum valence of each transition metal and the atomic ratio of each transition metal to silicon atom 1, for example, niobium having a valence of 5 is an atom with respect to a silicon atom. When titanium having a ratio x1 and a valence of 4 is present in the region (A) at an atomic ratio x2 with respect to silicon atoms, Σax = 5 × x1 + 4 × x2. When only one kind of transition metal exists in the region (A), the left side of the formula (1) is (4 + ax) − (3y + 2z).

  Furthermore, it is preferable to have a region (B) where (4 + Σax) − (3y + 2z)> 1 in the region (A). It is preferable to have such a region (B) because it is further excellent in durability under high temperature and high humidity conditions. The region (A) preferably has a region where (4 + Σax) − (3y + 2z)> 2 and more preferably has a region where (4 + Σax) − (3y + 2z)> 3.

  The maximum value of (4 + Σax) − (3y + 2z) in the region (A) is preferably 7 or less from the viewpoint of film coloring.

  Control of the value of (4 + Σax) − (3y + 2z) is, for example, when the layer containing the transition metal compound is formed by an ion plating method (the following method (1)) as an example. The value of (4 + Σax) − (3y + 2z) can be controlled by controlling the pressure in the reaction chamber, controlling the bias voltage to the substrate. By increasing the heating temperature of the substrate, increasing the bias voltage to the substrate, and decreasing the pressure in the reaction chamber, the value of (4 + Σax) − (3y + 2z) can be increased.

  The transition metal M included in the region (A) refers to a Group 3 element to a Group 12 element, and examples of the transition metal include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu. Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf , Ta, W, Re, Os, Ir, Pt, and Au.

  The transition metal M contained in the region (A) is preferably a metal having a lower redox potential than silicon. By including a transition metal having a lower oxidation-reduction potential than silicon, good barrier properties can be obtained. Specific examples of the transition metal having a lower oxidation-reduction potential than silicon include niobium, tantalum, barium, zirconium, titanium, hafnium, yttrium, lanthanum, cerium, and the like. These metals may be used alone or in combination of two or more. Among these, niobium, tantalum, and vanadium, which are Group 5 elements, can be preferably used because they have a high effect of suppressing oxidation of the silicon-containing layer, and niobium can be more preferably used. Furthermore, from the viewpoint of optical properties, the transition metal in the transition metal compound is particularly preferably niobium or tantalum from which a compound with good transparency can be obtained.

The thickness of the region (A) is preferably 2 nm or more from the viewpoint of suppressing oxygen intrusion into the silicon-containing layer, and preferably 20 nm or less from the viewpoint of thinning. More preferably, the thickness of area | region (A) is 4-20 nm, More preferably, it is 10-16 nm. Note that the thickness of the region (A) is an integral multiple of 2.0 nm because the depth profile is obtained every 2.0 nm in the depth direction in terms of SiO ₂ in the XPS analysis shown below (region) The number of plots satisfying the condition (A) is measured. When the number of plots is two, the film thickness of the region (A) is 2 nm, and when the number is three, the number is 4 nm.

  In the region (A), the composition distribution profile in the thickness direction is measured by XPS analysis, and the value of (4 + Σax) − (3y + 2z) is obtained to determine whether the region (A) has the region (A). XPS analysis conditions are as follows.

<< XPS analysis conditions >>
・ Equipment: ULVAC-PHI QUANTERASXM
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: After sputtering equivalent to 2.0 nm in terms of SiO ₂ , measurement is repeated to obtain a depth profile for every 2.0 nm in the depth direction of SiO ₂ Quantification: The peak obtained by obtaining the background by the Shirley method The area is quantified using the relative sensitivity coefficient method. Data processing uses MultiPak manufactured by ULVAC-PHI.

  The standard redox potential, the stoichiometric maximum valence, and the stoichiometric oxide of the major metals are shown in the table below.

  The region (A) is formed by an ion implantation method or an ion plating method. Specifically, a method of forming a layer containing a transition metal compound by an ion plating method on the silicon-containing precursor layer (method (1)) or a transition metal ion by an ion implantation method on the silicon-containing precursor layer. This is a method of injection (method (2)). According to these methods, the thickness of the region (A) can be increased, and the durability under high temperature and high humidity conditions is remarkably improved.

  In the methods (1) and (2), it is preferable that a layer containing a transition metal compound (hereinafter also simply referred to as a transition metal compound layer) is formed on the silicon-containing layer (the form of FIG. 1). Here, the transition metal compound is not particularly limited, and examples thereof include transition metal oxides, nitrides, carbides, oxynitrides, and oxycarbides. Among these, from the viewpoint of more effectively suppressing the oxidation of the silicon-containing layer, the transition metal compound is preferably a transition metal oxide. The transition metal compounds may be used alone or in combination of two or more.

  The content of the transition metal compound in the transition metal compound layer is not particularly limited as long as the effects of the present invention are exhibited, but the content of the transition metal compound is 50% by mass or more based on the total mass of the transition metal compound layer. It is preferably 80% by mass or more, more preferably 95% by mass or more, particularly preferably 98% by mass or more, and 100% by mass (that is, the transition metal compound layer is Most preferably, it comprises a transition metal compound.

  The transition metal compound layer may be a single layer or a laminated structure of two or more layers. When the transition metal compound layer has a laminated structure of two or more layers, the transition metal compounds contained in the transition metal compound layer may be the same or different.

  The thickness of the transition metal compound layer (the total thickness in the case of a laminated structure of two or more layers) is preferably 1 to 200 nm, and preferably 2 to 100 nm, from the viewpoint of in-plane uniformity of the barrier property. Is more preferable, and it is further more preferable that it is 3-50 nm.

  The ion plating method in the method (1) is a method in which a vaporized element is ionized by an electron beam or arc discharge and accelerated by an electric field to form a film on a substrate as high energy particles of several ev to several tens ev. By using an ion plating method, the thickness of the region (A) can be increased, and durability under high temperature and high humidity conditions is improved, which is preferable.

  Hereinafter, the ion plating method will be described.

  Examples of the ion plating method include a multi-cathode method, a high-frequency method, a high-frequency heating method, an auxiliary electrode method, an activated reaction vapor deposition method, a hollow cathode method (HCD), an arc plasma method, and a cluster ion beam method. The hollow cathode method is preferably used because of its high ionization rate and high film formation rate.

  The hollow cathode method is a method in which a high current electron beam is generated by a hollow cathode (hollow cathode) electron gun, and evaporation of an evaporation source and ionization of an evaporated substance are simultaneously performed by the electron beam.

  FIG. 3 shows a conceptual diagram of a hollow cathode ion plating apparatus. The ion plating apparatus 20 of FIG. 3 includes a vacuum chamber 21, a hollow cathode (hollow cathode) electron gun 22, an anode 23, a permanent magnet 24 disposed in the anode, a heater 26, and a vacuum exhaust system 29. The laminated body 25 in which the silicon-containing precursor layer is formed on the resin base material is installed at the time of film formation.

The region (A) can be formed by depositing a transition metal compound on the silicon-containing precursor layer formed on the resin substrate using the hollow cathode ion plating apparatus 20. Specifically, the evaporation source 27 is installed on the anode 23 to reduce the pressure in the vacuum chamber 21. At this time, the inside of the vacuum chamber is preferably set to 1 × 10 ⁻⁴ Torr or less. In this state, a plasma source gas such as argon gas (Ar) is introduced into the hollow cathode (hollow cathode) electron gun 22. When energized while introducing the plasma source gas, gas molecules inside the cathode are ionized by a high-frequency electric field, and an electron beam is generated by a hollow cathode (hollow cathode) electron gun 22. The generated electron beam is drawn into the vacuum chamber 21 by a magnetic field formed by an auxiliary coil (not shown), converges on the evaporation source 27 by a magnetic field created by the permanent magnet 24 below the anode 23, and heats the evaporation source 27. To do. As a result, the heated portion of the evaporation source 27 evaporates, and the evaporated molecules are ionized by the high-density plasma existing in the vicinity of the anode 23. The ionized vaporized substance collides with the stacked body 25 to which a bias voltage is applied by an RF (radio frequency, high frequency) power supply 28, and the region (A
) And a transition metal compound layer.

  Examples of the raw material (evaporation source) that generates ions to be implanted include transition metal oxides such as niobium oxide, silicon oxide, and titanium oxide.

  Alternatively, a reactive gas (oxygen, nitrogen, or the like) may be introduced into the chamber to form a transition metal compound thin film.

  Prior to film formation, it is preferable to heat-treat the laminate on which the silicon precursor layer is formed. The heating method is not particularly limited, but oven heating by electric resistance heating, vacuum oven heating, heating using hot water, heating by infrared heater, heating by ultrasonic vibration, radiation heating by IR heater, film roll Examples include a method of heating a shaft or a jig in a running process by electrically heating the jig directly in contact with the film, heating by high frequency heating, or the like. The substrate temperature during heating is preferably 20 to 120 ° C.

The pressure in the chamber at the time of film formation is preferably 10 ⁻⁴ to 10 ⁻² Torr. When the pressure in the chamber at the time of film formation is in such a range, ion implantation can be performed easily and efficiently uniformly.

  The power applied to the laminate 25 during film formation is preferably 200 to 2000 W, more preferably 500 to 1500 W, because the region (A) can be easily formed.

When the region (A) is formed by the ion plating method using the silicon-containing precursor layer, the stoichiometric oxide (for example, Nb ₂ O ₅ when the transition metal is Nb) is a polysilazane-derived layer. It is preferable to perform film formation under ion plating conditions such as those described above.

  Next, the ion implantation method (2) will be described. The ion implantation method is a method in which an object is placed in plasma and a high voltage pulse is applied to suck and accelerate ions in the plasma into the object.

  Examples of the raw material for generating the ions to be implanted include Ar.

  Among them, as the plasma ion implantation method, (A) a method of injecting ions present in plasma generated using an external electric field into a laminate in which a silicon-containing precursor layer is formed on a resin substrate, Or (B) without using an external electric field, ions existing in the plasma generated only by the electric field by the negative high voltage pulse applied to the laminate in which the silicon-containing precursor layer is formed on the resin substrate, A method of injecting into a laminate in which a silicon-containing precursor layer is formed on a resin substrate is preferable.

  In the method (A), the pressure during ion implantation (pressure during plasma ion implantation) is preferably 1 Pa or less, and more preferably 0.01 to 1 Pa. When the pressure at the time of plasma ion implantation is in such a range, ion implantation can be performed easily and efficiently uniformly.

In the method (B), it is not necessary to increase the degree of reduced pressure, the processing operation is simple, and the processing time can be greatly shortened. Moreover, it can process uniformly over the whole coating-film layer, and the ion in plasma can be continuously inject | poured into the surface part of a layer with high energy at the time of a negative high voltage pulse application. Furthermore, without applying special other means such as radio frequency (hereinafter abbreviated as “RF”) or a high-frequency power source such as a microwave, just applying a negative high voltage pulse to the layer, An ion implantation layer can be uniformly formed on the surface portion of the layer.

  In both methods (A) and (B), the pulse width when applying a negative high voltage pulse, that is, when implanting ions, is preferably 1 to 15 μsec. When the pulse width is in such a range, a transparent and uniform ion implantation layer can be formed more easily and efficiently.

  The applied voltage when generating plasma is preferably -1 kV to -50 kV, more preferably -1 kV to -30 kV, and particularly preferably -5 kV to -20 kV. When ion implantation is performed with an applied voltage greater than −1 kV, the ion implantation amount (dose amount) becomes insufficient, and desired performance cannot be obtained. On the other hand, if ion implantation is performed at a value smaller than −50 kV, the film is charged at the time of ion implantation, and defects such as coloring of the film are not preferable.

  When ions in plasma are implanted into the coating layer, a plasma ion implantation apparatus is used. As the plasma ion implantation apparatus, specifically, (a) a laminate in which a silicon-containing precursor layer is formed on a resin base material (hereinafter, also referred to as “layer to be ion-implanted”) has a negative high value. A device that uniformly surrounds the periphery of a layer to be ion-implanted by superimposing high-frequency power on a feedthrough to which a voltage pulse is applied, and attracts, implants, collides, and deposits ions in the plasma (Japanese Patent Laid-Open No. 2001-26887) (B) By providing an antenna in the chamber, generating a plasma by applying high-frequency power to reach the periphery of the layer to be ion-implanted, and then applying positive and negative pulses alternately to the layer to be ion-implanted, The layer to be ion-implanted is heated by attracting and colliding electrons in the plasma with a positive pulse, and the negative constant is applied to attract ions in the plasma while controlling the temperature by controlling the pulse constant. Injecting device (Japanese Patent Laid-Open No. 2001-156013), (c) Plasma is generated using an external electric field such as a high frequency power source such as a microwave, and a high voltage pulse is applied to attract and inject ions in the plasma And (d) a plasma ion implantation apparatus that implants ions in plasma generated only by an electric field generated by applying a high voltage pulse without using an external electric field.

  Among these, it is preferable to use the plasma ion implantation apparatus (c) or (d) because the processing operation is simple, the processing time can be greatly shortened, and it is suitable for continuous use.

[Resin substrate]
Specifically, as the resin base material according to the present invention, polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin , Polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin , A base material containing a thermoplastic resin such as an alicyclic modified polycarbonate resin, a fluorene ring modified polyester resin, or an acryloyl compound. These resin substrates can be used alone or in combination of two or more.

The resin substrate is preferably made of a material having heat resistance. Specifically, 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. The base material satisfies the requirements for use as a laminated film for electronic parts and displays. That is, when the gas barrier film according to the present invention is used for these applications, the gas barrier film may be exposed to a process at 150 ° C. or higher. In this case, when the coefficient of linear expansion of the base material in the gas barrier film exceeds 100 ppm / K, the substrate dimensions are not stable when the gas barrier film is passed through the temperature process as described above, and thermal expansion and contraction occur. Inconvenience that the shut-off performance deteriorates or a problem that it cannot withstand the heat process is likely to occur. If it is less than 15 ppm / K, the film may break like glass and the flexibility may deteriorate.

  The Tg and the linear expansion coefficient of the substrate can be adjusted with an additive or the like. More preferable specific examples of the thermoplastic resin that can be used as the substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic. Polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C, manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 190 ° C), cycloolefin copolymer (COC: Compound described in JP-A No. 2001-150584: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C. manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: JP In 2000-227603 Listed compound: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP 2000-227603 A: 205 ° C.), acryloyl compound (compound described in JP 2002-80616 A: 300 ° C.) And the like) (Tg is shown in parentheses).

  Moreover, the unstretched film may be sufficient as the resin base material mentioned above, and a stretched film may be sufficient as it. The resin substrate can be produced by a conventionally known general method. About the manufacturing method of these base materials, the matter described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately employed.

  The surface of the resin substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments may be combined as necessary. May go. The resin base material may be subjected to an easy adhesion treatment.

  The resin substrate may be a single layer or a laminated structure of two or more layers. When the resin base material has a laminated structure of two or more layers, the resin base materials may be the same type or different types.

  The thickness of the resin substrate according to the present invention (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 μm, and more preferably 20 to 150 μm.

[Layers with various functions]
In the gas barrier film of the present invention, layers having various functions can be provided.

(Anchor coat layer)
An anchor coat layer may be formed on the surface of the resin substrate on the side on which the silicon-containing layer is formed for the purpose of improving the adhesion between the resin substrate and the silicon-containing layer.

  As anchor coating agents used for the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, etc. are used alone Or in combination of two or more.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5.0 g / m ² (dry state).

  The anchor coat layer can also be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like. Alternatively, by forming an anchor coat layer as described in Japanese Patent Application Laid-Open No. 2004-314626, when an inorganic thin film is formed thereon by a vapor phase method, the gas generated from the substrate side is blocked to some extent. Thus, an anchor coat layer can be formed for the purpose of controlling the composition of the inorganic thin film.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Hard coat layer)
A hard coat layer may be provided on the surface (one side or both sides) of the resin substrate. Examples of the material contained in the hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more.

  The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray. A layer containing a cured product of the functional resin, that is, a hard coat layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable. You may use the commercially available resin base material in which the hard-coat layer is formed previously.

  The thickness of the hard coat layer is preferably from 0.1 to 15 μm, more preferably from 0.1 to 5 μm, from the viewpoint of smoothness and bending resistance.

(Smooth layer)
The gas barrier film of the present invention may have a smooth layer between the resin substrate and the silicon-containing layer. The smooth layer used in the present invention flattens the rough surface of the resin base material where protrusions and the like exist, or flattens the unevenness and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the resin base material. To be provided. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

  As the photosensitive material of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. Specifically, a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Co., Ltd., Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat-resistant epoxy resin), various silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd. Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

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

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

  The thickness of the smooth layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 7 μm, from the viewpoint of improving the heat resistance of the film and facilitating the balance adjustment of the optical properties of the film. Is preferred.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601: 2001, and the ten-point average roughness Rz is preferably 10 nm or more and 30 nm or less. If it is this range, even if it is a case where a gas barrier layer is apply | coated by the application type, even if it is a case where a coating means contacts the smooth layer surface by application methods, such as a wire bar and a wireless bar, applicability | paintability will be impaired. In addition, it is easy to smooth the unevenness after coating.

[Electronic device]
The gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, this invention provides the electronic device containing the gas barrier film of this invention, and an electronic device main body.

  Examples of the electronic device body used in the electronic device of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. be able to. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

  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.

[Example 1]
(1) Production of base material As a resin base material, a 100 μm-thick polyethylene terephthalate film (Lumirror (registered trademark) (U48), manufactured by Toray Industries, Inc.) with easy adhesion treatment on both surfaces was used. A clear hard coat layer having a thickness of 0.5 μm and having an antiblock function was formed on the surface of the resin substrate opposite to the surface on which the gas barrier layer was formed. That is, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied to a resin substrate so that the dry film thickness was 0.5 μm, dried at 80 ° C., and then high-pressure mercury in the air. Curing was performed using a lamp under the condition of an irradiation energy amount of 0.5 J / cm ² .

Next, a clear hard coat layer having a thickness of 2 μm was formed on the surface of the resin substrate on the side where the gas barrier layer is to be formed as follows. A UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a resin substrate so as to have a dry film thickness of 2 μm, then dried at 80 ° C., and then using a high-pressure mercury lamp in the air. Then, curing was performed under the condition of an irradiation energy amount of 0.5 J / cm ² . In this way, a resin base material with a hard coat layer was obtained. Hereinafter, in the examples and comparative examples, for convenience, this resin substrate with a hard coat layer is simply referred to as a resin substrate.

(2) Production of silicon precursor layer A magnetron sputtering apparatus is used on the resin substrate, a polycrystalline Si target is used as a target, and an oxygen flow rate is adjusted by DC sputtering using Ar and O ₂ as process gases. Then, a silicon oxide film having a thickness of 50 nm was formed.

(3) Formation of region (A) Subsequently, a gas barrier film was produced by ion plating using nitrogen (N ₂ ) as a plasma generation gas.

  Ion plating was performed as follows.

The silicon oxide film formed above was mounted in the chamber of a hollow cathode type ion plating apparatus so as to be a film formation surface. Next, the pressure in the chamber was reduced to an ultimate vacuum of 1 × 10 ⁻⁵ Torr by an oil rotary pump and an oil diffusion pump. The film was heated at 60 ° C. in advance by an IR heater before film formation. The degree of vacuum at this time was 1 × 10 ⁻⁴ Torr. Next, the pressure in the chamber was reduced to an ultimate vacuum of 1 × 10 ⁻⁵ Torr by an oil rotary pump and an oil diffusion pump.

Further, Nb ₂ O ₅ was prepared as an evaporation source and mounted on the anode (Heath). By controlling the degree of opening and closing of the valve between the vacuum pump and the chamber, a hollow cathode type plasma gun introduced with nitrogen gas is used while maintaining the pressure in the chamber at the time of film formation at 1 × 10 ⁻³ Torr. The evaporation source on the anode (Haas) is focused and irradiated to evaporate, and the evaporated molecules are ionized by the high-density plasma to form a thin film of niobium oxide (Nb ₂ O ₅ ) on the silicon oxide film ( A film thickness of 20 μm) was formed. The applied power to the substrate during ion plating was 300 W.

In this way, a gas barrier film was obtained in which Nb ₂ O ₅ was formed on the silicon oxide film and a region (A) having a thickness of 4 nm was formed in the silicon-containing layer. At this time, the gas barrier film had a structure of resin base material-silicon-containing layer-Nb ₂ O ₅ layer, and the region (A) was formed in the vicinity of the interface with the Nb ₂ O ₅ layer in the silicon-containing layer. .

[Example 2]
In Example 1, instead of forming a silicon oxide film (silicon-containing precursor layer), gas barrier properties were obtained in the same manner as in Example 1 except that the following silicon-containing precursor layer was formed on the resin substrate. A film was prepared.

(2) Production of silicon-containing precursor layer On the produced resin substrate, the produced intermediate layer-coated base is formed by plasma CVD using the facing roll type roll-to-roll vacuum film forming apparatus of FIG. The material was set in the plasma CVD film forming apparatus 31 and conveyed. Next, a magnetic field is applied between the film forming roller 39 and the film forming roller 40, and electric power is supplied to the film forming roller 39 and the film forming roller 40, respectively. Was discharged to generate plasma. Thereafter, a film forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (also functioning as a discharge gas) as a reaction gas) is supplied to the formed discharge region to form a film. A silicon-containing precursor layer having a film thickness of 150 nm was formed on the bleed-out preventing layer of the substrate for use under the following film forming conditions.

(Plasma CVD conditions)
・ Supply amount of source gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute),
The supply amount of Reaction gas _{(O 2):} 500sccm,
-Degree of vacuum in the vacuum chamber: 3 Pa,
-Applied power from the power source for plasma generation: 0.8 kW,
-Frequency of power source for plasma generation: 70 kHz,
-Film conveyance speed: 0.8 m / min.

In this way, a gas barrier film was obtained in which Nb ₂ O ₅ was formed on the silicon-containing precursor layer and a region (A) having a thickness of 4 nm was formed on the silicon-containing layer. At this time, the gas barrier film had a structure of resin base material-silicon-containing layer-Nb ₂ O ₅ layer, and the region (A) was formed in the vicinity of the interface with the Nb ₂ O ₅ layer in the silicon-containing layer. .

[Example 3]
In Example 1, instead of forming a silicon oxide film (silicon-containing precursor layer), a gas barrier film was formed in the same manner as in Example 1 except that a polysilazane-derived layer was formed on a resin substrate as described below. Produced.

(2) Preparation of polysilazane-derived layer A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials, NN120-20), and an amine catalyst (N, N, N ′, N′-tetramethyl-) A perhydropolysilazane 20% by mass dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) containing 1,6-diaminohexane (TMDAH) is mixed at a ratio of 4: 1 (mass ratio). Further, for the purpose of adjusting the dry film thickness, it was appropriately diluted with dibutyl ether to prepare a coating solution 1 having a solid content of 4.8% by mass.

  On the resin base material, the coating liquid 1 was applied to a dry film thickness of 150 nm by a spin coating method, and dried at 80 ° C. for 2 minutes.

In this way, a gas barrier film was obtained in which Nb ₂ O ₅ was formed on the polysilazane-derived layer and a region (A) having a thickness of 10 nm was formed in the silicon-containing layer. At this time, the gas barrier film had a structure of resin base material-silicon-containing layer-Nb ₂ O ₅ layer, and the region (A) was formed in the vicinity of the interface with the Nb ₂ O ₅ layer in the silicon-containing layer. .

[Example 4]
In Example 3, a gas barrier film was obtained in the same manner as in Example 3 except that the applied power to the substrate during ion plating was 1500 W.

In this way, a gas barrier film was obtained in which Nb ₂ O ₅ was formed on the polysilazane-derived layer and a region (A) having a thickness of 14 nm was formed in the silicon-containing layer. At this time, the gas barrier film had a structure of resin base material-silicon-containing layer-Nb ₂ O ₅ layer, and the region (A) was formed in the vicinity of the interface with the Nb ₂ O ₅ layer in the silicon-containing layer. .

[Example 5]
In Example 3, a gas barrier film was obtained in the same manner as in Example 3 except that the substrate temperature for preheating the resin substrate on which the polysilazane-derived layer was formed was changed to 100 ° C.

In this way, a gas barrier film was obtained in which Nb ₂ O ₅ was formed on the polysilazane-derived layer and a region (A) having a thickness of 12 nm was formed in the silicon-containing layer. At this time, the gas barrier film had a structure of resin base material-silicon-containing layer-Nb ₂ O ₅ layer, and the region (A) was formed in the vicinity of the interface with the Nb ₂ O ₅ layer in the silicon-containing layer. .

[Example 6]
In Example 4, a gas barrier film was obtained in the same manner as in Example 4 except that the substrate temperature for preheating the resin substrate on which the polysilazane-derived layer was formed was changed to 100 ° C.

In this way, a gas barrier film was obtained in which Nb ₂ O ₅ was formed on the polysilazane-derived layer and a region (A) having a thickness of 16 nm was formed in the silicon-containing layer. At this time, the gas barrier film had a structure of resin base material-silicon-containing layer-Nb ₂ O ₅ layer, and the region (A) was formed in the vicinity of the interface with the Nb ₂ O ₅ layer in the silicon-containing layer. .

[Example 7]
In Example 6, a DC sputtering using a magnetron sputtering apparatus on a niobium oxide (Nb ₂ O ₅ ) layer, an oxygen-deficient Nb ₂ O ₅ target as a target, and Ar and O ₂ as process gases. Thus, Nb ₂ O ₅ was formed to a film thickness of 15 nm.

In this way, a gas barrier film was obtained in which Nb ₂ O ₅ was formed on the niobium oxide (Nb ₂ O ₅ ) layer and a region (A) having a thickness of 16 nm was formed in the silicon-containing layer. At this time, the gas barrier film has a structure of resin base material-silicon-containing layer-Nb ₂ O ₅ layer-Nb ₂ O ₅ layer, and the region (A) is Nb ₂ adjacent to the silicon-containing layer in the silicon-containing layer. It was formed near the interface with the O ₅ layer.

[Example 8]
In Example 3, a gas barrier film was obtained in the same manner as in Example 3 except that the polysilazane-derived layer was formed as follows. In this way, Nb ₂ O ₅ was formed on the polysilazane-derived layer to obtain a gas barrier film in which a region (A) having a thickness of 12 nm was formed on the silicon-containing layer. At this time, the gas barrier film had a structure of resin base material-silicon-containing layer-Nb ₂ O ₅ layer, and the region (A) was formed in the vicinity of the interface with the Nb ₂ O ₅ layer in the silicon-containing layer. .

(2) Preparation of polysilazane-derived layer A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials, NN120-20), and an amine catalyst (N, N, N ′, N′-tetramethyl-) A perhydropolysilazane 20% by mass dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) containing 1,6-diaminohexane (TMDAH) is mixed at a ratio of 4: 1 (mass ratio). Further, for the purpose of adjusting the dry film thickness, it was appropriately diluted with dibutyl ether to prepare a coating solution 1 having a solid content of 4.8% by mass.

  On the resin base material, the coating liquid 1 was applied to a dry film thickness of 150 nm by a spin coating method, and dried at 80 ° C. for 2 minutes.

Next, the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment of 500 mJ / cm ² using a vacuum ultraviolet ray irradiation apparatus having an Xe excimer lamp having a wavelength of 172 nm, thereby forming a polysilazane-derived layer. At this time, the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The stage temperature for installing the sample was set to 80 ° C.

[Comparative Example 1]
(1) Base material The resin base material produced in Example 1 was used.

(2) Formation of silicon oxide film On the above resin substrate, a magnetron sputtering apparatus is used, a polycrystalline Si target is used as a target, and an oxygen flow rate is adjusted by DC sputtering using Ar and O ₂ as process gases. Then, a silicon oxide film having a thickness of 50 nm was formed.

A gas barrier property is obtained by forming a silicon oxide film (SiO ₂ ) on a resin base material by DC sputtering using a magnetron sputtering apparatus, a polycrystalline Si target as a target, and Ar and O ₂ as process gases. A film was prepared.

[Comparative Example 2]
(1) Base material The resin base material produced in Example 1 was used.

(2) Formation of silicon-containing precursor layer A CVD layer was formed on the resin substrate using the apparatus shown in FIG.

[Formation of CVD layer]
Supply amount of raw material gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute, 0 ° C., 1 atm standard)
Supply amount of oxygen gas: 150 sccm (0 ° C., 1 atm standard)
Degree of vacuum in the vacuum chamber: 1.5 Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film conveyance speed: 5.0 m / min × 2 passes [Comparative Example 3]
In Example 3, a gas barrier film was obtained in the same manner as in Example 3 except that after the polysilazane-derived layer was formed on the resin substrate, Ar ions were ion-implanted as described below.

(Plasma ion implantation system)
RF power source: JEOL Ltd., model number “RF” 56000
High-voltage pulse power supply: “PV-3-HSHV-0835” manufactured by Kurita Manufacturing Co., Ltd.
(Plasma ion implantation conditions)
Plasma generation gas: Ar
Gas flow rate: 100sccm
Duty ratio: 0.5%
Applied voltage: -6 kV
RF power supply: frequency 13.56 MHz, applied power 1000 W
Chamber internal pressure: 0.2Pa
Pulse width: 5μsec
Processing time (ion implantation time): 200 seconds [Comparative Example 4]
In Comparative Example 3, a gas barrier film was obtained in the same manner as in Comparative Example 3 except that the polysilazane-derived layer was formed as follows.

(2) Preparation of polysilazane-derived layer A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials, NN120-20), and an amine catalyst (N, N, N ′, N′-tetramethyl-) A perhydropolysilazane 20% by mass dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) containing 1,6-diaminohexane (TMDAH) is mixed at a ratio of 4: 1 (mass ratio). Further, for the purpose of adjusting the dry film thickness, it was appropriately diluted with dibutyl ether to prepare a coating solution 1 having a solid content of 4.8% by mass.

  On the resin base material, the coating liquid 1 was applied to a dry film thickness of 150 nm by a spin coating method, and dried at 80 ° C. for 2 minutes.

Next, a polysilazane-derived layer was formed by subjecting the dried coating film to a vacuum ultraviolet irradiation treatment of ³ J / cm ² using a vacuum ultraviolet irradiation apparatus having an Xe excimer lamp having a wavelength of 172 nm. At this time, the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The stage temperature for installing the sample was set to 80 ° C.

[Comparative Example 5]
In Comparative Example 1, a silicon oxide film (SiO ₂ ) was formed on the resin base material by further doubling the oxygen flow rate during film formation. Next, the following film formation was performed.

A magnetron sputtering apparatus is used, an oxygen-deficient Nb ₂ O ₅ target is used as a target, and Nb ₂ O with a film thickness of 15 nm is formed on the silicon oxide film (SiO ₂ ) by DC sputtering using Ar and O ₂ as process gases. ₅ was deposited. At this time, the oxygen partial pressure in the process gas was adjusted to form Nb ₂ O ₅ .

  Thus, the niobium oxide layer was formed by sputtering on the silicon oxide film.

[Comparative Example 6]
In Comparative Example 2, a silicon-containing precursor layer was formed on the resin substrate in the same manner as in Comparative Example 2, except that the oxygen flow rate during CVD film formation was doubled. Next, as in Comparative Example 5, a niobium oxide layer was formed by sputtering on the silicon oxide film.
(Evaluation method)
<Ca method evaluation of gas barrier film>
After the surface of the gas barrier film was UV washed, a thermosetting sheet-like adhesive (epoxy resin) was bonded to the gas barrier layer surface as a sealing resin layer with a thickness of 20 μm. This was punched out to a size of 50 mm × 50 mm, then placed in a glove box and dried for 24 hours.

One side of a 50 mm × 50 mm non-alkali glass plate (thickness 0.7 mm) was UV cleaned. Ca was vapor-deposited by the size of 20 mm x 20 mm through the mask in the center of the glass plate using the vacuum vapor deposition apparatus made from an EILS technology. The thickness of Ca was 80 nm. The glass plate on which Ca was vapor-deposited was taken out into the glove box, and was placed so that the sealing resin layer surface of the gas barrier film to which the sealing resin layer was bonded and the Ca vapor-deposited surface of the glass plate were in contact with each other, and were adhered by vacuum lamination. At this time, heating at 110 ° C. was performed. Furthermore, the adhered sample is placed on a hot plate set at 110 ° C. with the glass plate facing down, and cured for 30 minutes,
An evaluation sample was prepared.

  According to the following measuring method, the water vapor permeability of each gas barrier film was evaluated.

  The sample for evaluation produced as described above was stored in an environment of 85 ° C. and 85% RH. The corrosion area ratio was measured after 24 hours and 100 hours in an 85 ° C. and 85% RH environment and evaluated based on the following evaluation criteria.

5: Corrosion area ratio after 100 hours is less than 10% 4: Corrosion area ratio after 100 hours is 10% or more and less than 20% 3: Corrosion area ratio after 24 hours is 10% or more and less than 20%, Corrosion area ratio after 20 hours or more and less than 30% 2: Corrosion area ratio after 24 hours is 10% or more and less than 20%, and corrosion area ratio after 100 hours is 30% or more 1: After 24 hours Corrosion area ratio is 30% or more Manufacturing conditions of gas barrier films of each example and comparative example, maximum value of left side of formula (1), and region (A), region (A) film thickness, region The maximum and minimum values in (A) and the evaluation results are shown in Table 1 below.

  As described in the above table, the gas barrier films of Examples 1 to 7 had high durability under high temperature and high humidity conditions over a long period of time.

10 Gas barrier film,
11 resin base material,
12 silicon-containing layer,
13 a layer containing a transition metal compound,
20 ion plating device,
21 vacuum chamber,
22 Hollow cathode (hollow cathode) electron gun,
23 anode,
24 Permanent magnets arranged in the anode,
25 Laminated body of resin base material and silicon-containing precursor layer 26 heater,
27 Evaporation source,
28 RF power supply,
29 Vacuum exhaust system,
31 plasma CVD equipment,
32 Feeding roller,
33, 34, 35, 36 transport rollers,
39, 40 Deposition roller,
41 Gas supply port,
42 Power supply for plasma generation,
43, 44 Magnetic field generator,
45 Take-up roller.

Claims (5)

A gas barrier film having a resin substrate and a silicon-containing layer,
In the atomic composition distribution profile obtained when the XPS composition analysis is performed in the thickness direction, the silicon-containing layer has a region (A) that satisfies the following relational expression (1) when the composition is represented by SiMxNyOz. A gas barrier film in which the region (A) is formed by an ion implantation method or an ion plating method.
  The gas barrier film according to claim 1, wherein the silicon-containing layer is obtained by applying and drying a coating liquid containing polysilazane.   The gas barrier film according to claim 2, wherein the silicon-containing layer is obtained by irradiating a vacuum ultraviolet ray onto a coating film obtained by applying and drying a coating liquid containing polysilazane.   The gas barrier film according to any one of claims 1 to 3, wherein the transition metal is a metal having a lower oxidation-reduction potential than silicon. The gas barrier film according to claim 1, wherein the silicon-containing layer has a region (B) where (4 + Σax) − (3y + 2z)> 1.