WO2016136841A1 - Gas barrier film - Google Patents

Abstract

Provided is a gas barrier film having excellent durability in high-temperature, high-humidity environments. This gas barrier film comprises, on a resin base, a layer (A) that contains a transition metal compound and is formed by a vapor phase film formation method, and a gas barrier layer (B) that is in contact with the layer (A) and is formed by applying vacuum ultraviolet light to a coating film which is obtained by applying and drying a coating liquid containing a polysilazane. The amount of irradiation energy from the vacuum ultraviolet light on the surface of the coating film is 1.0 J/cm² or more.

Description

Gas barrier film

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.

Generally, a gas barrier film is manufactured 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, in WO2011 / 122547 (US Patent Application Publication No. 2014/374665), a molded body having a layer obtained by implanting hydrocarbon compound ions into a layer containing a polysilazane compound. It is disclosed. In Japanese translations of PCT publication No. 2009-503157 (US Patent Application Publication No. 2010/1666977), a solution containing polysilazane and a catalyst is applied onto a substrate, and then the solvent is removed to form a polysilazane layer. A method of forming a gas barrier layer on a substrate by irradiating the polysilazane layer with VUV radiation containing a wavelength component of less than 230 nm and UV radiation containing a wavelength component of 230 to 300 nm in an atmosphere containing water vapor Is disclosed. Furthermore, JP 2009-255040 A discloses a first step in which a polysilazane is coated on a resin substrate to form a polymer film having a thickness of 250 nm or less, and the formed polymer film is irradiated with vacuum ultraviolet light. And a third step of repeating the first step and the second step to form a film on the film formed in the second step, and a method for producing a flexible gas barrier film. It is disclosed.

However, a gas barrier layer formed by modifying polysilazane described in International Publication No. 2011/122547, JP-T 2009-503157, and JP-A 2009-255040 with excimer light is 40 Although the gas barrier property at a low temperature up to about 0 ° C. is good, it was found that the gas barrier property decreases with time in a very severe environment of high temperature and high humidity such as 80 ° C. and 85% RH.

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.

Therefore, an object of the present invention is to provide a gas barrier film having excellent durability in a high temperature and high humidity environment.

The present inventor has intensively studied to solve the above problems. As a result, on the resin substrate, a layer (A) containing a transition metal compound formed by a vapor deposition method and a coating liquid containing polysilazane in contact with the layer (A) and drying are applied and dried. The gas barrier layer (B) formed by applying vacuum ultraviolet rays with an irradiation energy amount of 1.0 J / cm ² or more to the coating film obtained in the above, finds that the above problem is solved, The present invention has been completed.

That is, the present invention applies a layer (A) containing a transition metal compound formed by a vapor deposition method on a resin substrate, and a coating liquid containing polysilazane in contact with the layer (A). And a gas barrier layer (B) formed by applying vacuum ultraviolet rays to the coating film obtained by drying, and the irradiation energy amount of the vacuum ultraviolet rays on the surface of the coating film is 1.0 J / cm ² or more It is a gas barrier film.

FIG. 1 is a schematic cross-sectional view showing a gas barrier film according to an embodiment of the present invention. In FIG. 1, 10 is a gas barrier film, 11 is a substrate, 12 is a layer (B), and 13 is a layer (A). FIG. 2 is a schematic sectional view showing a gas barrier film according to another embodiment of the present invention. In FIG. 2, 10 is a gas barrier film, 11 is a substrate, 12 is a layer (B), and 13 is a layer (A). FIG. 3 is a schematic cross-sectional view of the vacuum ultraviolet irradiation apparatus used in the examples. In FIG. 3, 1 is an apparatus chamber, 2 is a Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, 3 is an excimer lamp holder that also serves as an external electrode, 4 is a sample stage, and 5 is a polysilazane compound coating layer. 6 is a light shielding plate.

In the present invention, a layer (A) (hereinafter also simply referred to as layer (A)) containing a transition metal compound formed by a vapor deposition method on a resin substrate is in contact with the layer (A). A gas barrier layer (B) (hereinafter, also simply referred to as layer (B)) formed by irradiating vacuum ultraviolet rays on a coating film obtained by applying and drying a coating liquid containing polysilazane, It is a gas barrier film whose irradiation energy amount of the said vacuum ultraviolet rays in the surface of a coating film is 1.0 J / cm < ² > or more. The gas barrier film of the present invention having such a configuration is excellent in durability in a high temperature and high humidity environment.

In another embodiment of the present invention, a layer (A) containing a transition metal compound is formed on a resin substrate by a vapor deposition method, and the layer (A) is in contact with the layer (A). The coating film obtained by applying and drying a coating solution containing polysilazane is irradiated with vacuum ultraviolet rays to form a gas barrier layer (B), or a coating solution containing polysilazane is applied on a resin substrate A layer containing a transition metal compound by a vapor deposition method so as to form a gas barrier layer (B) by irradiating a vacuum ultraviolet ray onto a coating film obtained by drying and forming a gas barrier layer (B) on the layer (B). (A) is formed, and the irradiation energy amount of vacuum ultraviolet rays on the surface of the coating film is 1.0 J / cm ² or more.

The details of the reason why the above-described effect can be obtained by the gas barrier film of the present invention are unknown, but the following mechanism is conceivable. The following mechanism is based on speculation, and the present invention is not limited to the following mechanism.

In the layer (B), silicon oxynitride is formed by irradiating the coating film obtained by applying and drying a coating liquid containing polysilazane with vacuum ultraviolet rays, thereby exhibiting gas barrier properties. Unlike the case where it is formed by a vapor phase film forming method, by applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane, particles such as It is possible to form a gas barrier layer with almost no foreign matter and very few defects. However, this gas barrier layer is not completely stable against oxidation, and may be gradually oxidized in a high-temperature and high-humidity environment to lower the gas barrier property.

On the other hand, in the gas barrier film of the present invention, the layer (layer (A)) adjacent to the gas barrier layer (layer (B)) obtained by irradiating polysilazane with vacuum ultraviolet rays contains a transition metal compound. Since the layer (A) is more easily oxidized than the layer (B), the oxidation of the layer (B) is suppressed when the layer (A) is oxidized first, and the durability in a high-temperature and high-humidity environment is excellent. It is considered a thing.

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 the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted.

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 base material 11, a layer (B) 12, and a layer (A) 13 are arranged in this order. FIG. 2 is a schematic cross-sectional view showing a gas barrier film according to another embodiment of the present invention. In the gas barrier film 10 of FIG. 2, a base material 11, a layer (A) 13 and a layer (B) 12 are arranged in this order. That is, as long as the layer (A) and the layer (B) are disposed adjacent to each other, even if the layer (A) and the layer (B) are in this order from the base material side, the layer (B) and the layer (A) It may be in order. Moreover, not only the form in which the layer (A) and the layer (B) are formed on one surface of the substrate, the layer (A) and the layer (B) may be formed on both surfaces of the substrate. Furthermore, another layer may be disposed between the substrate and each layer or on each layer. That is, “on the resin base material” is not limited to just above the resin base material.

By arranging the layer (A) on the layer (B) on the surface facing the substrate, the layer (A) is more easily oxidized, and the protection of the layer (B) by the layer (A) is more prominently exhibited. Therefore, it is preferable to arrange the base material, the layer (B), and the layer (A) in this order.

[(A) Layer containing transition metal compound]
The gas barrier film of the present invention has a layer (A) containing a transition metal compound formed by a vapor phase film forming method. The layer (A) is more easily electrochemically oxidized than the layer (B), and suppresses the oxidation of the layer (B).

The transition metal compound contained in the layer (A) 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 layer (B), 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 layer (A) preferably contains a metal oxide MO _x1 where x1 <x2, where M is the transition metal and MO _x2 is the stoichiometrically obtained transition metal oxide. By including such a metal oxide, the gas barrier performance of the gas barrier film is improved, and high gas barrier performance is maintained even under high temperature and high humidity conditions. By including the metal oxide MO _x1 where x1 <x2, there is a region with a lower degree of oxidation than the stoichiometric degree of oxidation, that is, a region with room for further oxidation, which is higher. It is thought that gas barrier performance is exhibited.

For example, taking the oxide of Nb (niobium) as an example, the Nb stoichiometric oxide is niobium pentoxide, which is NbO _2.5 , so x2 = 2.5. is there. Nb can take the composition of niobium trioxide, but x2 in the present invention means x2 of a stoichiometric compound having the highest degree of oxidation. The inclusion of the metal oxide MO _x1 where x1 <x2 means that when a composition profile in the thickness direction is measured by a composition analysis method such as XPS, a measurement point where x1 <x2 is obtained, in the case of Nb Means that a measurement point where x1 <2.5 is obtained. Even when (A) contains a plurality of kinds of metals, the stoichiometric x2 can be calculated from the ratio of each metal and the total thereof.

Expressing the relationship of x1 <x2 as an index of the degree of oxidation as an x1 / x2 ratio, the x1 / x2 ratio is preferably 0.99 or less because the gas barrier performance under high temperature and high humidity is further improved. It is more preferably 0.9 or less, and further preferably 0.8 or less. Further, the minimum value of the x1 / x2 ratio is preferably 0.99 or less, more preferably 0.9 or less, and further preferably 0.8 or less. The smaller the x1 / x2 ratio, the higher the oxidation suppression effect, but the higher the absorption with visible light. Accordingly, when used in applications where transparency is desired, it is preferably 0.2 or more. .3 or more is more preferable. That is, the minimum value of the x1 / x2 ratio is preferably 0.2 or more, and more preferably 0.3 or more.

The ratio in the thickness direction of the layer (A) in the region where x1 / x2 <1 is preferably 1 to 100% with respect to the thickness of the region (A) from the viewpoint of barrier properties. 100% is more preferable, and 50 to 100% is more preferable.

The x1 / x2 ratio can be adjusted by using a metal or a transition metal oxide that is stoichiometrically deficient in oxygen as a target when the layer (A) is formed by sputtering. This can be done by appropriately adjusting the amount of oxygen to be introduced.

x1 can be determined by the atomic ratio of O to M using XPS analysis in the thickness direction. If the minimum value of x1 is x1 <x2, it can be said that the metal oxide MO _x1 where x1 <x2 is included.

<< XPS analysis conditions >>
・ Equipment: ULVAC-PHI QUANTERASXM
・ X-ray source: Monochromatic Al-Kα
・ Measurement area: Si2p, C1s, N1s, O1s, etc., set by a regular method according to the metal to be measured ・ Sputtering ion: Ar (2 keV)
Depth profile: repeats measurement after sputtering for a certain time. In one measurement, the sputtering time is adjusted so that the thickness is about 2.5 nm in terms of SiO _2.・ Quantification: The background is obtained by the Shirley method, and the relative sensitivity coefficient method is calculated from the obtained peak area. And quantified. Data processing uses MultiPak manufactured by ULVAC-PHI.

A transition metal atom 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, Cu, Zn, Y, Zr, Nb, and 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.

Among these, the transition metal in the transition metal compound is preferably a metal having a lower redox potential than silicon. By forming a layer containing a transition metal compound having a lower oxidation-reduction potential than silicon, better barrier properties can be obtained. Specific examples of the metal having a lower redox potential than silicon include, for example, niobium (Nb), tantalum (Ta), vanadium (V), zirconium (Zr), titanium (Ti), hafnium (Hf), yttrium (Y ), Lanthanum (La), cerium (Ce) 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 oxidation suppressing effect on the polysilazane-modified barrier layer. That is, a preferred embodiment of the present invention is a gas barrier film in which the transition metal is at least one metal selected from the group consisting of vanadium, niobium and tantalum. 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 standard redox potential and x2 of major metals are shown in the table below.

The content of the transition metal compound in the layer (A) 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 layer (A). 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 layer (A) is Most preferably, it comprises a transition metal compound.

The formation method of the layer (A) is a vapor phase film formation method from the viewpoint of easy adjustment of the composition ratio between the metal element and oxygen. The vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, and ion plating, plasma CVD (chemical vapor deposition), and ALD (Atomic Layer Deposition). Chemical vapor deposition methods such as Among them, it is preferable to form by sputtering since film formation is possible without damaging the lower layer and high productivity is obtained.

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 transition metal oxide thin film can be formed by using a transition metal for the target and further introducing oxygen into the process gas. Alternatively, when performing DC sputtering or DMS sputtering, an oxygen-deficient transition metal oxide may be used as the target. In the case of forming a film by RF (high frequency) sputtering, a transition metal 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 oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a transition metal compound thin film such as a transition metal oxide, nitride, nitride oxide, or carbonate can be formed. 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.

Among these, a sputtering method using a transition metal oxide as a target is preferable because it has a higher film formation rate and higher productivity. At this time, an oxygen-deficient transition metal oxide may be used as the transition metal oxide.

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

Since the layer (A) is considered to be a layer having a function of suppressing the oxidation of the layer (B) and maintaining the gas barrier property, the gas barrier property is not necessarily required. Therefore, even if the layer (A) is a relatively thin layer, the effect can be exhibited. Specifically, in the case of the layer structure of the base material-layer (B) -layer (A), the thickness of the layer (A) (the total thickness in the case of a laminated structure of two or more layers) is the barrier From the viewpoint of in-plane uniformity of the property, the thickness is preferably 1 to 200 nm, more preferably 2 to 100 nm, and further preferably 3 to 50 nm. In particular, when the thickness is 50 nm or less, the productivity of forming the layer (A) is further improved. Further, in the case of the layer structure of the base material-layer (A) -layer (B), the thickness of the layer (A) (the total thickness in the case of a laminated structure of two or more layers) is the barrier property surface. From the viewpoint of internal uniformity, the thickness is preferably 1 to 200 nm, more preferably 2 to 150 nm, and still more preferably 20 to 150 nm.

[(B) Gas barrier layer]
The gas barrier layer (B) according to the present invention is formed by irradiating a coating film obtained by applying and drying a coating liquid containing polysilazane with vacuum ultraviolet rays. The layer (B) exhibits gas barrier properties by irradiation with vacuum ultraviolet rays. Further, unlike the case where the film is formed by the vapor deposition method, foreign substances such as particles are not mixed at the time of film formation, so that the gas barrier layer has very few defects.

The layer (B) may be a single layer or a laminated structure of two or more layers.

The thickness of each layer (B) is preferably 10 to 300 nm from the viewpoint of gas barrier performance. In the case of a laminated structure of two or more layers, the total thickness is preferably 10 to 1000 nm from the viewpoint of suppressing cracks. In the case of the layer structure of substrate-layer (B) -layer (A), the thickness per layer of the layer (B) is more preferably 50 to 300 nm from the viewpoint of gas barrier performance, It is more preferably from ˜300 nm, most preferably from 200 to 300 nm. Furthermore, in the case of the layer structure of substrate-layer (A) -layer (B), the thickness of the layer (B) formed in contact with the layer (A) is preferably 5 nm to 200 nm, It is more preferably 10 nm to 150 nm, and further preferably 20 nm to 120 nm. In the case of the base material-layer (A) -layer (B) layer structure, it is preferable that a modified region of polysilazane is formed on the interface side between the layer (A) and the layer (B). For this reason, in the case of the vacuum ultraviolet irradiation treatment, it is preferable that the vacuum ultraviolet light is transmitted to the vicinity of the layer (A) / layer (B) interface. This is because the polysilazane modified region exhibiting barrier properties is formed in contact with the layer (A), thereby improving the oxidation resistance. Since the vacuum ultraviolet light is absorbed by the polysilazane layer, it is preferable that the polysilazane coating layer is relatively thin so that the vacuum ultraviolet light is transmitted to the vicinity of the (A) / (B) interface. Therefore, in the case of the base material-layer (A) -layer (B) layer structure, the preferred range is thinner than the base material-layer (B) -layer (A) layer structure. Become.

The thickness of the layer (B) can be measured by TEM observation.

The layer (B) is formed by irradiating a coating film obtained by applying and drying a coating liquid containing polysilazane with vacuum ultraviolet rays. Polysilazane is a polymer having a silicon-nitrogen bond, such as SiO ₂ , Si ₃ N ₄ having a bond such as Si—N, Si—H, or N—H, and ceramics such as both intermediate solid solutions SiO _x N _y. It is a precursor inorganic polymer.

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. The number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), and there are liquid or solid substances, and the state varies depending on the molecular weight.

Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as it is as the coating solution for forming the layer (B). Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. Is mentioned. These polysilazane solutions can be used alone or in combination of two or more.

Other examples of the polysilazane that can be used in the present invention include, but are not limited to, for example, a silicon alkoxide-added polysilazane obtained by reacting the polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-23827), and a glycidol reaction. 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 obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal obtained by adding metal fine particles Fine particle added policy Zhang such (JP-A-7-196986), and a polysilazane ceramic at low temperatures.

In the case of using polysilazane, the content of polysilazane in the layer (B) before application of vacuum ultraviolet light can be 100% by mass when the total mass of the layer (B) is 100% by mass. Moreover, when the layer (B) before applying the vacuum ultraviolet ray contains a material other than polysilazane, the content of polysilazane in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass. More preferably, it is 70 mass% or less and 95 mass% or less.

(Layer (B) forming coating solution (coating solution containing polysilazane))
The solvent for preparing the coating liquid for forming the layer (B) is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups (for example, hydroxyl group, or easily reacting with polysilazane). An organic solvent that does not contain an amine group and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable. 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 coating solution for forming the layer (B) is not particularly limited and varies depending on the layer thickness and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass.

The coating liquid for forming the layer (B) preferably contains a catalyst in order to promote reforming. 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, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, 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 setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.

In the coating liquid for forming the layer (B), the following additives can be used 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 the layer (B) forming coating solution)
As a method of applying the layer (B) 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 applying the coating solution, 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 layer (B) can be obtained. The remaining solvent can be removed later.

The drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C. 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 coating solution for forming the layer (B) 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 preferred dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), the more preferred dew point temperature is −5 ° C. or less (temperature 25 ° C./humidity 10%), and the time maintained is the film of layer (B) It is preferable to set appropriately depending on the thickness. Specifically, it is preferable that the dew point temperature is −5 ° C. or lower and the maintaining 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 layer (B) converted to silanol by removing water before or during the reforming treatment.

<Vacuum UV irradiation>
Subsequently, the coating film formed as described above is irradiated with vacuum ultraviolet rays to carry out a conversion reaction of polysilazane to silicon oxynitride or the like. That is, the coating film obtained by applying and drying a coating solution containing polysilazane is modified into an inorganic thin film that can exhibit gas barrier properties by irradiation with vacuum ultraviolet rays. The coating film modified by such vacuum ultraviolet irradiation treatment is also referred to as a polysilazane modified layer.

UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the 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 layer (B) used.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
The modification by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms only to 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.

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

¡Excimer lamps have high light generation efficiency and can be lit 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 irradiation with vacuum ultraviolet rays 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 1000 to 4000 ppm by volume.

The gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas 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 the vacuum ultraviolet irradiation step, the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane coating is preferably 1 mW / cm ² to 10 W / cm ² , more preferably 30 mW / cm ² to 200 mW / cm ^{2. preferably,} further preferably at 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.

In the present invention, the irradiation energy amount (irradiation amount) of vacuum ultraviolet rays on the surface of the coating film is 1.0 J / cm ² or more. When the irradiation energy amount is less than 1.0 J / cm ² , the storage stability of the gas barrier property of the layer (B) is lowered, and the gas barrier property during storage under high temperature and high humidity conditions is significantly lowered. The irradiation energy amount is preferably 1.5 J / cm ² or more from the viewpoint of production stability (a property in which the gas barrier performance does not decrease or is low even in a storage environment after forming the modified layer), 2.0 J / cm ² or more, and further preferably 2.5 J / cm ² or more, 4.0 J / cm ² or more is particularly preferable. On the other hand, the upper limit value of the irradiation energy amount is not particularly limited, it is preferably 10.0J / cm ² or less, and more preferably 8.0J / cm ² or less. If it is this range, generation | occurrence | production of the crack by excessive reforming and the thermal deformation of a 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.

[Resin substrate]
Specific examples of the resin substrate according to the present invention include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, and 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 Examples include base materials containing thermoplastic resins such as resins, alicyclic modified polycarbonate resins, fluorene ring modified polyester resins, and acryloyl compounds. These resin substrates can be used alone or in combination of two or more.

The resin base material is preferably made of a heat-resistant material. 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 linear expansion coefficient of the substrate can be adjusted by additives. 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).

Since the gas barrier film according to the present invention is used as an electronic device such as an organic EL element, the resin 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, 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 plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.

Further, the resin base material listed above may be an unstretched film or a stretched film. The resin substrate can be produced by a conventionally known general method. The method for producing these base materials is described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 (paragraphs “0056” to “0060” of US Patent Application Publication No. 2014/106151). Can be adopted as appropriate.

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 base material 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)
For the purpose of improving the adhesion between the resin substrate and the layer (A) or the layer (B), the anchor is formed on the surface of the resin substrate on the side where the layer (A) and the layer (B) according to the present invention are formed. A coat layer may be formed.

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).

Also, the anchor coat layer can 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 is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or 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. Specific examples of the active energy ray-curable resin include photosensitive materials for the smooth layer described below. 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 0.1 to 15 μm and more preferably 1 to 5 μm from the viewpoint of smoothness and bending resistance.

(Smooth layer)
In the gas barrier film of this invention, you may have a smooth layer between a resin base material and a layer (A) or a layer (B). 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 coat 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 Coat, 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, 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 material 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 defined by JIS B 0601: 2001, and the 10-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 barrier layer is apply | coated with an application | coating form, 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 effect 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.

(Examples 1 to 13: Production of gas barrier films 1 to 13)
[Resin substrate]
As the 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. Specifically, 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 (smooth layer) having a thickness of 2 μm was formed on the surface of the resin substrate on the side on which the gas barrier layer was 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 substrate with a clear hard coat layer was obtained. Hereinafter, in this example and the comparative example, this resin substrate with a clear hard coat layer is simply referred to as a resin substrate for convenience.

[Formation of layer (B) modified polysilazane layer]
The layer (B) was formed by applying a coating liquid containing polysilazane as shown below on the resin substrate to form a coating film, and then performing modification by vacuum ultraviolet irradiation.

A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) )) And a dibutyl ether solution (NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) containing 20% by mass of perhydropolysilazane in a ratio of 4: 1 (mass ratio), and further for adjusting the dry film thickness A coating solution was prepared by appropriately diluting with dibutyl ether.

The coating solution was applied onto the resin substrate by spin coating so as to have a dry film thickness shown in Table 2 below, and dried at 80 ° C. for 2 minutes. Next, vacuum ultraviolet irradiation treatment was performed on the dried coating film under the irradiation energy conditions shown in Table 2 using the vacuum ultraviolet irradiation apparatus of FIG. 3 having an Xe excimer lamp with 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.

In FIG. 3, reference numeral 1 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. 2 is an Xe excimer lamp (excimer lamp light intensity: 130 mW / cm ² ) having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, and 3 is an excimer lamp holder that also serves as an external electrode. Reference numeral 4 denotes a sample stage. The sample stage 4 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 1 by a moving means (not shown). The sample stage 4 can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 5 denotes a sample on which a polysilazane compound coating layer is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 3 mm. Reference numeral 6 denotes a light-shielding plate which prevents the application of the sample from being irradiated with vacuum ultraviolet rays during aging of the Xe excimer lamp 2.

The energy applied to the surface of the sample coating layer in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using a UV integrating photometer: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics. In the measurement, the sensor head is installed in the center of the sample stage 4 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 1 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as in the process, and the sample stage 4 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 2, 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 in this measurement, the irradiation energy shown in Table 2 was adjusted by adjusting the moving speed of the sample stage. The vacuum ultraviolet irradiation was performed after aging for 10 minutes.

[Formation of layer (A)]
The layer (A) was directly formed on the layer (B) by DC or RF, using a magnetron sputtering apparatus, using the targets and film formation conditions shown in Table 1 below, depending on the target used. The film formation conditions used for film formation in each gas barrier film are shown in Table 1 below.

(Comparative Example 1: Production of gas barrier film 14)
On the resin base material used in Example 1, a silicon oxide layer was formed using the targets and film formation conditions shown in Tables 1 and 2 below to obtain a gas barrier film 14.

(Comparative Example 2: Production of gas barrier film 15)
A niobium oxide layer was formed on the resin substrate used in Example 1 using the targets and film formation conditions shown in Tables 1 and 2 below, to obtain a gas barrier film 15.

(Comparative Example 3: Production of gas barrier film 16)
A gas barrier film 16 was obtained in the same manner as in Example 1 except that the layer (A) was not formed on the layer (B) in Example 1.

(Comparative Example 4: Production of gas barrier film 17)
The same procedure as in Example 1 was conducted except that a silicon oxide layer was formed on the layer (B) in Example 1 using the targets and film formation conditions shown in Tables 1 and 2 below instead of the layer (A). A gas barrier film 17 was obtained.

(Comparative Example 5: Production of gas barrier film 18)
In Example 1, instead of the layer (A) on the layer (B), a silicon oxycarbide layer was formed as follows, and the targets shown in Tables 1 and 2 below were formed on the formed silicon oxycarbide layer. The gas barrier film 18 was obtained in the same manner as in Example 1 except that the niobium oxide layer was formed using the film forming conditions.

Formation of silicon oxycarbide layer: Polymethylsilsesquioxane (SR-13, manufactured by Konishi Chemical Industry Co., Ltd.) was dissolved in methyl ethyl ketone and filtered to obtain a 5% by mass coating solution. This was applied by spin coating so that the dry film thickness was 100 nm, and dried at 100 ° C. for 2 minutes.

(Comparative Examples 6 to 8: Production of gas barrier films 19 to 21)
In Example 1, the gas barrier film was formed in the same manner as in Example 1 except that the reforming energy in forming the layer (B) was set to the conditions shown in Table 2 and the layer (A) was not formed. 19-21 were obtained.

(Comparative Example 9: Production of gas barrier film 22)
In Example 1, the gas barrier film 22 was obtained in the same manner as in Example 1 except that the reforming energy at the time of forming the layer (B) was changed to the conditions shown in Table 2.

(X1 / x2 ratio minimum value)
It was obtained from the composition distribution profile in the thickness direction by the above XPS composition analysis.

(Ratio where x1 / x2 <1 in the thickness direction)
From the composition distribution profile in the thickness direction, the ratio of x1 / x2 <1 in the thickness direction was determined, and ranked based on the following indices.

5 75% or more, 100% or less 4 50% or more, less than 75% 3 25% or more, less than 50% 2 Over 20% and less than 25% 10%
The results are shown in Table 2.

(Evaluation methods)
1. Barrier property evaluation by Ca method 1
<Water vapor permeability evaluation 1 of gas barrier film (hereinafter simply referred to as evaluation 1)>
According to the following measuring method, the water vapor permeability of each gas barrier film was evaluated.

After the surface of the barrier layer of the barrier film was UV-cleaned, a thermosetting sheet-like adhesive (epoxy resin) was bonded to the 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 with a size of 20 mm × 20 mm through a mask at the center of the glass plate using a vacuum vapor deposition apparatus manufactured by LS Technology Co., Ltd. The thickness of Ca was 80 nm.

The glass plate on which Ca was vapor-deposited was taken out into the glove box, placed so that the sealing resin layer surface of the barrier film to which the sealing resin layer was bonded and the Ca vapor-deposited surface of the glass plate were in contact, and adhered by vacuum lamination. At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down and cured for 30 minutes to prepare an evaluation cell.

In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample is similarly 85. Storage at high temperature and high humidity of 85 ° C. and 85% RH was conducted, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

(Measurement of transmission density)
The transmission density was measured using the evaluation cell.

For transmission density measurement, a black and white transmission densitometer TM-5 manufactured by Konica Minolta was used.

The transmission density was measured at any four points in the cell, and the average value was calculated. The same applies hereinafter.

Next, the evaluation cell was stored in an environment of 85 ° C. and 85% RH, and observed for 1 hour, 5 hours, 10 hours, 20 hours, and every 20 hours thereafter, and the transmission density was measured. The observation time when the transmission density was less than 50% of the initial value was determined. The results are shown in Table 2.

<Water vapor permeability evaluation 2 of gas barrier film (hereinafter simply referred to as evaluation 2)>
In each Example and Comparative Example, after forming a lower layer on the substrate, the upper layer was formed after storage for 7 days in an environment of 30 ° C. and 60% RH. For each sample, the observation time when it was less than 50% of the initial transmission density was determined in the same manner as in Evaluation 1. The results are shown in Table 2. In addition, this evaluation was performed in order to evaluate manufacturing stability by whether the barrier property of a lower layer deteriorated.

From the above results, it can be seen that the gas barrier films 1 to 13 are excellent in durability in a high temperature and high humidity environment. Such an effect is obtained by comparing the gas barrier film 16 not provided with the layer (A) and the gas barrier film 18 in which the layer (A) and the layer (B) are not adjacent to each other. It can be seen that this is achieved by the fact that the layer (A) and the layer (B) are adjacent to each other. In addition, the gas barrier film 22 whose irradiation energy during polysilazane modification is less than 1.0 J / cm ² is significantly less durable in a high-temperature and high-humidity environment than the gas barrier film 13. I understand that.

When the gas barrier films 2 to 4 are compared, it can be seen that the gas barrier films 2 and 3 where x1 <x2 are more excellent in durability in a high temperature and high humidity environment. Further, when the gas barrier film 4 and the gas barrier film 13 are compared, it can be seen that the gas barrier film 4 having a higher irradiation energy amount is superior in durability in a high temperature and high humidity environment.

(Examples 14 to 20: Production of gas barrier films 23 to 29)
[Resin substrate]
The same resin base material as that described in the column of resin base material in Examples 1 to 13 was used.

[Formation of layer (A)]
The layer (A) was formed on the layer (B) using a magnetron sputtering apparatus and using the targets and film formation conditions shown in Table 1 above by DC or RF depending on the target to be used. The film formation conditions used for film formation in each gas barrier film are shown in Table 3 below.

[Formation of layer (B) modified polysilazane layer]
The layer (B) was formed immediately above the layer (A) in the same manner as in “Formation of layer (B) modified polysilazane layer” in Example 1. In addition, the irradiation energy amount at the time of the modification was performed as described in Table 3 below.

(Comparative Example 12: Production of gas barrier film 30)
In Example 14, instead of the niobium oxide layer, using the targets and film formation conditions shown in Table 1 and Table 3 below, the silicon oxide layer was formed, and the dry film thickness of the layer (B) was 150 nm. A gas barrier film 30 was obtained in the same manner as in Example 14 except that the coating film was formed as described above.

(Comparative Example 13: Production of gas barrier film 31)
In Example 14, instead of the layer (A), a niobium oxide layer was formed on the resin base material using the targets and film formation conditions shown in Table 1 and Table 3 below. A gas barrier film 31 was obtained in the same manner as in Example 14 except that the layer was formed.

Formation of silicon oxycarbide layer: Polymethylsilsesquioxane (SR-13, manufactured by Konishi Chemical Industry Co., Ltd.) was dissolved in methyl ethyl ketone and filtered to obtain a 5% by mass coating solution. This was applied by spin coating so that the dry film thickness was 50 nm, and dried at 100 ° C. for 2 minutes.

(Comparative Example 14: Production of gas barrier film 32)
In Example 15, a gas barrier film 32 was obtained in the same manner as in Example 15 except that the irradiation energy at the time of forming the layer (B) was changed to the conditions shown in Table 3.

Evaluation 1 was performed on the gas barrier films of Examples 14 to 20 and Comparative Examples 12 to 14. The results are shown in Table 3.

<Water vapor permeability evaluation 3 of gas barrier film (hereinafter simply referred to as evaluation 3)>
The gas barrier film obtained in each Example and Comparative Example was stored for 48 hours in an environment of 40 ° C. and 90% RH. With respect to the gas barrier film after storage, the transmission density initial value was determined in the same manner as in Evaluation 1. Thereafter, the observation time when each sample was less than 50% of the initial transmission density was determined in the same manner as in Evaluation 1 above. The results are shown in Table 3. In addition, this evaluation was performed in order to evaluate manufacturing stability by whether the barrier property of an upper layer deteriorated.

From the above results, it can be seen that the gas barrier films 23 to 29 are excellent in durability in a high temperature and high humidity environment. Such an effect is obtained by comparing the gas barrier film 30 not provided with the layer (A) and the gas barrier film 31 in which the layer (A) and the layer (B) are not adjacent to each other. It can be seen that this is achieved by the fact that the layer (A) and the layer (B) are adjacent to each other. In addition, the gas barrier film 32 having an irradiation energy of less than 1.0 J / cm ² during the polysilazane modification has a significantly reduced durability in a high temperature and high humidity environment as compared with the gas barrier film 24. I understand that.

In the case of the substrate-layer (A) -layer (B), the degree of modification in the vicinity of the interface due to the difference in the excimer permeation amount of the polysilazane layer (the thinner the polysilazane layer is modified) and the polysilazane modification It is considered that the barrier performance of the layer itself is exhibited in combination with the barrier property of the layer itself (a better thickness of the polysilazane layer is better). For this reason, in the said Example, it is guessed that the gas barrier film 27 whose film thickness of a layer (B) is 100 nm brought the most favorable result.

This application is based on Japanese Patent Application No. 2015-035034 filed on February 25, 2015, the disclosure content of which is referenced and incorporated as a whole.

Claims (10)

1. A layer (A) containing a transition metal compound formed by a vapor phase film-forming method on a resin substrate, and in contact with the layer (A), obtained by applying and drying a coating liquid containing polysilazane. And a gas barrier layer (B) formed by applying vacuum ultraviolet rays to the coating film, wherein the irradiation energy amount of the vacuum ultraviolet rays on the surface of the coating film is 1.0 J / cm ² or more. .
2. The gas barrier film according to claim 1, wherein the transition metal in the transition metal compound is a metal having a lower oxidation-reduction potential than silicon.
3. The layer (A) includes a metal oxide MO _x1 where x1 <x2, where M is the transition metal and MO _x2 is a stoichiometrically obtained transition metal oxide. The gas barrier film according to the description.
4. The gas barrier film according to claim 2 or 3, wherein the transition metal is at least one metal selected from the group consisting of vanadium, niobium and tantalum.
5. The gas barrier film according to any one of claims 1 to 4, wherein the resin substrate, the layer (B), and the layer (A) are arranged in this order.
6. A layer (A) containing a transition metal compound is formed on a resin substrate by a vapor deposition method, and a coating liquid containing polysilazane is applied and dried on the layer (A) so as to be in contact with the layer (A). The coating film obtained is irradiated with vacuum ultraviolet rays to form the gas barrier layer (B), or the coating film obtained by applying and drying a coating liquid containing polysilazane on the resin substrate is vacuum ultraviolet rays. Forming a gas barrier layer (B), and forming a layer (A) containing a transition metal compound on the layer (B) by a vapor deposition method so as to be in contact with the layer (B). The manufacturing method of the gas barrier film whose irradiation energy amount of the said vacuum ultraviolet rays in the surface of the said coating film is 1.0 J / cm < ² > or more.
7. The method for producing a gas barrier film according to claim 6, wherein the transition metal in the transition metal compound is a metal having a lower oxidation-reduction potential than silicon.
8. The layer (A) includes a metal oxide MO _x1 where x1 <x2, where M is the transition metal and MO _x2 is a stoichiometrically obtained transition metal oxide. The manufacturing method of the gas-barrier film of description.
9. The method for producing a gas barrier film according to claim 7 or 8, wherein the transition metal is at least one metal selected from the group consisting of vanadium, niobium and tantalum.
10. The method for producing a gas barrier film according to any one of claims 6 to 9, wherein the resin substrate, the layer (B), and the layer (A) are arranged in this order.

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