JPWO2016178391A1 - Elongated gas barrier film and method for producing the same, and short gas barrier film and method for producing the same - Google Patents

Abstract

The present invention provides a long gas barrier film excellent in durability in a high temperature and high humidity environment. The present invention provides a gas barrier layer containing silicon and nitrogen provided on a long resin substrate, and is provided in contact with the gas barrier layer, and includes V, Nb, Ta, Ti, Zr, Hf, Mg, Y And a metal oxide layer containing an oxide of at least one metal selected from the group consisting of Al, and a long gas barrier film having an X in the thickness direction of the gas barrier film. In the atomic composition distribution profile obtained when the compositional analysis by line photoelectron spectroscopy is performed, the carbon composition ratio when the atomic composition ratio of silicon to metal is 1: 1 is silicon, metal, nitrogen, oxygen , And the total amount of carbon is 100 atm%, and is a long gas barrier film that is less than 2.0 atm%.

Description

  The present invention relates to a long gas barrier film and a method for producing the same, and a short gas barrier film and a method for producing the same.

  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, International Publication No. 2011/122547 (corresponding to US Patent Application Publication No. 2013/047889) has a gas barrier layer obtained by implanting hydrocarbon compound ions into a layer containing a polysilazane compound. An elongated shaped body is disclosed.

  However, a gas barrier layer obtained by implanting hydrocarbon compound ions into a layer containing a polysilazane compound described in International Publication No. 2011/122547 (corresponding to US Patent Application Publication No. 2013/047889) Although the gas barrier property at a low temperature up to about 40 ° 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 60 ° C. and 90% RH.

  Thus, there has been a demand for a long gas barrier film that can be used as an electronic device by suppressing deterioration of performance 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 elongate gas barrier property film which is excellent in durability in a high temperature, high humidity environment.

  Another object of the present invention is to provide a short 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, in the atomic composition distribution profile obtained when the composition analysis by X-ray photoelectron spectroscopy is performed in the thickness direction of the gas barrier film, the carbon when the atomic composition ratio of silicon to metal is 1: 1. The composition ratio of silicon, metal, nitrogen, oxygen, and carbon is 100 atm%, and it is found that the above problem is solved by a long gas barrier film that is less than 2.0 atm%. The invention has been completed.

  That is, the present invention provides a gas barrier layer containing silicon and nitrogen provided on a long resin substrate, and is provided in contact with the gas barrier layer, and includes V, Nb, Ta, Ti, Zr, Hf, Mg And a metal oxide layer containing an oxide of at least one metal selected from the group consisting of Y, Y, and Al, and a gas barrier film having a long shape, the thickness direction of the gas barrier film In the atomic composition distribution profile obtained when the composition analysis is performed by X-ray photoelectron spectroscopy, the composition ratio of carbon when the atomic composition ratio of silicon to metal is 1: 1 is silicon, metal, nitrogen. , Oxygen, and carbon, the total amount of which is 100 atm%, and is a long gas barrier film that is less than 2.0 atm%.

It is a figure which shows an example of the atomic composition distribution profile obtained when performing a composition analysis by X-ray photoelectron spectroscopy (XPS), and shows the atomic composition distribution profile obtained from the gas barrier film of Example 14 described later FIG. It is a cross-sectional schematic diagram showing an example of a vacuum ultraviolet irradiation apparatus, 10 is an apparatus chamber, 12 is a Xe excimer lamp, 13 is an excimer lamp holder that also serves as an external electrode, 14 is a sample stage, 15 is a base material sample on which a polysilazane coating film is formed, and 16 is a light shielding plate. It is the schematic which shows an example of the apparatus used when manufacturing a elongate gas barrier film, 1 is a film laminated body, 20 is a gas barrier film manufacturing apparatus, 21 is a resin base material, 22a and 22c are feed rollers, 22b is a take-up roller, 23a, 23b, 23c, 23d, 23e, 23f, 23g and 23h are transport rollers, 23i and 23j are nip rolls, and 23k is a touch roller 24 is a coating means, 25 is a drying means, 27 is a protective film, and 28 is a modification treatment means.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described below.

  In the following description, the “long shape” means a film having a length of at least 5 times or more with respect to the width direction of the film, preferably having a length of 10 times or more, specifically It has a length that can be stored in a roll and stored or transported.

  The present invention provides a gas barrier layer containing silicon and nitrogen provided on a long resin substrate, and is provided in contact with the gas barrier layer, and includes V, Nb, Ta, Ti, Zr, Hf, Mg, Y And a metal oxide layer containing an oxide of at least one metal selected from the group consisting of Al, and a long gas barrier film having an X in the thickness direction of the gas barrier film. In the atomic composition distribution profile obtained when performing composition analysis by linear photoelectron spectroscopy (hereinafter also referred to as XPS), the composition ratio of carbon when the atomic composition ratio of silicon to metal is 1: 1 is A long gas barrier film having a total amount of silicon, metal, nitrogen, oxygen and carbon of 100 atm% and less than 2.0 atm%. The long gas barrier film of the present invention having such a configuration is excellent in durability in a high temperature and high humidity environment.

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

  The present inventors diligently studied to solve the problem that the durability in a high-temperature and high-humidity environment is lowered in the conventional gas barrier film. In the process, the inventors found that the amount of carbon in the vicinity of the surface of the gas barrier layer is related to the durability of the gas barrier film, and focused on this point.

  When manufacturing a long gas barrier film, after forming the gas barrier layer by roll-to-roll, generally, a protective film is laminated on the gas barrier layer and wound up for the purpose of protecting the gas barrier layer. Has been done. The protective film is usually provided with an adhesive layer, but it was estimated that the surface of the gas barrier layer was contaminated by substances contained in the adhesive layer, and the durability in a high-temperature and high-humidity environment was reduced.

  Therefore, the present inventor has obtained the atomic composition distribution obtained when the composition analysis by XPS is performed in the thickness direction of the gas barrier film in the gas barrier film having the gas barrier layer containing silicon and nitrogen and the metal oxide layer. From the profile, it was found that durability is improved by reducing the carbon composition ratio when the atomic composition ratio of silicon and metal is 1: 1, and the present invention has been completed. The point where the atomic composition ratio of silicon to metal is 1: 1 is in the vicinity of the interface between the gas barrier layer and the metal oxide layer. By reducing the carbon composition ratio at this point, the contamination of the gas barrier layer surface is reduced. It is considered that the durability of the long gas barrier film is improved.

  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.

[Gas barrier layer]
The gas barrier layer according to the present invention contains silicon and nitrogen. Such a gas barrier layer is preferably formed by applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane.

  By applying energy, the gas barrier layer exhibits gas barrier properties. 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 gas barrier layer may be a single layer or a laminated structure of two or more layers.

Polysilazane is a polymer having a silicon-nitrogen bond, and ceramics such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y having bonds such as Si—N, Si—H, and N—H. 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 preferable embodiments is R ₁, R₂And R₃Is perhydropolysilazane, all of which 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 part bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base resin substrate by having an alkyl group such as a methyl group, and The ceramic film made of hard and brittle polysilazane can be toughened, and there is an advantage that generation 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 solution for forming a gas barrier layer. 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.

  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.

(Gas barrier layer forming coating solution)
The solvent for preparing the coating liquid for forming the gas barrier layer is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups (for example, hydroxyl group or amine group) that easily react with polysilazane. Etc.), an organic solvent inert to polysilazane is preferred, and an aprotic organic solvent is more preferred. 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 gas barrier 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 is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, Preferably it is 10-40 mass%.

  The gas barrier layer forming coating solution 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, 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 the silicon compound. 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.

  The following additives may be added to the gas barrier 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, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyester resins or modified polyester resins, epoxy resins, polyisocyanates or blocked polyisocyanates, or polysiloxanes.

(Method of applying gas barrier layer forming coating solution)
As a method for applying the gas barrier 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. For example, the thickness of the coating solution (coating film) after drying (when forming a coating film a plurality of times, the thickness per one time) is preferably 40 to 1000 nm, more preferably 100 to 300 nm. It is.

  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 gas barrier layer can be obtained. The remaining solvent can be removed later.

  Although the drying temperature of a coating film changes with resin base materials to apply, it is preferable that it is 50-200 degreeC. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the resin substrate, the drying temperature may be set to 150 ° C. or less in consideration of deformation of the resin substrate due to heat. preferable. 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.

<Application of energy>
Subsequently, an energy is applied to the coating film formed as described above to perform a conversion reaction of polysilazane to silicon oxide, silicon oxynitride, or the like, so that the gas barrier layer is an inorganic thin film that can exhibit gas barrier properties. Reforming.

  The conversion reaction of polysilazane to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment.

  As the modification treatment, from the viewpoint of adapting to a plastic substrate, a plasma treatment capable of a conversion reaction at a lower temperature and a conversion reaction by an ultraviolet irradiation treatment are preferable. Hereinafter, plasma treatment and ultraviolet irradiation treatment, which are preferable modification treatment methods, will be described.

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

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

≪Ultraviolet irradiation treatment≫
As one of the modification treatment methods, treatment by ultraviolet irradiation is preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures It is.

  The substrate is heated by this ultraviolet irradiation, and O contributes to ceramicization (silica conversion). ₂And H₂O, the ultraviolet absorber, and the polysilazane itself are excited and activated, so that the polysilazane is excited to promote the conversion of the polysilazane into a ceramic, and the resulting gas barrier layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

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

  The ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 375 nm. Use ultraviolet light.

  In the irradiation with ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time within a range in which the substrate carrying the irradiated gas barrier layer is not damaged.

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

  Examples of such ultraviolet ray generating means include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by M.D. Com Co., Ltd.), UV light laser, and the like, but are not particularly limited. Moreover, when irradiating the generated ultraviolet rays to the gas barrier layer, it is preferable to apply the ultraviolet rays from the generation source to the gas barrier layer after reflecting the ultraviolet rays from the generation source with a reflecting plate from the viewpoint of achieving efficiency improvement and uniform irradiation.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, a laminate having a gas barrier layer on the surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. In addition, when the laminated body having the gas barrier layer on the surface is a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. can do. 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 gas barrier layer used.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment 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 with only photons called photon processes. This is a method of forming a silicon oxide film 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 by action. In addition, when performing an excimer irradiation process, it is preferable to use together the above-mentioned heat processing.

  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 possessed by 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 resin substrate can be reduced.

The amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the coating surface is preferably 100 mJ / cm ^{2 to} 50 J / cm ² , more preferably 200 mJ / cm ^{2 to 20} J / cm ² , and 500 mJ / cm 2. More preferably, it is ^{2 to} 10 J / cm ² . If it is 100 mJ / cm ² or more, the modification is sufficient, and if it is 50 J / cm ² or less, generation of cracks due to excessive modification and thermal deformation of the resin substrate can be suppressed.

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.

  The thickness of the gas barrier layer (in the case of a laminated structure of two or more layers, the total thickness) is preferably 10 to 1000 nm, and more preferably 50 to 600 nm. If it is this range, the balance of gas barrier property and durability becomes favorable and is preferable. The thickness of the gas barrier layer can be measured by TEM observation.

[Metal oxide layer]
The gas barrier film of the present invention is a metal containing an oxide of at least one metal selected from the group consisting of Nb, Ta, V, Zr, Ti, Hf, Mg, Y, and Al on the gas barrier layer. It has an oxide layer. These metals have a lower redox potential than Si and are more easily oxidized than silicon. Therefore, oxidation of the gas barrier layer can be suppressed, and durability in a high temperature and high humidity environment can be improved.

  Among these, Nb, Ta, and V, which are Group 5 elements, can be preferably used because they have a higher effect of suppressing oxidation of the gas barrier layer. Furthermore, from the viewpoint of optical properties, Nb and Ta from which a layer with good transparency can be obtained are more preferable, and Nb is more preferable.

  Standard oxidation-reduction potentials of the above metals are shown in the following table.

  The content of the metal oxide in the metal oxide layer is not particularly limited as long as the effect of the present invention is achieved, but is preferably 50% by mass or more, and 80% by mass or more with respect to the total mass of the metal oxide layer. More preferably, it is more preferably 95% by mass or more, particularly preferably 98% by mass or more, and 100% by mass (that is, the metal oxide layer is made of a metal oxide). Most preferred.

  Examples of compounds other than metal oxides that can be included in the metal oxide layer include nitrides, nitrides, and carbonates of the above metals.

  The method for forming the metal oxide layer is preferably a vapor deposition method from the viewpoint of ease. 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). ) And the like. 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 thin film of an oxide containing the above metal can be formed by using the above metal for the target and further introducing oxygen into the process gas. In the case of forming a film by RF (high frequency) sputtering, the 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. Further, by introducing oxygen, nitrogen, carbon dioxide, carbon monoxide, or the like into the process gas, a transition metal compound thin film such as a 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 metal oxide as a target is preferable because it has a higher film formation rate and higher productivity.

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

  The thickness of the metal oxide layer (the total thickness in the case of a laminated structure of two or more layers) is not particularly limited, but is preferably 1 to 500 nm, preferably 3 to 300 nm, and 5 to 200 nm. It is more preferable that If it is this range, the oxidation of a gas barrier layer can be suppressed more efficiently.

[Long resin substrate]
Specific examples of the long resin base material according to the present invention (also simply referred to as “resin base material” or “base material” in the present specification) include polyester resins, methacrylic resins, and methacrylic acid-maleic acid. Copolymer, polystyrene resin, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic Thermoplastic resins such as polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring-modified polycarbonate resin, fluorene ring-modified polyester resin, acryloyl compound A substrate comprising the like. 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 resin base material satisfies the necessary conditions 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, if the linear expansion coefficient of the resin 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 the 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 resin base material can be adjusted by an additive or the like. More preferable specific examples of the thermoplastic resin that can be used as the resin substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic ring. 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: special Kai 2000-227603 Compound described in JP: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP-A No. 2000-227603: 205 ° C.), acryloyl compound (compound described in JP-A No. 2002-80616): 300 (In the parentheses indicate Tg).

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

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

  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. Regarding the method for producing these resin base materials, the items 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 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 layers 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.

[Composition ratio of carbon]
The gas barrier film of the present invention is carbon at a point where the atomic composition ratio of silicon and metal is 1: 1 in the atomic composition distribution profile obtained when composition analysis is performed in the thickness direction by X-ray photoelectron spectroscopy. The composition ratio (hereinafter also simply referred to as “carbon composition ratio”) is less than 2.0 atm%, where the total amount of silicon, metal, nitrogen, oxygen, and carbon is 100 atm%. The gas barrier film of the present invention having such a configuration is excellent in durability in a high temperature and high humidity environment.

  When the carbon composition ratio is 2.0 atm% or more, durability in a high temperature and high humidity environment is lowered. The carbon composition ratio is preferably 1.7 atm% or less, more preferably 1.5 atm% or less.

  The carbon composition ratio can be determined by the following method. FIG. 1 is a diagram showing an example of an atomic composition distribution profile obtained when a composition analysis is performed by X-ray photoelectron spectroscopy (XPS), and is an atomic composition obtained from a gas barrier film of Example 14 described later. It is a figure which shows a distribution profile. The intersection of the silicon distribution curve indicated by Si in FIG. 1 and the metal distribution curve indicated by Nb in FIG. 1 is the point where the atomic composition ratio of silicon and metal is 1: 1. The curve indicated by C in FIG. 1 is a carbon distribution curve, and the composition ratio of carbon at the sputter depth at the intersection is obtained from this carbon distribution curve. Although not shown in FIG. 1, the composition ratio of nitrogen and the composition ratio of oxygen at the sputter depth at the intersection are obtained from the nitrogen distribution curve and the oxygen distribution curve obtained by the same XPS composition analysis. From these analysis results, the total amount of silicon, metal, nitrogen, oxygen, and carbon is set to 100 atm%, and the composition ratio of carbon at the sputter depth at the intersection is calculated as the carbon composition ratio in this specification.

  The XPS composition analysis in the present invention was performed under the following conditions, but even if the apparatus and measurement conditions are changed, any measurement method that conforms to the gist of the present invention can be applied without any problem.

  << XPS composition analysis conditions >>
  ・ Apparatus: QUANTERASXM manufactured by ULVAC-PHI Co., Ltd.
  ・ X-ray source: Monochromatic Al-Kα
  Measurement area: Si2p, C1s, N1s, O1s
  ・ Sputtering ion: Ar (2 keV)
  Depth profile: repeats measurement after sputtering for a certain time. One measurement is SiO ₂Adjust the sputtering time so that the thickness is about 0.84 nm.
  Quantification: The background is obtained by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI Co., Ltd.

  Such a carbon composition ratio is controlled by appropriately selecting a method such as selection of the type of protective film, time until peeling of the protective film, and cleaning of the surface of the gas barrier layer in the method for producing a gas barrier film described later. can do.

  Among these, from the viewpoint that the carbon composition ratio can be further reduced, the gas barrier layer has the surface of the gas barrier layer subjected to ultraviolet cleaning (UV cleaning), water cleaning, ozone plasma cleaning, air excimer cleaning, and oxygen concentration of 1 volume. It is preferable that it is obtained by further performing at least one cleaning treatment selected from the group consisting of excimer cleaning performed in an environment of not more than%. This cleaning process will be described later.

[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 where the gas barrier layer according to the present invention is formed for the purpose of improving the adhesion between the resin substrate and the gas barrier 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, a gas generated from the resin base material side is to some extent An anchor coat layer can also be formed for the purpose of blocking and 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 an active energy ray such as an ultraviolet ray or an electron beam. 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.

(Smooth layer)
The gas barrier film of the present invention may have a smooth layer between the resin substrate and the gas barrier 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 prevents unevenness and pinholes that may occur in the gas barrier layer due to 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.

  Examples of the photosensitive material for the smooth layer include 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, and urethane acrylate. And 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 and more preferably in the range of 2 to 7 μm from the viewpoint of improving the heat resistance of the film and facilitating balance adjustment of the optical properties of the film.

  The smoothness of the smooth layer is a value expressed by the surface roughness defined by JIS B 0601: 2013, 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.

[Method for producing gas barrier film]
The method for producing the gas barrier film of the present invention is not particularly limited, but includes a step of forming a gas barrier layer containing silicon and nitrogen on a long resin substrate, and a protective film is pasted on the surface of the gas barrier layer. A step of peeling off the protective film after winding up the resulting laminate, and at least one metal selected from the group consisting of V, Nb, Ta, Ti, Zr, Hf, Mg, Y, and Al And a step of forming a metal oxide layer containing the above oxide.

  Since the step of forming the gas barrier layer and the step of forming the metal oxide layer are as described above, description thereof is omitted here. Below, the process which sticks a protective film, winds and peels, and the washing | cleaning process which can be performed after that are demonstrated.

(Process of attaching and peeling protective film)
In this step, after forming a gas barrier layer containing silicon and nitrogen on a long resin base material, a protective film is pasted on the gas barrier layer to obtain a laminate, and the laminate is wound up and then protected. Remove the film.

  The substrate of the protective film is not particularly limited, and examples thereof include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, cellulose resins such as triacetyl cellulose, acrylic resins such as polymethyl (meth) acrylate, polystyrene, acrylonitrile and styrene. Styrene resins such as polymers, olefin resins such as polycarbonate resins, polyethylene, polypropylene, ethylene / propylene copolymers, vinyl chloride resins, polyamide resins, imide resins, polyphenylene sulfide resins, polyethersulfone resins, vinylidene chloride resins, vinyl alcohol Examples thereof include resins, vinyl butyral resins, arylate resins, polyoxymethylene resins, epoxy resins, and blends of these resins. In the present invention, a material having cushioning properties such as polyethylene and polypropylene is preferable in order to obtain a good winding shape.

  The protective film may have an adhesive layer. Examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include re-peeling pressure-sensitive adhesives (acrylic, rubber-based, synthetic rubber-based, etc.) that are usually used.

  A commercial item may be used for a protective film. Examples of commercially available products include, for example, Toraytec (registered trademark) series (7111, 7412K6, 7531, 7721, 7332, 7121) manufactured by Toray Film Processing Co., Ltd., and Iupilon (registered trademark) series manufactured by Mitsubishi Engineering Plastics Co., Ltd. GF series manufactured by Tamapoli Co., Ltd., 010M manufactured by Futamura Chemical Co., Ltd. and the like.

  The method for attaching the protective film is not particularly limited. For example, the protective film is attached to a drive shaft having a motor such as a feeding machine (or unwinding machine) installed below or above the film line running on the film forming apparatus. Examples of the method include setting a protective film roll, and bonding the film having the gas barrier layer formed thereon and the protective film by pressing them with two rubber rolls.

  After sticking a protective film, the obtained laminated body is wound up in roll shape. More specifically, for example, a winding core is set on a winding machine, a laminate with a protective film is wound around the winding core, and the winding speed is adjusted so as to be almost the same as the line speed of the laminate. To do.

  Next, the protective film is peeled off. The method of peeling is not particularly limited, and examples thereof include a method of winding a protective film on a winding device equipped with a drive shaft (winding roller) such as a torque motor and peeling.

  The time from application of the protective film to peeling is preferably within 24 hours, more preferably within 18 hours, and even more preferably within 12 hours. By shortening the time until peeling in this way, contamination of the gas barrier layer surface due to the compound contained in the adhesive layer of the protective film can be further reduced, and the carbon composition ratio can be further reduced. Thereby, a gas barrier film excellent in durability in a high temperature and high humidity environment can be obtained.

  However, even if the time from application of the protective film to peeling exceeds 24 hours, the carbon barrier layer can be carbonized by performing the following cleaning process for cleaning the surface of the gas barrier layer before forming the metal oxide layer. The composition ratio can be reduced, which is preferable. Of course, even if the time from applying the protective film to peeling is within 24 hours, the carbon composition ratio can be further reduced by further performing the following washing step, which is preferable.

(Washing process)
In this step, after the protective film is peeled off, the surface of the gas barrier layer is washed before the metal oxide layer is formed on the gas barrier layer. This cleaning can further reduce the contamination of the gas barrier layer surface by the compound contained in the adhesive layer of the protective film, and can further reduce the carbon composition ratio.

  The cleaning process performed in this step is specifically selected from the group consisting of ultraviolet cleaning, water cleaning, ozone plasma cleaning, air excimer cleaning, and excimer cleaning performed in an environment having an oxygen concentration of 1% by volume or less. At least one is preferred.

  The ultraviolet cleaning is a dry process for cleaning the surface of the gas barrier layer using, for example, a low-pressure mercury lamp. The irradiation time (cleaning time) of ultraviolet rays is preferably 30 seconds to 20 minutes.

  The water treatment is a wet treatment that cleans the surface of the gas barrier layer using, for example, an ultrasonic cleaner that emits ultrasonic waves having a frequency of 150 kHz. The temperature during washing is preferably 10 to 50 ° C., and the washing time is preferably 30 seconds to 20 minutes.

  Ozone plasma cleaning is a dry process in which the surface of the gas barrier layer is cleaned using a highly reactive “plasma state” that is excited by ozone using a high frequency power source or the like as a trigger in vacuum.

  Excimer cleaning is a dry process in which the surface of the gas barrier layer is cleaned using a xenon excimer lamp that emits light at 172 nm. The atmosphere at the time of cleaning may be an air atmosphere (excimer cleaning in the air) or an environment having an oxygen concentration of 1% by volume or less.

[Short gas barrier film]
The long gas barrier film of the present invention may be cut into a short shape and used. That is, the present invention provides a short gas barrier film obtained by cutting the long gas barrier film of the present invention. Moreover, this invention provides the manufacturing method of a short gas barrier film including cutting the said long gas barrier film after obtaining a long gas barrier film with the manufacturing method of this invention. To do. The short gas barrier film of the present invention is excellent in durability in a high-temperature and high-humidity environment, like the long gas barrier film.

  Examples of means for cutting the long gas barrier film include cutting by an automatic cutting machine in addition to manual cutting. The size of the obtained short gas barrier film is not particularly limited.

[Electronic device]
The long or short 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 using the elongate gas barrier film of this invention, or the elongate gas barrier film obtained by the manufacturing method of this invention.

  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: Production of gas barrier film 1)
[Preparation of coating solution for gas barrier layer formation]
The gas barrier layer was formed by applying and drying a coating liquid containing polysilazane as shown below on the resin substrate described below to form a coating film, and performing modification by irradiation with vacuum ultraviolet rays.

  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 perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) at a ratio of 4: 1 (mass ratio), and further for dry film thickness adjustment A coating solution was prepared by appropriately diluting with dibutyl ether.

[Resin substrate]
A polyethylene terephthalate film with a double-sided hard coat layer (total thickness: 136 μm, PET thickness: 125 μm, manufactured by Kimoto Co., Ltd., trade name: KB film (trademark) 125G1SBF, width: 1230 mm, length: 100 m) was used.

  The gas barrier film 1 was manufactured using the gas barrier film manufacturing apparatus 20 shown in FIG. FIG. 3 is a schematic view showing an example of an apparatus used when producing a gas barrier film, which is a so-called roll-to-roll system apparatus. The apparatus shown in FIG. 3 includes a delivery roller 22a, transport rollers 23a to 23h, an application unit 24, a drying unit 25, a modification processing unit 28, nip rolls 23i and 23j, a delivery roller 22c, and a touch roller 23k. And a take-up roller 22b.

[First step]
The resin base material 21 with the double-sided hard coat layer was conveyed from the feed roller 22a to the coating means 24. The gas barrier layer forming coating solution prepared above is applied with a slot die coater so as to have a dry film thickness of 250 nm, and then heated at 80 ° C. for 2 minutes with a drying means 25 to form a coating film. did.

  The coating film formed above is transported to the modification treatment means 28, and is irradiated with vacuum ultraviolet rays (excimer irradiation apparatus MODEL: MECL-M-1-200 manufactured by M.D. 172 nm, stage temperature 100 ° C., oxygen concentration 0.1% by volume) to form a gas barrier layer.

(Modification method by vacuum ultraviolet irradiation)
The vacuum ultraviolet irradiation was performed using the vacuum ultraviolet irradiation apparatus shown in the schematic sectional view of FIG.

  Water vapor was removed from the inside of the apparatus chamber 10 of FIG. 2, and the oxygen concentration was maintained at 0.1% by volume. The base material sample 15 on which the polysilazane coating film was formed was conveyed to the sample stage 14 and moved horizontally at a constant speed in accordance with the desired irradiation energy while maintaining the sample stage 14 at 100 ° C. At this time, the height of the sample stage 14 was adjusted so that the polysilazane coating film faced upward and the shortest distance between the surface of the polysilazane coating film and the tube surface of the excimer lamp 12 was 3 mm.

  The energy applied to the surface of the polysilazane coating film 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 Co., Ltd. In the measurement, the sensor head is installed at the center of the sample stage 14 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 10 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the process, and the sample stage 14 was moved at a speed of 0.5 m / min for measurement. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 12, an aging time of 10 minutes was provided after the Xe excimer lamp 12 was turned on, and then the sample stage 14 was moved to start the measurement.

Based on the irradiation energy obtained by this measurement, the irradiation energy of 6.0 J / cm ² was adjusted by adjusting the moving speed of the sample stage. The vacuum ultraviolet irradiation was performed after aging for 10 minutes.

[Second step]
Subsequently, after the vacuum ultraviolet irradiation treatment, the resin base material 21 on which the gas barrier layer was formed was conveyed to the nip rolls 23i and 23j. At the same time, 010M (manufactured by Futamura Chemical Co., Ltd.) was transported from the feed roller 22c to the nip rolls 23i and 23j as the protective film 27 and formed as described above at 23 ° C. and a linear pressure of 20 N / cm at a speed of 2 m / min. The film was laminated on the gas barrier layer and brought into contact with the touch roller 23k, and 100 m was wound up in a roll shape so that the surface pressure was 0.6 MPa, whereby a film laminate 1 was obtained.

After 12 hours had passed since the protective film was pasted, the protective film was peeled off using a winding device equipped with a winding roller, and one film was cut into a size of 10 cm × 10 cm using scissors. Using the cut film, a metal oxide layer having a thickness of 15 nm was formed on the gas barrier layer by sputtering. The film formation uses a Ta ₂ O ₅ target as a target, and RF sputtering using Ar and O _{2 as} process gases, so that the oxygen partial pressure is adjusted so that the composition of the metal oxide layer becomes Ta ₂ O _4.4. Adjusted.

  Thus, the gas barrier film 1 was produced.

(Example 2: Production of gas barrier film 2)
A gas barrier film 2 was produced in the same manner as in Example 1 except that the metal oxide layer was formed as follows.

A metal oxide layer was formed by sputtering. A metal oxide layer having a film thickness of 15 nm was formed on a resin substrate by DC sputtering using an oxygen-deficient TiO ₂ target as a target and Ar and O _{2 as} process gases. In the film formation, the oxygen partial pressure was adjusted so that the composition was TiO ₂ .

(Example 3: Production of gas barrier film 3)
A gas barrier film 3 was produced in the same manner as in Example 1 except that the metal oxide layer was formed as follows.

A metal oxide layer was formed by sputtering. A metal oxide layer having a film thickness of 15 nm was formed on a resin substrate by DC sputtering using a Zr target as a target and using Ar and O _{2 as} process gases. In the film formation, the oxygen partial pressure was adjusted so that the composition was ZrO ₂ .

(Example 4: Production of gas barrier film 4)
A gas barrier film 4 was formed in the same manner as in Example 1 except that the irradiation energy of vacuum ultraviolet rays during the modification of polysilazane was changed to 3.0 J / cm ² and the metal oxide layer was formed as follows. Produced.

A metal oxide layer was formed by sputtering. A gas barrier layer having a film thickness of 15 nm was formed on a resin substrate by DC sputtering using an oxygen-deficient Nb ₂ O ₅ target as a target and using Ar and O _{2 as} process gases. In the film formation, the oxygen partial pressure was adjusted so that the composition of the gas barrier layer was Nb ₂ O ₃ .

(Example 5: Production of gas barrier film 5)
A gas barrier film 5 was produced in the same manner as in Example 4 except that the irradiation energy of vacuum ultraviolet rays during the modification of polysilazane was changed to 6.0 J / cm ² .

(Example 6: Production of gas barrier film 6)
A gas barrier film 6 was produced in the same manner as in Example 5 except that the gas barrier layer was washed with water before the metal oxide layer was formed.

≪Washing water≫
The film on which the gas barrier layer was formed was immersed in an ultrasonic bath emitting ultrasonic waves having a frequency of 150 Hz filled with pure water for 2 minutes (pure water temperature 23 ° C.), washed with water, and then dried. In the following Table 1, this water washing is represented as (A).

(Example 7: Production of gas barrier film 7)
A gas barrier film 7 was produced in the same manner as in Example 6 except that the time until the protective film was peeled off was 48 hours.

(Example 8: Production of gas barrier film 8)
A gas barrier film 8 was produced in the same manner as in Example 7 except that the protective film was changed to Toraytec (registered trademark) 7332 manufactured by Toray Film Processing Co., Ltd.

(Example 9: Production of gas barrier film 9)
A gas barrier film 9 was produced in the same manner as in Example 8 except that the time until the protective film was peeled off was 48 hours.

(Example 10: Production of gas barrier film 10)
A gas barrier film 10 was produced in the same manner as in Example 9 except that the following UV cleaning of the gas barrier layer was performed instead of the above water cleaning.

≪UV cleaning≫
Using a tabletop surface treatment device manufactured by Sen Special Light Source Co., Ltd., model number PL32-200, using a low-pressure mercury lamp (model number: EUV200WS-18) as a light source, a distance of 10 mm between the gas barrier layer surface and the lamp tube surface, and an irradiation time of 5 In minutes, a process of irradiating ultraviolet rays having a main wavelength of 254 nm was performed. In the following Table 1, this UV cleaning is represented as (A).

(Example 11: Production of gas barrier film 11)
A gas barrier film 11 was produced in the same manner as in Example 9 except that the UV cleaning described in Example 10 was performed before water cleaning.

(Example 12: Production of gas barrier film 12)
A gas barrier film 12 was produced in the same manner as in Example 11 except that the metal oxide layer was formed as follows.

A metal oxide layer was formed by sputtering. A Ta ₂ O ₅ target was used as a target, and the oxygen partial pressure was adjusted by RF sputtering using Ar and O _{2 as} process gases so that the composition of the metal oxide layer was Ta ₂ O _4.4 .

(Example 13: Production of gas barrier film 13)
A gas barrier film 13 was produced in the same manner as in Example 11 except that the metal oxide layer was formed as follows.

A metal oxide layer was formed by sputtering. A metal oxide layer having a film thickness of 15 nm was formed on a resin substrate by DC sputtering using an oxygen-deficient TiO ₂ target as a target and Ar and O _{2 as} process gases. In the film formation, the oxygen partial pressure was adjusted so that the composition was TiO ₂ .

(Example 14: Production of gas barrier film 14)
A gas barrier film 14 was produced in the same manner as in Example 11 except that the protective film was changed to 010M manufactured by Futamura Chemical Co., Ltd. and a metal oxide layer was formed as follows.

A metal oxide layer was formed by sputtering. A gas barrier layer having a film thickness of 15 nm was formed on a resin substrate by DC sputtering using an oxygen-deficient Nb ₂ O ₅ target as a target and using Ar and O _{2 as} process gases. In the film formation, the oxygen partial pressure was adjusted so that the composition of the gas barrier layer was Nb ₂ O ₃ .

(Example 15: Production of gas barrier film 15)
A gas barrier film 15 was produced in the same manner as in Example 14 except that the time until the protective film was peeled off was 12 hours.

(Comparative Example 1: Production of gas barrier film 16)
A gas barrier film 16 was produced in the same manner as in Example 5 except that the time until the protective film was peeled off was 48 hours.

(Comparative Example 2: Production of gas barrier film 17)
A gas barrier film 17 was produced in the same manner as in Example 8 except that water washing was not performed.

(Comparative Example 3: Production of gas barrier film 18)
A gas barrier film 18 was produced in the same manner as in Example 9 except that water washing was not performed.

(Comparative Example 4: Production of gas barrier film 19)
A gas barrier film 19 was produced in the same manner as in Example 1 except that the protective film was changed to Toraytec (registered trademark) 7332 manufactured by Toray Film Processing Co., Ltd.

(Comparative Example 5: Production of gas barrier film 20)
A gas barrier film 20 was produced in the same manner as in Example 2 except that the protective film was changed to Toray Film (registered trademark) 7332 manufactured by Toray Film Processing Co., Ltd.

(Comparative Example 6: Production of gas barrier film 21)
A gas barrier film 21 was produced in the same manner as in Example 3 except that the protective film was changed to Toray Film (registered trademark) 7332 manufactured by Toray Film Processing Co., Ltd.

(Comparative Example 7: Production of gas barrier film 22)
A gas barrier film 22 was produced in the same manner as in Comparative Example 3 except that the irradiation energy of vacuum ultraviolet rays during the polysilazane modification was changed to 3.0 J / cm ² .

(Comparative Example 8: Production of gas barrier film 23)
A gas barrier film 23 was produced in the same manner as in Comparative Example 7 except that the protective film was not used.

(Evaluation method)
<Carbon composition ratio>
The composition distribution profile in the thickness direction was measured by XPS composition analysis, and the composition ratio of carbon at the sputtering depth at which the atomic composition ratio of silicon to metal was 1: 1 was calculated. From the nitrogen distribution curve and the oxygen distribution curve obtained by the same XPS composition analysis, the composition ratio of nitrogen and the composition ratio of oxygen at the sputter depth at the above intersection are obtained, and from these analysis results, silicon, metal, nitrogen, oxygen, And the total amount of carbon was 100 atm%, and the composition ratio of carbon at the sputter depth at the intersection was calculated.

  << XPS composition analysis conditions >>
  ・ Apparatus: QUANTERASXM manufactured by ULVAC-PHI Co., Ltd.
  ・ X-ray source: Monochromatic Al-Kα
  ・ Sputtering ion: Ar (2 keV)
  Depth profile: repeats measurement after sputtering for a certain time. One measurement is SiO ₂The sputtering time was adjusted so that the thickness was about 0.84 nm in terms of conversion.
  Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. For data processing, MultiPak manufactured by ULVAC-PHI Co., Ltd. was used.

<Water vapor barrier property (WVTR)>
According to the following measuring method, the water vapor barrier property of each gas barrier film was evaluated.

-Apparatus Vapor deposition apparatus: JEOL Ltd., vacuum vapor deposition apparatus JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
-Manufacture of water vapor barrier property evaluation cell Using a vacuum deposition apparatus (manufactured by JEOL Ltd., vacuum deposition apparatus JEE-400), metallic calcium was deposited on the surface of each gas barrier film. After that, in a dry nitrogen gas atmosphere, the metal calcium vapor deposition surface is bonded and bonded to quartz glass having a thickness of 0.2 mm via a sealing ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) and irradiated with ultraviolet rays. Thus, an evaluation cell was produced.

  The obtained sample (evaluation cell) was stored under high temperature and high humidity of 60 ° C. and 90% RH, and the time taken for the metal calcium to corrode 100% was measured.

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

  Thus, the 100% corrosion time of each gas barrier film was evaluated in the following five stages. Ranks 5 to 4 are practical.

≪Evaluation criteria≫
Rank 5: 100% corrosion time 1000 hours or more Rank 4: 100% corrosion time 500 hours or more and less than 1000 hours Rank 3: 100% corrosion time 300 hours or more and less than 500 hours Rank 2: 100% corrosion time 100 hours or more Less than 300 hours Rank 1: 100% corrosion time is less than 100 hours.

  The production conditions and evaluation results of the gas barrier films of each Example and Comparative Example are shown in Table 1 below.

  From the results shown in Table 1, it can be seen that the gas barrier films of Examples 1 to 15 are excellent in durability in a high temperature and high humidity environment of 60 ° C. and 90% RH.

  In addition, this application is based on the JP Patent application No. 2015-094409 for which it applied on May 1, 2015, The content of an indication is referred as a whole by reference.

Claims (14)

A gas barrier layer containing silicon and nitrogen provided on a long resin substrate;
A metal oxide layer provided on and in contact with the gas barrier layer and containing an oxide of at least one metal selected from the group consisting of V, Nb, Ta, Ti, Zr, Hf, Mg, Y, and Al When,
A long gas barrier film having
The composition of carbon when the atomic composition ratio of silicon and metal is 1: 1 in the atomic composition distribution profile obtained when the composition analysis is performed by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier film. A long gas barrier film having a ratio of less than 2.0 atm%, where the total amount of silicon, metal, nitrogen, oxygen, and carbon is 100 atm%.   The long gas barrier film according to claim 1, wherein the metal is Nb.   The long gas barrier film according to claim 1 or 2, wherein the gas barrier layer is a layer formed by applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane.   The long gas barrier film according to claim 3, wherein the energy is applied by irradiating vacuum ultraviolet rays.   The gas barrier layer is at least one selected from the group consisting of ultraviolet cleaning, water cleaning, ozone plasma cleaning, air excimer cleaning, and excimer cleaning performed in an environment with an oxygen concentration of 1% by volume or less on the surface of the gas barrier layer. The long gas barrier film according to any one of claims 1 to 4, which is obtained by further performing a cleaning treatment.   A short gas barrier film obtained by cutting the long gas barrier film according to any one of claims 1 to 5. Forming a gas barrier layer containing silicon and nitrogen on a long resin substrate;
A step of attaching and winding a protective film on the surface of the gas barrier layer, and peeling the protective film;
Forming a metal oxide layer containing an oxide of at least one metal selected from the group consisting of V, Nb, Ta, Ti, Zr, Hf, Mg, Y, and Al;
The manufacturing method of the elongate gas-barrier film containing this.   The method according to claim 7, wherein the protective film is peeled off within 24 hours after the protective film is attached.   After the step of removing the protective film, the surface of the gas barrier layer is selected from the group consisting of ultraviolet cleaning, water cleaning, ozone plasma cleaning, air excimer cleaning, and excimer cleaning performed in an environment with an oxygen concentration of 1% by volume or less. The manufacturing method according to claim 7, further comprising a cleaning step of performing at least one cleaning treatment.   The manufacturing method of any one of Claims 7-9 whose said metal is Nb.   The manufacturing method according to claim 7, wherein the step of forming the gas barrier layer includes applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane.   The manufacturing method according to claim 11, wherein the application of energy is performed by irradiation with vacuum ultraviolet rays.   A short gas barrier film comprising: cutting a long gas barrier film after obtaining the long gas barrier film by the manufacturing method according to any one of claims 7 to 12. Production method.   The electronic device using the gas barrier film of any one of Claims 1-6, or the gas barrier film obtained by the manufacturing method of any one of Claims 7-13.