JP2013208867A - Gas barrier film, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film which has excellent gas barrier properties and is excellent in transparency and bending property of a barrier layer.SOLUTION: A gas barrier film 11 has a barrier layer 13 which is formed of polysilazane including SiON(where x is 0.5 to 2.3 and y is 0.1 to 3.0), and a curable resin layer 14 in this order on at least one surface of a base material 12.

Description

  The present invention relates to a gas barrier film and an electronic device. More specifically, the present invention mainly relates to a gas barrier film used for electronic devices such as packages such as electronic devices, solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, and the like, and electronic devices using the same. It is about.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging an article that requires blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent the deterioration of food, industrial goods and pharmaceuticals. In addition to the above packaging applications, it is also used in liquid crystal display elements, solar cells, organic electroluminescence (EL) substrates and the like.

  In recent years, in addition to demands for weight reduction and size increase, long-term reliability, high degree of freedom in shape, and the ability to display curved surfaces have been added, resulting in a glass substrate that is heavy, easily broken, and difficult to increase in area. Instead, film base materials such as transparent plastics are beginning to be adopted.

  However, a film substrate such as a transparent plastic has a problem that the gas barrier property is inferior to glass. If a base material with inferior gas barrier properties is used, water vapor or air will permeate, causing deterioration of the liquid crystal in the liquid crystal cell, for example, resulting in display defects and deterioration of display quality.

As gas barrier films used for packaging materials and liquid crystal display elements, those obtained by depositing silicon oxide or aluminum oxide on plastic films are known. However, these techniques have a water vapor barrier property of about 1 g / m ² / day at most. In recent years, the demand for gas barrier performance on a film substrate has increased to about 0.1 g / m ² / day for the gas substrate performance due to the development of large-sized liquid crystal displays and high-definition displays.

  As a method for forming a barrier layer other than the above evaporation, for example, a method of converting a perhydropolysilazane (hereinafter also referred to as PHPS) or an organic polysilazane film to silica is known. Silica conversion methods include heating and humidification treatment and sintering treatment, but these methods require a long time for barrier layer formation, and in addition, the substrate is exposed to a high temperature environment. There has been a problem that deterioration of the gas cannot be avoided, and a gas barrier film obtained by a simpler method has been demanded.

  For the purpose of improving gas barrier properties, Patent Document 1 discloses that a transparent polymer layer is provided as an upper layer of the barrier layer. Moreover, it is the polymer multilayer (Polymer Multilayer, PML) technique described in Patent Document 2. In this technique, a coating consisting of a polymer layer and an aluminum oxide layer is applied to a flexible substrate and the substrate is sealed. Both deposition processes can be operated at very high speeds using web processing equipment. It is disclosed that the resistance to water and oxygen permeability is improved by 3 to 4 orders of magnitude compared to uncoated PET membranes.

  On the other hand, in Patent Document 3, a coating liquid containing PHPS or organic polysilazane is applied to a polyester film, and PHPS or organic polysilazane is cured and polymerized by plasma treatment to form an inorganic polymer layer made of silicon oxide or the like. A method is disclosed. However, in the disclosed method, the inorganic polymer layer is used as an intermediate layer between the base material and the metal vapor deposition layer to provide adhesion between the metal vapor deposition layer and the chemical stability of the base material. Is a layer.

  Also disclosed is a method for converting a thin film (0.05 to 5 μm) containing PHPS or organic polysilazane as a main component into a dense glass-like layer excellent in transparency and high barrier action against gas ( For example, see Patent Document 3). The conversion method described in US Pat. No. 6,057,096 is based on the irradiation time of VUV light having a wavelength of 230 nm or less and UV light having a wavelength of less than 300 nm at the lowest possible temperature suitable for each substrate (0 .1 to 10 minutes) is disclosed, but the obtained gas barrier property is not satisfactory.

  Further, in the production of a thin protective layer of a magnetic strip, an oxidation method is disclosed in which irradiation is performed using ozone, atomic oxygen, or vacuum ultraviolet photons in the presence of oxygen and water vapor (see, for example, Patent Document 4). ). It is described that the processing time at room temperature can be shortened to several minutes by the method described in Patent Document 4. In this case, the vacuum ultraviolet radiation used is used only to generate these reactive species. It is stated that conversion times in the range of seconds to minutes can be achieved in a polysilazane layer of about 20 nm by supplying heat simultaneously to the allowable temperature limit of the substrate (eg for polyethylene terephthalate: 180 ° C.). ing.

  However, if organic EL or the like is designed with a plastic substrate in this way, it is possible to significantly reduce the weight of conventional glass, but on the other hand, element degradation associated with the permeation gas as described above occurs. There was a problem. For this reason, the expression of the technology that achieves both durability and weight reduction of the element has been desired.

JP-A-6-234186 US Reissue Patent No. 40,531 Specification JP-A-8-269690 European Patent No. 0745974

  However, the conventional gas barrier films described in Patent Documents 1 to 4 show sufficient gas barrier properties as described above, and there are no films with sufficient transparency and flexibility of the barrier layer.

  Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a gas barrier film having excellent gas barrier properties, transparency and excellent flexibility of the barrier layer.

As a result of diligent research to solve the above problems, the present inventor formed a barrier layer (ceramic film) containing SiO _x N _y on at least one surface of the base material, and provided an adhesive ability adjacent to the barrier layer. It has been found that an excellent gas barrier film in which the above-mentioned problems are solved can be obtained by forming (providing) a layer (curable resin layer) made of a curable resin. Furthermore, the present inventor forms a barrier layer (ceramic film) containing SiO _x N _y on at least one surface of the base material, and a layer (curable resin layer) composed of an organosilicon compound layer and a curable resin adjacent to the barrier layer. It was found that an excellent gas barrier film in which the above problems were further solved could be obtained by sequentially forming (providing). Based on the above findings, the present invention has been completed.

That is, the above-described object is to provide a barrier layer containing SiO _x N _y (where x is 0.5 to 2.3 and y is 0.1 to 3.0) on at least one of the substrates. (Hereinafter also simply referred to as “barrier layer”) and a gas barrier film having a curable resin layer in this order.

  The gas barrier film of the present invention has excellent gas barrier properties and is excellent in transparency and flexibility.

It is a schematic sectional drawing which shows one Embodiment of the laminated constitution of the gas barrier film of this invention. It is a schematic sectional drawing which shows other embodiment of the layer structure of the gas barrier film of this invention.

The present invention provides a barrier layer (hereinafter referred to as “SiO _x N _y” , where x is 0.5 to 2.3 and y is 0.1 to 3.0) on at least one of the substrates. And a gas barrier film having a curable resin layer in this order.

  Hereinafter, although the preferable form for implementing this invention is demonstrated in detail, this invention is not limited to these.

<Gas barrier film>
The layer structure of the gas barrier film of the present invention will be described with reference to FIGS.

  In FIG. 1, the gas barrier film 11 of the present invention includes a base material 12, and a barrier layer 13 and a curable resin layer 14 that are sequentially formed on the base material 12.

  In FIG. 2, the gas barrier film 11 of the present invention includes a base material 12, a barrier layer 13, an organic silicon compound layer 15, and a curable resin layer 14 that are sequentially formed on the base material 12. That is, the gas barrier film 11 of FIG. 2 has a structure in which an organosilicon compound layer 15 is further formed between the barrier layer 13 and the curable resin layer 14 of the gas barrier film 11 of FIG.

Here, the barrier layer is SiO _x N _y containing silicon, oxygen, and nitrogen as main components (where x is 0.5 to 2.3, and y is 0.1 to 3.0). It is a layer containing. In this specification, “having silicon, oxygen, and nitrogen as main components” means that the total of silicon, oxygen, and nitrogen is preferably 90% by weight or more, more preferably, of all elements constituting the entire layer. It means a component occupying 95% by weight or more, more preferably 98% by weight or more.

  The organosilicon compound layer means a layer containing carbon atoms and silicon atoms. The organosilicon compound layer is preferably a silicon oxide organic layer mainly composed of carbon, hydrogen, oxygen, and silicon. In the present specification, “mainly composed of carbon, hydrogen, oxygen, and silicon” means that the total of elements of silicon, oxygen, and carbon is preferably 90% by weight or more of all elements constituting the entire layer. It means a component that preferably accounts for 95% by weight or more, more preferably 98% by weight or more. The element composition ratio of the barrier layer and the organosilicon compound layer can be measured by a known standard method by X-ray photoelectron spectroscopy (XPS) while etching.

  The gas barrier film of the present invention can be further provided with functionalized layers such as another organic layer, a protective layer, a hygroscopic layer, and an antistatic layer as necessary. In addition, the gas barrier film of the present invention has a three-layer structure (three-layer constitution unit) in which a barrier layer, an organosilicon compound layer, and a barrier layer are arranged adjacent to each other in this order on a substrate. May be. In this case, the barrier layer and the organosilicon compound layer of the three-layer structure (three-layer structural unit) may have the same composition or different compositions. Of the barrier layer and the organosilicon compound layer, at least one layer preferably satisfies the above-mentioned preferable conditions.

[Barrier layer]
Barrier layer according to the present _invention comprises a _SiO x _{N y,} is preferably made of _SiO x _{N y.} This silicon oxynitride (SiO _x N _y ) has a composition in which main constituent elements are silicon, oxygen, and nitrogen. The constituent elements other than the above, such as a small amount of hydrogen and carbon, taken in from the raw material for film formation, the substrate, the atmosphere, and the like are each desirably less than 5%, and desirably each less than 2%. By having such a composition (especially including nitrogen), the flexibility of the barrier layer is increased, so that the degree of freedom of shape (flexibility, bendability, flexibility) is increased, and curved surface processing is possible. Since it is a dense layer, barrier properties against oxygen and water (water vapor) can be improved.

In _SiO x _{N y} constituting the barrier layer, x is from 0.5 to 2.3, preferably from 0.5 to 2.0, is preferably 1.2 to 2.0. Moreover, y is 0.1-3.0, it is preferable that it is 0.15-1.5, and it is preferable that it is 0.2-1.3. Here, the relationship between x and y is not particularly limited, but a composition ratio [x / (x + y)] of x to the sum of x and y is preferably 0.05 to 0.95, More preferably, it is 0.9. Alternatively, the composition ratio [x / y] of x to y is preferably 0.2 to 12, more preferably 0.3 to 10, still more preferably 0.3 to 2.2, 0.5-1 is particularly preferable. If the composition ratio [x / (x + y)] of x with respect to the sum of x and y and the composition ratio [x / y] of x with respect to y are not more than the above upper limit, sufficient gas barrier ability can be obtained more easily. Moreover, if the composition ratio [x / (x + y)] of x with respect to the sum of x and y and the composition ratio [x / y] of x with respect to y are equal to or higher than the above lower limit, an adjacent base material or an organic material if present Since peeling does not easily occur between the silicon compound layers, it can be preferably applied to roll conveyance and bent use. Moreover, it is preferable that x and y satisfy | fill the relationship of 4- (2x + 3y) =-0.5-1.0. Moreover, since 4- (2x + 3y) is 0.8 or less, more preferably 0.4 or less, since coloring is suppressed, it is easy to use the film for a wide range of applications. If 4- (2x + 3y) is −0.35 or more, the constituent ratio of silicon / nitrogen / oxygen is high, the defect ratio can be easily suppressed, and more sufficient gas barrier ability can be expected. For this reason, 4- (2x + 3y) is preferably a combination of −0.35 to 0.4, and more preferably a combination of −0.36 to 0.40. Particularly in the case of -0.32 to 0.2, the visible light transmittance is high, and a stable gas barrier ability is obtained, which is most preferable.

  The refractive index of the barrier layer is not particularly limited, but is preferably 1.7 to 2.1, more preferably 1.8 to 2, and particularly preferably 1.9 to 2.0. . A barrier layer having such a refractive index has a high visible light transmittance, and a high gas barrier ability can be stably obtained.

  As the method for forming the barrier layer of the present invention, any method can be used as long as the target thin film can be formed. For example, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, a wet coating method, and the like are suitable. Specifically, each of Japanese Patent No. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774. The formation method described in the publication can be employed in the same manner or with appropriate modification.

  The thickness (application thickness) of the barrier layer can be appropriately set according to the purpose. For example, the thickness of the barrier layer (coating thickness) is preferably about 10 nm to 10 μm, more preferably 50 nm to 1 μm, and even more preferably 20 nm to 2 μm as the thickness after drying. , 300 nm or less is particularly preferable. If the thickness of the barrier layer is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 μm or less, stable coating properties can be obtained when forming the barrier layer, and high light transmittance can be realized.

Further, the film density of the barrier layer can be appropriately set according to the purpose. For example, the film density of the barrier layer is preferably in the range of 1.5 to 2.6 g / cm ³ . Outside this range, the film composition of the silicon nitride (SiO _x N _y ) film collapses, the film density decreases, and the barrier property may deteriorate, or the film may deteriorate due to humidity. In this specification, the film composition of the silicon nitride (SiO _x N _y ) film can be measured by photoelectron spectroscopy (XPS), and a specific apparatus is ESCA3200 manufactured by Shimadzu Corporation. . The film density can be measured by the X-ray reflectivity method. In this specification, as a specific measuring apparatus, a value (g / g) measured using ATX-G manufactured by Rigaku Corporation. cm ³ ).

The barrier layer according to the present invention contains SiO _x N _y but is preferably formed from polysilazane.

(Polysilazane)
The “polysilazane” according to the present invention is a polymer having a silicon-nitrogen bond in the structure, and has SiO ₂ , Si ₃ N ₄ having a bond such as Si—N, Si—H, or N—H, and an intermediate thereof. It is a ceramic precursor inorganic polymer such as solid solution SiO _x N _y . Specifically, the polysilazane according to the present invention preferably has the following structure.

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

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

Perhydropolysilazane, in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms, is particularly preferred from the viewpoint of denseness as a barrier layer film. Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring, and its molecular weight is about 600 to 2000 in terms of number average molecular weight (Mn) (gel Polystyrene conversion by permeation chromatography), which is a liquid or solid substance. Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing coating solution. As a commercial item of polysilazane solution, AZ Electronic Materials Co., Ltd. Aquamica (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110 NP140, SP140 and the like.

  Alternatively, the polysilazane according to the present invention 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 a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) It is an alkyl group. In this case, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

  In the above general formula (II), n and p are integers and are determined so that the polysilazane having the structure represented by the general formula (II) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable. 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 and R ₄ each represent a methyl group, and R ₅ represents a vinyl group; R ₁ , R ₃ , R ₄ and R ₆ each represent a hydrogen atom, R ₂ and R Compounds in which ₅ each represents a methyl group are preferred.

  Alternatively, the polysilazane according to the present invention 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 a hydrogen atom, a substituted or unsubstituted alkyl group, or aryl group , A vinyl group or a (trialkoxysilyl) alkyl group. In this case, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

  In the above general formula (III), n, p and q are integers so that the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. Preferably, it is defined. Note that n, p, and q may be the same or different.

Among the polysilazanes of the general formula (III), R ₁ , R ₃ and R ₆ each represent a hydrogen atom, R ₂ , R ₄ , R ₅ and R ₈ each represent a methyl group, and R ₉ represents (triethoxy A compound which represents a (silyl) propyl group and R ₇ represents an alkyl group or a hydrogen atom is preferred.

  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, perhydropolysilazane and organopolysilazane may be selected as appropriate 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. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  Other examples of polysilazanes that can be used in the present invention include, but are not limited to, for example, silicon alkoxide-added polysilazanes obtained by reacting the above polysilazanes with silicon alkoxides (Japanese Patent Laid-Open No. 5-238827) and glycidol. 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.

  The content of polysilazane in the barrier layer according to the present invention can be 100% by weight when the total weight of the barrier layer is 100% by weight. When the barrier layer contains other than polysilazane, the content of polysilazane in the barrier layer is preferably 10% by weight or more and 99% by weight or less, and 40% by weight or more and 95% by weight or less. Is more preferably 70 wt% or more and 95 wt% or less.

The method for forming the polysilazane layer according to the present invention is not particularly limited, and a known method can be applied. A polysilazane and a coating solution for forming a polysilazane layer containing a catalyst as necessary in an organic solvent can be applied by a known wet coating method. Apply and remove the solvent by evaporation, thereby forming a polysilazane layer on the substrate, and then in the presence of air or ozone, the polysilazane layer is irradiated with ultraviolet light of 400 nm or less to convert silica. In addition, a barrier layer containing SiO _x (x is 1.2 to 2.0) can be formed.

  In the above method, as a method for applying a polysilazane layer-forming coating solution containing polysilazane onto a substrate, 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, wireless bar coating method, gravure printing method, etc. Is mentioned.

  The solvent for preparing the coating liquid for forming the polysilazane 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, as a solvent for preparing a coating liquid for forming a polysilazane layer, an aprotic solvent; for example, an aliphatic hydrocarbon such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, turben, an alicyclic ring, etc. Hydrocarbon solvents such as hydrocarbons and aromatic hydrocarbons; 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; Dibutyl ether, dioxane and tetrahydrofuran Ethers such as aliphatic ethers and alicyclic ethers: for example, 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 liquid for forming the polysilazane layer is not particularly limited and varies depending on the film thickness of the gas barrier layer and the pot life of the coating liquid, but is preferably 1 to 80% by weight, more preferably 5 to 50% by weight, Particularly preferably, it is 10 to 40% by weight.

  The polysilazane layer-forming coating solution preferably contains a catalyst together with polysilazane in order to promote modification into silicon oxynitride. 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 mol%, more preferably 0.5 to 7 mol%, based on polysilazane. By setting the addition amount of the catalyst within 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 polysilazane layer forming coating solution according to the present invention, the following additives may 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, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

  By using such a coating liquid for forming a polysilazane layer, it is possible to produce a dense glass-like barrier layer excellent in a high barrier action against a gas having no cracks or holes.

  The thickness (film thickness) of the polysilazane layer can be appropriately set according to the purpose. For example, the thickness (film thickness) of the polysilazane layer is preferably about 10 nm to 10 μm, more preferably 20 nm to 2 μm, and even more preferably 50 nm to 1 μm as the thickness after drying. , 300 nm or less is particularly preferable. If the thickness of the polysilazane layer is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 μm or less, stable coating properties can be obtained when forming the polysilazane layer, and high light transmittance can be realized.

In the gas barrier layer according to the present invention, the polysiloxane described above is converted into silica (modified treatment), and SiO _x N _y (x is 0.5 to 2.3, y is 0.1 to 0.1). 3.0).

  Here, the method for forming the barrier layer by converting the polysiloxane into silica is not particularly limited, but the polysilazane layer is irradiated with ultraviolet rays using light energy having a wavelength of 400 nm or less, preferably light energy having a wavelength of 300 nm or less. It is preferable to convert the polysiloxane to silica by irradiation with ultraviolet light, particularly irradiation with vacuum ultraviolet light (VUV) having a wavelength of less than 180 nm. Here, in silica conversion, cleavage of Si—H and N—H bonds and generation of Si—O bonds occur, and conversion to ceramics such as silica is carried out. The degree of this conversion is defined below by IR measurement. According to the equation (1), it can be evaluated semi-quantitatively by the SiO / SiN ratio.

Here, the SiO absorbance is calculated by absorption (absorbance) at about 1160 cm ⁻¹ and the SiN absorbance at about 840 cm ⁻¹ . It shows that conversion to the ceramic close | similar to a silica composition is progressing, so that SiO / SiN ratio is large.

  In the present invention, the SiO / SiN ratio, which is an index of the degree of conversion to ceramics, is 0.3 or more, preferably 0.5 or more. If it is less than 0.3, the expected gas barrier property may not be obtained.

Or as a measuring method of the silica conversion rate ( _x in SiOx) concerning this invention, it can measure using XPS method, for example.

  The composition of the metal oxide (SiOx) of the barrier layer can be measured by measuring the atomic composition ratio using an XPS surface analyzer. It can also be measured by cutting the barrier layer and measuring the cut surface with an XPS surface analyzer.

[Modification of barrier layer (polysilazane layer)]
In the method for producing a gas barrier film of the present invention, a barrier layer (SiO _x N _y layer) is produced on at least one surface side of the substrate. After forming a polysilazane layer by applying a coating liquid containing polysilazane onto a substrate, the polysilazane layer is formed by irradiating ultraviolet rays using light energy having a wavelength of 400 nm or less to convert to silica. Here, the ultraviolet irradiation may be performed only once or may be repeated twice or more. However, at least one of the ultraviolet light of 400 nm or less to be irradiated is irradiated with ultraviolet light having a wavelength component of 300 nm or less (UV In particular, it is preferably vacuum ultraviolet irradiation light (VUV) having a wavelength component of less than 180 nm. For example, when using a radiation source having a radiation component of a wavelength of 300 nm or less, such as a Xe ₂ ^* excimer radiator having a maximum emission at about 172 nm or a low pressure mercury vapor lamp having an emission line at about 185 nm, in the presence of oxygen and / or water vapor In the above-mentioned wavelength range, ozone and oxygen radicals and hydroxyl radicals are generated very efficiently by photolysis due to the high extinction coefficient of these gases, and these promote the oxidation of the polysilazane layer. Both mechanisms, i.e., the cleavage of the Si-N bond and the action of ozone, oxygen radicals, and hydroxyl radicals, can only occur when ultraviolet light reaches the surface of the polysilazane layer.

  Therefore, in order to apply UV radiation (especially VUV radiation) on the surface of the layer at the highest possible dose, in some cases the UV (especially VUV radiation) treatment path can be replaced with nitrogen, where oxygen and water vapor can be adjusted. In this wavelength range, it is necessary to reduce the path length of the ultraviolet rays according to the intended purpose by correspondingly reducing the oxygen and water vapor concentrations.

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

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

Here, the presumed mechanism in which the coating film containing polysilazane is modified in the vacuum ultraviolet irradiation step and becomes a specific composition of SiO _x N _y will be described by taking perhydropolysilazane as an example.

Perhydropolysilazane can be represented by a composition of “— (SiH ₂ —NH) _n —”. In the case of SiO _x N _y , x = 0 and y = 1. In order to satisfy x> 0, an external oxygen source is required. This is because (i) oxygen and moisture contained in the polysilazane coating solution, and (ii) oxygen taken into the coating film from the atmosphere during the coating and drying process. As an outgas from the substrate side due to oxygen, moisture, ozone, singlet oxygen taken into the coating film from the atmosphere in the vacuum ultraviolet irradiation process, (iv) heat applied in the vacuum ultraviolet irradiation process, etc. Oxygen and moisture moving into the coating film, (v) When the vacuum ultraviolet irradiation process is performed in a non-oxidizing atmosphere, when moving from the non-oxidizing atmosphere to the oxidizing atmosphere, Oxygen, moisture, etc. taken into the coating film become oxygen sources.

  On the other hand, for y, the condition under which nitriding proceeds rather than the oxidation of Si is considered to be very special, so basically 1 is the upper limit.

  Also, from the relationship of Si, O, and N bond, x and y are basically in the range of 2x + 3y ≦ 4. In the state of y = 0 where the oxidation has progressed completely, the coating film contains silanol groups, and there are cases where 2 <x <2.5.

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

(I) Dehydrogenation and accompanying Si—N bond formation Si—H bonds and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation by vacuum ultraviolet irradiation, etc., and in an inert atmosphere, Si— It is considered that they are recombined as N (a dangling bond of Si may be formed). That is, the cured as SiN _y composition without oxidizing. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H ₂ .

(II) Formation of Si—O—Si Bonds by Hydrolysis / Dehydration Condensation Si—N bonds in perhydropolysilazane are hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. Two Si—OHs are dehydrated and condensed to form Si—O—Si bonds and harden. This is a reaction that occurs in the air, but during vacuum ultraviolet irradiation in an inert atmosphere, water vapor generated as outgas from the base material by the heat of irradiation is considered to be the main moisture source. When the moisture is excessive, Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO2.1 to 2.3 is obtained.

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

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

  Adjustment of the composition of the silicon oxynitride of the layer subjected to vacuum ultraviolet irradiation on the layer containing polysilazane can be performed by appropriately controlling the oxidation state by appropriately combining the oxidation mechanisms (I) to (IV) described above. .

In the vacuum ultraviolet ray irradiation step of the present invention, the excellent barrier action against gas, particularly water vapor and oxygen is such that the polysilazane layer (amorphous polysilazane layer) applied as described above is about 100 ° C. or less, preferably 90 to 90 ° C. It is successfully converted to a glass-like silicon dioxide network in a temperature of 40 ° C. in 0.1 to 10 minutes. By initiating the oxidative conversion of the polysilazane skeleton into a three-dimensional SiO _x network directly with VUV photons, this conversion is successfully performed in a very short time in a single step. The mechanism of this conversion process is that in the range of penetration depth of VUV photons, the Si—N bond is broken and the -SiH ₂ —NH— component is so strong that layer conversion occurs in the presence of oxygen and water vapor. It can be explained that it is excited by its absorption. The present invention is not limited by the following mechanism.

In vacuum ultraviolet irradiation step in the present invention, it is preferable that the illuminance of the vacuum ultraviolet rays in the coating film surface for receiving the polysilazane coating film is 30~200mW / cm ^2, more preferably 50~160mW / cm ² . If it is less than 30 mW / cm ^2, there is a concern that the reforming efficiency is greatly reduced, and if it exceeds 200 mW / cm ² , there is a concern that the coating film may be ablated or the substrate may be damaged.

Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably 200~5000mJ / cm ^2, more preferably 500~3000mJ / cm ^2. Is less than 200 mJ / cm ^2, there is a fear that the reforming becomes insufficient, 5000 mJ / cm ² than the cracking or due to excessive modification concerns the thermal deformation of the substrate emerges.

  As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used. Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules.

  However, excited atoms of rare gases that have gained energy by discharge or the like can form molecules by combining with other atoms. When the rare gas is xenon,

Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted.

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

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a gas space that is generated in a gas space by applying a high frequency high voltage of several tens of kHz to the electrode by placing a gas space between both electrodes via a dielectric such as transparent quartz. It is a discharge called a thin micro discharge. When the micro discharge streamer reaches the tube wall (derivative), electric charges accumulate on the dielectric surface, and the micro discharge disappears.

  This micro discharge spreads over the entire tube wall, and is a discharge that is repeatedly generated and extinguished. For this reason, flickering of light that can be confirmed with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge is possible in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp and electrodes and their arrangement may be basically the same as for dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes. Therefore, in order to cause discharge in the entire discharge space, the outer electrode covers the entire outer surface and transmits light to extract light to the outside. Must be a thing.

  For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.

  The outer diameter of the tube of the thin tube lamp is about 6 nm to 12 mm, and if it is too thick, a high voltage is required for starting.

  As the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

  Suitable radiation sources in the present invention include an excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp), a low pressure mercury vapor lamp having an emission line at about 185 nm, and medium and high pressure mercury having a wavelength component of 230 nm or less. Vapor lamps 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. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane layer can be modified in a short time.

  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.

  Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

Further, the action of UV light not containing a wavelength component of 180 nm or less from a low-pressure mercury lamp (HgLP lamp) (185 nm, 254 nm) or a KrCl ^* excimer lamp (222 nm) that emits light having wavelengths of 185 nm and 254 nm is The photodegradation action is limited, ie, it does not generate oxygen radicals or hydroxyl radicals. In this case, since the absorption is negligible, no restrictions on oxygen and water vapor concentration are required. Yet another advantage over shorter wavelength light is the greater depth of penetration into the polysilazane layer.

  Oxygen is necessary for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process is likely to decrease. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen concentration during vacuum ultraviolet irradiation is preferably 10 to 210,000 volume ppm, more preferably 50 to 10,000 volume ppm, and even more preferably 500 to 5,000 volume ppm. . Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

  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 the present invention, the formation of a glass-like layer in the form of a SiO _x N _y lattice is accelerated by simultaneously increasing the temperature of the layer, and the quality of the layer is improved with respect to its barrier properties. Heat input can be done through the coating and substrate with the UV lamp used or with an infrared radiator, or through the gas phase space with a heat resistor. The upper limit of temperature is determined by the heat resistance of the used base material. In the case of a PET film, it is about 180 ° C.

  In one preferred embodiment of the invention, during the oxidative conversion process, the substrate is heated by infrared to a temperature of 50-200 ° C. (depending on the heat resistance of the substrate to be coated), and at the same time Exposed to radiation. In yet another preferred embodiment, the gas temperature in the irradiation chamber during the conversion process is increased to a temperature of 50-200 ° C. By doing so, the coating is simultaneously heated on the substrate, and the conversion of the polysilazane layer is accelerated.

  The method of the present invention involves coating, drying and oxidative conversion in a single work step by irradiating a polysilazane layer on a plastic film, i.e., for example in film coating, this is "roll to roll". ) ”Method. The coating obtained according to the present invention has a high barrier action against gases such as oxygen, carbon dioxide, air or water vapor.

  The barrier layer according to the present invention may have a single layer structure, or may have a multilayer structure of two or more layers by performing the method of the present invention several times before and after. Thereby, the barrier action can be further enhanced.

[Organic silicon compound layer]
As described above, the gas barrier film of the present invention may have an organic silicon compound layer formed on the barrier layer in addition to the base material and the barrier layer formed on the base material. That is, the gas barrier film of the present invention preferably further includes an organosilicon compound layer between the barrier layer and the curable resin layer. Thus, by further providing an organosilicon compound layer between the barrier layer and the curable resin layer, the flexibility is increased, and thus the barrier ability, particularly the barrier ability against water vapor and oxygen can be improved.

  Here, the organosilicon compound layer means a layer containing carbon atoms. The organosilicon compound layer is preferably a silicon oxide organic layer mainly composed of carbon, hydrogen, oxygen, and silicon. In the present specification, “mainly composed of carbon, hydrogen, oxygen, and silicon” means that the total of elements of silicon, oxygen, and carbon is preferably 90% by weight or more of all elements constituting the entire layer. It means a component that preferably accounts for 95% by weight or more, more preferably 98% by weight or more.

  The material constituting the organosilicon compound layer is not particularly limited, but is preferably formed from a compound having a siloxane bond. Since the barrier layer is glass-like, it tends to crack locally. However, by providing an organosilicon compound layer between the barrier layer and the curable resin layer in this way, a siloxane structure with good adhesion to the barrier layer is disposed on the barrier layer, thereby causing cracks. Can be suppressed / prevented.

  Although it does not restrict | limit especially as a compound which has a siloxane bond, A polysiloxane and an organic inorganic hybrid polymer are used preferably. Below, polysiloxane and an organic-inorganic hybrid polymer are explained in full detail.

(Polysiloxane)
The polysiloxane is not particularly limited, and known polysiloxanes can be used in the same manner. For example, (1) organopolysiloxane that exhibits high strength by hydrolyzing and polycondensing chloro or alkoxysilane, etc. by sol-gel reaction, etc., (2) organo crosslinked with reactive silicone with excellent water and oil repellency Organopolysiloxanes such as polysiloxane can be preferably used.

In the case of (1) above, the general formula: Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, An acetyl group or a halogen atom, n is an integer from 0 to 3.) An organopolysiloxane which is one or more hydrolyzed condensates or cohydrolyzed condensates of an alkylalkoxysilane compound represented by It is preferable that Here, the number of carbon atoms of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.

  Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxy Silane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyl Lutriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n -Decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane Phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane; tetrachlorosilane Tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, Diphenyldimethoxysilane, diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxy Hydrosilane, tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribromosilane, vinyltri Methoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane; trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyl Triisopropoxysilane, trifluoropropyltri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane; γ-methacryloxypropylmethyldimethyl Xysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyl Tri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ- Aminopropyltri-t-butoxysilane; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrieth Xysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane And partial hydrolysates thereof; and mixtures thereof can be used.

  A commercial item can be used as alkyl alkoxysilane. Specifically, there is Glasca HPC402H manufactured by JSR Corporation.

  In particular, a polysiloxane containing a fluoroalkyl group can be preferably used. Specific examples include one or two or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes: In general, those known as fluorine-based silane coupling agents can be used.

Fluoroalkylsilane: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ; (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ; _{3) 2 CF (CF 2)} 6 CH 2 CH 2 Si (OCH 3) 3; (CF 3) 2 CF (CF 2) 8 CH 2 CH 2 Si (OCH 3) 3; CF 3 (C 6 H 4) _{C 2 H 4 Si (OCH 3} ) 3; CF 3 (CF 2) 3 (C 6 H 4) C 2 H 4 Si (OCH 3) 3; CF 3 (CF 2) 5 (C 6 H 4) C 2 H ₄ Si (OCH ₃ ) ₃ CF ₃ (CF ₂ ) ₇ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) _{5 CH 2 CH 2 SiCH 3 (} OCH 3) 2; CF 3 (CF 2) 7 CH 2 CH 2 SiCH 3 (OCH 3) 2; CF 3 (CF 2) 9 CH 2 CH 2 SiCH 3 (OCH 3) 2 _{; (CF 3) 2 CF (} CF 2) 4 CH 2 CH 2 SiCH 3 (OCH 3) 2; (CF 3) 2 CF (CF 2) 6 CH 2 CH 2 Si CH 3 (OCH 3) 2; (CF _{3) 2 CF (CF 2)} 8 CH 2 CH 2 Si CH 3 (OCH 3) 2; CF 3 (C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2; CF 3 (CF 2) 3 ( C _{6 4) C 2 H 4 SiCH 3} (OCH 3) 2; CF 3 (CF 2) 5 (C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2; CF 3 (CF 2) 7 (C 6 H _{4) C 2 H 4 SiCH 3} (OCH 3) 2; CF 3 (CF 2) 3 CH 2 CH 2 Si (OCH 2 CH 3) 3; CF 3 (CF 2) 5 CH 2 CH 2 Si (OCH 2 CH _{3) 3; CF 3 (CF} 2) 7 CH 2 CH 2 Si (OCH 2 CH 3) 3; CF 3 (CF 2) 9 CH 2 CH 2 Si (OCH 2 CH 3) 3; and _CF 3 (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ CH ₂ Si (OCH ₃ ) ₃ .

  By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the ink repellency of the non-exposed part of the organosilicon compound layer is greatly improved, and the function of preventing the adhesion of the light-shielding part paint or coloring ink Is expressed.

  Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula (IV).

In the general formula (IV), n is an integer of 2 or more, and R ¹ and R ² are a substituted or unsubstituted alkyl group, alkenyl group, aryl group or cyanoalkyl group having 1 to 10 carbon atoms. In a molar ratio, 40% or less of the total is vinyl, phenyl, or phenyl halide. Further, it is preferable that R ¹ and R ² are methyl groups since the surface energy is the smallest, and it is preferable that the methyl groups are 60% or more by molar ratio. In addition, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.

  Moreover, you may mix the stable organosilicon compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.

  The organosilicon compound layer in the present invention can further contain a surfactant. Specifically, hydrocarbons such as NIKKOL (registered trademark) BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL (registered trademark) FSN, FSO, manufactured by DuPont, Surflon manufactured by Asahi Glass Co., Ltd. (Registered Trademark) S-141, 145, Dainippon Ink & Chemicals, Inc. MegaFace (Registered Trademark) F-141, 144, Neos Co., Ltd., Fantent (Registered Trademark) F-200, F251, Daikin Industries Fluorine or silicone nonionic surfactants such as Unidyne (registered trademark) DS-401, 402 manufactured by Co., Ltd., Fluorard (registered trademark) FC-170, 176 manufactured by 3M Co., Ltd. can be mentioned. Cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.

  In addition to the above surfactants, the organosilicon compound layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. Can be contained.

  Such an organosilicon compound layer can be formed by preparing the coating liquid by dispersing the above-described components together with other additives in a solvent as necessary, and coating the coating liquid on the barrier layer. it can. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. In the case where an ultraviolet curable component is contained, the organic silicon compound layer can be formed by performing a curing treatment by irradiating ultraviolet rays.

  In the present invention, the thickness of the organosilicon compound layer is preferably 0.1 to 5 μm, particularly preferably 0.3 to 1.5 μm, in consideration of the relationship such as the wettability change rate by the photocatalyst. Is within. When the thickness of the organosilicon compound layer is 0.1 μm or more, sufficient adhesion with the barrier layer can be obtained. By setting the thickness of the organosilicon compound layer to 5 μm or less, cracks are less likely to occur in the organosilicon compound layer.

(Organic inorganic hybrid polymer)
The organosilicon compound layer can be a layer made of an organic-inorganic hybrid polymer. The organic-inorganic hybrid polymer is excellent in adhesion with the barrier layer. The organic-inorganic hybrid polymer is a polymer obtained by hydrolyzing / co-condensing one or more selected from the group consisting of organosilane, hydrolyzate of organosilane, and condensate of organosilane, and a silyl group-containing organic polymer. .

  Here, the organosilane is preferably a compound represented by the following general formula (V) (hereinafter referred to as compound (1)).

In the general formula (V), R ¹ represents an organic group having 1 to 8 carbon atoms, R ² represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is 0 to 2 Represents an integer.

R ¹ is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, an octyl group or a 2-ethylhexyl group; an acyl group such as an acetyl group, a propionyl group, a butyryl group or a benzoyl group A vinyl group, an allyl group, a cyclohexyl group, a phenyl group and the like. When two R ¹ are present, they may be the same group or different groups.

Examples of R ² include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group; and an acyl group having 1 to 6 carbon atoms such as an acetyl group, a propionyl group, and a butyryl group. It is done. R ² may be the same group or different groups.

Specific examples of the compound (1) include tetraalkoxysilanes (n = 0) such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane;
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Trialkoxysilanes such as butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane (n = 1) ;
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldi Examples include dialkoxysilanes (n = 2) such as ethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, and di-n-octyldiethoxysilane. It is done.

  These compounds (1) may be used individually by 1 type, and may use 2 or more types together. Moreover, you may use a compound (1) as a hydrolyzate or a condensate.

  The silyl group-containing organic polymer is an organic polymer having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal and / or side chain of the organic polymer. Examples of the silyl group-containing organic polymer include silyl group-containing acrylic resins, silyl group-containing vinyl resins, silyl group-containing urethane resins, silyl group-containing epoxy resins, specific silyl group-containing polyester resins, and specific silyl group-containing fluororesins.

  As the silyl group, a group represented by the following general formula (VI) is preferable.

In the general formula (VI), X represents a hydrolyzable group or a hydroxyl group, R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having 1 to 10 carbon atoms, and m is 1 to 3 Represents an integer. Here, examples of the hydrolyzable group include a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxyl group, and an amino group.

  The organic-inorganic hybrid polymer is obtained by adding a hydrolysis / condensation catalyst and water to the compound (1) and the silyl group-containing organic polymer, and hydrolyzing / co-condensing the compound (1) and the silyl group-containing organic polymer. Examples of the hydrolysis / condensation catalyst include acidic compounds, alkaline compounds, salt compounds, amine compounds, organometallic compounds, and partial hydrolysates thereof.

  Among these, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, etc. are mentioned as an acidic compound. Examples of the alkaline compound include sodium hydroxide and potassium hydroxide. Examples of the salt compound include alkali metal salts. Examples of the organometallic compound include tetravalent tin organometallic compounds. Examples of the amine compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) -aminopropyltrimethoxysilane, and the like.

  The organosilicon compound layer may be thermally crosslinked with a curing agent from the viewpoint of increasing the hardness to some extent. By being thermally crosslinked, surface tack of the organosilicon compound layer is suppressed, thermal expansion and contraction are suppressed, and cracks in the barrier layer are suppressed. Examples of the curing agent include tin compounds, aluminum compounds, zirconium compounds (such as zirconia). The amount of the curing agent is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the organic-inorganic hybrid polymer.

  The organosilicon compound layer may contain an inorganic filler. Examples of the inorganic filler include silica, alumina, titanium oxide that does not function as a photocatalyst, zirconia, zinc oxide, cerium oxide, and the like, and silica is preferable from the viewpoint of maintaining hydrophilicity. The amount of the inorganic filler is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the organic-inorganic hybrid polymer.

  The organosilicon compound layer may contain other resins excluding the organic-inorganic hybrid polymer, known additives, and the like as long as the object of the present invention is not impaired.

  The thickness of the organosilicon compound layer is preferably 0.05 to 5 μm. By setting the thickness of the organosilicon compound layer to 0.05 μm or more, sufficient adhesion with the barrier layer can be obtained. By setting the thickness of the organosilicon compound layer to 5 μm or less, cracks are less likely to occur in the organosilicon compound layer.

  The organic silicon compound layer is applied, for example, by applying a coating solution for an organic silicon compound layer containing an organic-inorganic hybrid polymer, a solvent, and, if necessary, a curing agent on a film substrate by a known coating method, followed by heating and drying. It can be formed by a method. Further, after drying, it may be crosslinked and cured by an actinic ray such as an ultraviolet ray or an electron beam.

  In addition, the organic silicon compound layer formed as described above is further irradiated with ultraviolet light using light energy having a wavelength of 400 nm or less, preferably ultraviolet light using light energy having a wavelength of 300 nm or less. It is preferably formed by irradiation with vacuum ultraviolet light (VUV) of less than 180 nm. Thereby, the organosilicon compound layer becomes dense. Irradiation with ultraviolet light is effective at any time after the formation of the coating film. Further, for the ultraviolet irradiation, the same conditions as described in the above-mentioned “Modification treatment of the barrier layer (polysilazane layer)” can be applied, and thus the description thereof is omitted.

  The organosilicon compound layer is preferably a composition whose main constituent elements are carbon, hydrogen, oxygen and silicon. The proportion of silicon is preferably between 10% and 30%.

The film density of the organosilicon compound layer is preferably 0.5 to 1.5 g / cm ³ . If the film density of the organosilicon compound layer is in the above range, the gas barrier film can exhibit sufficient barrier properties without causing cracks. In this specification, the film composition of the organosilicon compound layer can be measured by photoelectron spectroscopy (XPS), and a specific apparatus is ESCA3200 manufactured by Shimadzu Corporation. Alternatively, the film density can also be measured by the X-ray reflectivity method, and a specific measuring apparatus includes ATX-G manufactured by Rigaku Corporation.

  In consideration of the compatibility between the barrier property and the flexibility of the present invention, the element ratio C / Si of the organosilicon compound layer is preferably 0.2 to 0.8, and particularly preferably 0.35 to 0.7.

[Curable resin layer]
In the gas barrier film of the present invention, a curable resin layer is disposed on the barrier layer. By arranging the curable resin layer in this manner, the occurrence of cracks on the surface can be suppressed, and the barrier ability, particularly the barrier ability against water vapor and oxygen can be improved. In addition, since the curable resin layer has an adhesive ability, it can be satisfactorily bonded to the display element when used in a display element, as will be described in detail below.

  Examples of the curable resin used in the present invention include various light (for example, ultraviolet ray) curable resins, electron beam curable resins, thermosetting resins, and two-component curable resins. More specifically, thermosetting resins such as urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, unsaturated polyester resin, polyurethane resin or acrylic resin; ester acrylate, urethane Radical type photocurable resins using resins such as various acrylates such as acrylates, epoxy acrylates, melamine acrylates, acrylic resin acrylates, or urethane polyesters; and cationic photocurable resins using resins such as epoxies and vinyl ethers. . Specifically, a thermosetting resin such as a thermosetting epoxy resin (manufactured by ThreeBond Co., Ltd., two-part epoxy resin; 20X-325), an ultraviolet curable adhesive (manufactured by Kyoritsu Chemical Industry Co., Ltd., WORD) And UV curable resins such as ROCK 8723L2).

  The curable resin used in the present invention is not particularly limited as long as the layer shape can be maintained. In this case, it is preferable to use a photocurable resin composition having a relatively high viscosity. A photocurable resin having a relatively high viscosity may be selected and used, a delayed curable photocurable resin may be used, and an additive such as a filler is appropriately added to the curable resin so as to increase the viscosity. You may add and use.

  The thickness of the cured resin layer is usually in the range of 1 to 200 μm, preferably in the range of 2 to 150 μm, and more preferably in the range of 5 to 100 μm. If it is such a range, a gas barrier film will be excellent in a flexibility, without generating a crack.

〔Base material〕
As a base material of the gas barrier film of the present invention, in order to avoid deformation due to heating or moisture absorption, it is preferable to use a thermal expansion coefficient or a material having a low humidity expansion coefficient, and the thermal expansion coefficient is 100 ppm / ° C. or less. It is 50 ppm / ° C. or lower and 1 ppm / ° C. or higher, preferably 20 ppm / ° C. or lower and 3 ppm / ° C. or higher, more preferably 15 ppm / ° C. or lower and 5 ppm / ° C. or higher. These expansion coefficients can be adjusted by selecting a material and selecting a draw ratio. Here, the coefficient of thermal expansion is determined by using a thermomechanical analyzer and using a sample synthetic resin film heated at 80 ° C. for 10 minutes and dried, temperature: dimensional change at 50 ° C. to 150 ° C. It is obtained by reading.

  The base material has a glass transition temperature (Tg) of the resin constituting the base material of 150 in addition to the above-mentioned definition of the coefficient of thermal expansion coefficient or humidity expansion coefficient, or the definition of the thermal expansion coefficient and the humidity expansion coefficient. It is preferable that the temperature is at least ° C. When the Tg is less than 150 ° C., the base material is easily softened by heat generated when the barrier layer is formed on the base material, and the base material is easily deformed by an external force applied to the base material. In this sense, Tg is preferably higher, but in the range specifically exemplified below, it is 300 ° C. or lower. If the glass transition temperature exceeds 300 ° C., the flexibility of the base material itself is lowered and the flexibility is lost, so that continuous processing may be difficult.

  As a synthetic resin of a material constituting a specific base material, in a crystalline resin, polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, (PEN) or syndiotactic polystyrene, polyphenylene sulfide, polyether Ether ketone, liquid crystal polymer, fluororesin, polyether nitrile and the like can be mentioned as preferable resins.

  In addition, as a synthetic resin of the material constituting the base material, in the case of an amorphous resin, polycarbonate, modified polyphenylene ether, polycyclohexene, or polynorbornene resin, polysulfone, polyethersulfone, polyarylate, polyamideimide, polyether Imide, thermoplastic polyimide, or the like can be cited as a more preferable resin. Among these, polycarbonate has a low water absorption, and therefore, a substrate formed using the polycarbonate has a low humidity expansion coefficient and is particularly preferable. Furthermore, acrylate type, methacrylate type, etc. can be used in the photocurable resin.

  The thermal properties required for the substrate, particularly the behavior with respect to external force, can be defined by the deflection temperature under load, which is a more practical index, and those with a deflection temperature under load of 150 ° C. or higher are preferred. Incidentally, the deflection temperature under load of each resin is as follows: polycarbonate resin; 160 ° C., polyarylate resin; 175 ° C., polyethersulfone resin; 210 ° C., cycloolefin polymer (manufactured by Nippon Zeon Co., Ltd., trade name; “ZEONOR (registered trademark)” ) ”); 150 ° C. or norbornene resin (manufactured by JSR Corporation, trade name:“ ARTON (registered trademark) ”);

  Or the thermal property requested | required of a base material can be prescribed | regulated also by the maximum continuous use temperature, and what is 150 degreeC or more as a maximum continuous use temperature is preferable. The maximum continuous use temperature of each resin is equal to the deflection temperature under load of each resin in the range of the resins listed in the previous paragraph.

  When the substrate is applied to the viewing side of the display, it is preferable that the substrate has transparency from the viewpoint of ensuring the visibility of the image. Moreover, the thickness of a base material is about 1-400 micrometers, and it is good to select suitably according to a use.

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

  Moreover, it is preferable that the base material which concerns on this invention is transparent. Since the base material is transparent and the layer formed on the base material is also transparent, it becomes possible to make a transparent gas barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. It is.

  In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

  The base material used in the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Further, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

  Various known treatments for improving adhesion, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, or both sides of the substrate, at least on the side where the barrier layer (curable resin layer) according to the present invention is provided, or Lamination of the primer layer and the like can be performed in combination as necessary.

[Anchor coat layer]
On the surface of the substrate according to the present invention, an anchor coat layer may be formed as an easy-adhesion layer for the purpose of improving adhesion (adhesion) with the barrier layer. Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One or two or more can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) can be used.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). A commercially available base material with an easy-adhesion layer may be used.

  Alternatively, 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.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

[Primer layer (smooth layer)]
The gas barrier film of the present invention may have a primer layer (smooth layer). The primer layer flattens the rough surface of the transparent resin film substrate on which protrusions and the like exist, or fills irregularities and pinholes generated in the transparent first barrier layer with protrusions existing on the transparent resin film substrate. Provided for flattening. Such a primer layer is basically formed by curing a photosensitive material or a thermosetting material.

  Examples of the photosensitive material used for forming the primer 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, Examples thereof include resin compositions in which polyfunctional acrylate monomers such as urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are 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. 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.

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

  The composition of the photosensitive resin contains a photopolymerization initiator.

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

  Specifically, as a thermosetting material, Tutprom series (Organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid silicone manufactured by Adeka, Unidick manufactured by DIC, Inc. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistance epoxy resin), various silicon resins X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. Organic nanocomposite material SSG coat, thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicon resin, and the like. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

  The method for forming the primer layer is not particularly limited, but it 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 primer layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. Further, regardless of the position where the primer layer is laminated, any primer layer may use an appropriate resin or additive for improving the film forming property and preventing the generation of pinholes in the film.

  Solvents used when forming a primer layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, α -Or terpenes such as β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Group hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, di Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, diethylene glycol Dialkyl ether, dipropylene glycol Lumpur dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smoothness of the primer layer is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. If it is smaller than 10 nm, the coatability may be impaired when the coating means comes into contact with the surface of the primer layer by a coating method such as a wire bar or wireless bar at the stage of coating a silicon compound described later. . Moreover, when larger than 30 nm, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound. Note that the lower limit of the maximum cross-sectional height Rt (p) is not particularly limited and is 0 nm, but it may normally be 0.5 nm or more.

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

  Although it does not restrict | limit especially as thickness of a primer layer, The range of 0.5-10 micrometers is preferable.

(Additive to primer layer)
One preferred embodiment includes reactive silica particles (hereinafter also simply referred to as “reactive silica particles”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the photosensitive resin. Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be. Moreover, as a photosensitive resin, what adjusted solid content by mixing a general-purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.

  Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By setting the average particle size in such a range, the antiglare property and the resolution, which are the effects of the present invention, can be obtained by using in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm described later. It becomes easy to form a primer layer having both optical properties satisfying a good balance and hard coat properties. From the viewpoint of making it easier to obtain such an effect, it is more preferable to use an average particle size of 0.001 to 0.01 μm. The primer layer used in the present invention preferably contains the inorganic particles as described above in a weight ratio of 20% to 60%. Addition of 20% or more improves adhesion with the gas barrier layer. On the other hand, if it exceeds 60%, the film may be bent or cracks may occur when heat treatment is performed, or the optical properties such as transparency and refractive index of the gas barrier film may be affected.

  In the present invention, a polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to a silica particle by generating a silyloxy group by a hydrolysis reaction of a hydrolyzable silyl group. Can be used as reactive silica particles.

  Examples of the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl group, and a hydridosilyl group.

  Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

  In the present invention, the thickness of the primer layer is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the primer property as a film having a primer layer sufficiently, and by making it 10 μm or less, it becomes easy to adjust the balance of optical properties of a smooth gas barrier film, and the primer layer When the film is provided only on one surface of the transparent polymer film, curling of the primer film can be easily suppressed.

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

  Examples of the unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer include a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or in the molecule And monounsaturated organic compounds having one polymerizable unsaturated group.

  Here, as the polyunsaturated organic compound, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meta ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane Tiger (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of unit unsaturated organic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl. (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-eth Ciethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by weight or more, preferably 4 parts by weight or more, more preferably 6 parts by weight or more and 20 parts by weight or less, preferably 100 parts by weight of the solid content of the hard coating agent. It is desirable that they are mixed in a proportion of 18 parts by weight or less, more preferably 16 parts by weight or less.

  In addition, the bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.

  Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof. Vinyl resins such as polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicon resin etc. are mentioned.

  In addition, as an ionizing radiation curable resin, an ionizing radiation (ultraviolet ray or electron beam) is irradiated to an ionizing radiation curable coating material in which one or more of a photopolymerizable prepolymer or a photopolymerizable monomer is mixed. Those that cure can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl). ) -1-propane, α-acyloxime ester, thioxanthone and the like.

  The bleed-out prevention layer as described above is prepared as a coating solution by mixing a hard coating agent, a matting agent, and other components as necessary, and appropriately using a diluent solvent as necessary. It can be formed by coating the film surface with a conventionally known coating method and then curing it by irradiating with ionizing radiation. As a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer is one of the transparent polymer films. When it is provided on this surface, curling of the barrier film can be easily suppressed.

<< Packing form of gas barrier film >>
The gas barrier film of the present invention can be continuously produced and wound into a roll form (so-called roll-to-roll production). In that case, it is preferable to stick and wind up a protective sheet on the surface in which the gas barrier layer was formed. In particular, when the gas barrier film of the present invention is used as a sealing material for an organic thin film device, it often becomes a defect due to dust (particles) adhering to the surface, and a protective sheet is pasted in a highly clean place. It is very effective to prevent the adhesion of dust. In addition, it is effective in preventing scratches on the gas barrier layer surface that enters during winding.

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

  The gas barrier film of the present invention as described above has excellent gas barrier properties, transparency, and flexibility. For this reason, the gas barrier film of the present invention is a gas barrier film used for electronic devices such as packages such as electronic devices, solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, and the like, and an electronic device using the same. It can be used for various purposes such as devices. Therefore, this invention also provides the electronic device which uses a gas-barrier film for a display element. In the above application, the gas barrier film of the present invention may be installed in any place, but it is preferable that the curable resin layer is installed in contact with the display element.

  When the gas barrier film of the present invention is used as a substrate for a display element (display), a layer necessary for each display method can be laminated on either the front or back of the gas barrier film. Since another layer may be laminated between the substrate and the gas barrier film, the gas barrier film of the present invention has a layer for providing a display function between the substrate and the gas barrier film. Including those intervening.

  There are various types of displays to which the gas barrier film of the present invention is applied, and there are no particular limitations, but typical examples include liquid crystal displays and organic EL elements.

  A liquid crystal display is one in which transparent electrodes are placed on the inside of two glass substrates, the liquid crystal is sandwiched between alignment layers, etc., and the periphery is sealed. With a color filter to convert. The gas barrier film of the present invention can be applied to the outside of the glass substrate of such a liquid crystal display, or the gas barrier film 1 of the present invention can be used in place of the glass substrate. In particular, if both of the two glass substrates are replaced with the gas barrier film of the present invention, the entire display can be made flexible.

  In the organic EL display, a transparent electrode is disposed on both glass substrates, and between the two substrates, for example, (a) injection function, (b) transport function, and (c) light emission. The organic EL element layer composed of a composite layer, etc., in which layers having various functions are stacked is sandwiched and the periphery is sealed, and accompanied by a color filter or other means for colorizing the image There is. As in the liquid crystal display, the gas barrier film of the present invention can be applied to the outside of the glass substrate, or the gas barrier film 1 of the present invention can be used in place of the glass substrate. If both glass substrates are replaced with the gas barrier film of the present invention, the entire display can be made flexible. Since the organic EL element has an unstable fluorescent substance and is extremely sensitive to moisture, a high water vapor barrier property after the product is desired, and therefore, application of a gas barrier film is very effective.

  Each characteristic value of the gas barrier film of the present invention can be measured according to the following method.

(Measurement of water vapor transmission rate)
Various methods have been proposed for measuring the water vapor transmission rate according to the method B described in JIS K 7129 (1992). For example, the cup method, dry / wet sensor method (Lassy method), infrared sensor method (mocon method) can be mentioned as representatives, but as the gas barrier properties improve, these methods may reach the measurement limit. A method is also proposed. In addition,
<Method of measuring water vapor transmission rate other than the above>
1. Ca method A method in which metal Ca is vapor-deposited on a gas barrier film and the phenomenon in which metal Ca is corroded by moisture that has permeated through the film. The water vapor transmission rate is calculated from the corrosion area and the time to reach the corrosion area.

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

3. HTO method (US General Atomics)
A method of calculating water vapor transmission rate using tritium.

4). Method proposed by A-Star (Singapore) (International Publication No. 2005/95924)
A method of calculating a water vapor transmission rate from a change in electric resistance and a fluctuation component inherent therein using a material (for example, Ca, Mg) whose electric resistance is changed by water vapor or oxygen as a sensor.

In the gas barrier film of the present invention, the method for measuring the water vapor transmission rate is not particularly limited, but in the present specification, as the water vapor transmission rate measurement method, the measurement by the Ca method described above is performed, and the value obtained by the method is used. Was the water vapor transmission rate (g / m ² · 24 h).

The water vapor permeability of the gas barrier film of the present invention is preferably as low as possible. For example, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻² g / m ² · 24 h, and preferably 1 × 10 ⁻⁶ to 1 ×. More preferably, it is 10 ⁻² g / m ² · 24 h. In the gas barrier film of the present invention, the method for measuring the water vapor transmission rate is not particularly limited, but the water vapor transmission rate is expressed as a value measured by the Ca method described above.

[Measurement of oxygen permeability]
Using an oxygen permeability measuring device (model name, “Oxytran” (registered trademark) (“OXTRAN” 2/20)) manufactured by MOCON, USA, under conditions of a temperature of 23 ° C. and a humidity of 0% RH , Measured according to the B method (isobaric method) described in JIS K7126 (1987). In addition, each of the two test pieces was measured once, and the average value of the two measured values was used as the oxygen permeability value.

The oxygen permeability of the gas barrier film of the present invention is preferably as low as possible, but is preferably 0.01 g / m ² · 24 h · atm or less, for example, 0.001 g / m ² · 24 h · atm or less. In particular, it is more preferably less than 0.001 g / m ² · 24 h · atm (below the detection limit).

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Further, in the examples, the display of “part” or “%” is used, but “part by weight” or “% by weight” is expressed unless otherwise specified.

  Each characteristic value of the gas barrier film is measured according to the following method.

<< Method for measuring characteristic values of gas barrier film >>
[Measurement of x and y in SiO _x N _y ]
About the barrier layer of each produced gas barrier film, it measured by XPS method. Specifically, using a VG Scientific fix Co. ESCALAB-200R, Mg as an X-ray anode, output 600W (acceleration voltage 15kV, emission current 40 mA) as measured by and calculated x and y in _SiO x _{N y} .

[Evaluation of water vapor barrier properties (WVTR)]
In accordance with the following measurement method, the permeated moisture amount of each gas barrier film was measured, and the water vapor barrier property was evaluated according to the following criteria.

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

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

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

The permeated water amount (g / m ² · 24 h; “WVTR” in the table) of each gas barrier film measured as described above was evaluated by the Ca method.

[Evaluation of bending resistance (flexibility)]
Each gas barrier film was bent 100 times at an angle of 180 degrees so that the radius of curvature was 10 mm, and then the amount of permeated water was measured by the same method as above, and the permeated moisture before and after the bending treatment. From the change in amount, the degree of deterioration resistance was measured according to the following formula, and the bending resistance was evaluated according to the following criteria.

Deterioration resistance = (permeated water amount after bending test / permeated water amount before bending test) × 100 (%)
5: Deterioration resistance is 90% or more 4: Deterioration resistance is 80% or more and less than 90% 3: Deterioration resistance is 60% or more and less than 80% 2: Deterioration resistance is 30% or more and less than 60% 1: Deterioration resistance is less than 30% [Measurement of visible light transmittance (transparency)]
The visible light transmittance (%) of each gas barrier film was measured using a spectrophotometer V-570 (manufactured by JASCO Corporation).

[Evaluation of adhesiveness]
The gas barrier film (200 mm long, 200 mm wide) obtained in each example was fixed in a frame and immersed in water heated to 70 ° C. for 30 minutes for boil treatment. After the treatment, the film was taken out and T-peeled at 20 ° C. and 65% relative humidity (RH) using a universal material testing machine (manufactured by Shimadzu Corp., Autograph) at a tensile speed of 200 mm / min. The test was conducted and the delamination strength (N / cm) was measured. When the delamination strength was 1.5 N / cm or more, it was determined that the present invention has the adhesive ability.

Examples 1-7
[Production of gas barrier film]
(Formation of polysilazane layer)
As a base film, a polyethylene naphthalate resin film having a glass transition temperature of 155 ° C., a thermal expansion coefficient of 8 ppm, a humidity expansion coefficient of 0.5 ppm, and a thickness of 200 μm (manufactured by Teijin DuPont Co., Ltd., trade name: “Teonex” Registered trademark))), and a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) is applied on one side by gravure printing, and 120 After drying with hot air at a temperature of 0 ° C., UV curing was performed to form a primer layer having a thickness of 0.1 μm. A polysilazane layer was formed on the primer layer according to the following method.

  A 10 wt% dibutyl ether solution of perhydropolysilazane (Aquamica (registered trademark) NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was used as a coating solution for forming a polyosilazan layer.

  The polysilazane layer-forming coating solution is applied with a wireless bar so that the (average) film thickness after drying is 150 nm, and is dried by treatment for 1 minute in an atmosphere of temperature 85 ° C. and humidity 55% RH. Furthermore, it was kept for 10 minutes in an atmosphere of temperature 25 ° C. and humidity 10% RH (dew point temperature −8 ° C.) to perform dehumidification treatment, thereby forming a polysilazane layer.

(Barrier layer formation: Silica conversion of polysilazane layer by ultraviolet light)
Next, silica conversion treatment was performed on the polysilazane layer formed above under the conditions of a dew point temperature of −8 ° C. or lower according to the following method.

With respect to the barrier layer thus formed, _{x and y} in SiO _x N _y were measured by XPS method using ESCALAB-200R manufactured by VG Scientific, and the results are shown in Table 1 below. Further, the film density of the barrier layer thus formed was measured, and the results are shown in Table 1 below.

(Formation of curable resin layer)
Subsequently, on the barrier layer formed as described above, a thermosetting epoxy resin (manufactured by ThreeBond Co., Ltd., two-pack epoxy resin; 20X-325) and the film thickness (when dried) described in Table 1 Thus, it applied using a dispenser, it was made to harden | cure at 80 degreeC for 1 hour, the curable resin layer was formed, and the gas barrier films 1-7 were obtained.

  The gas barrier film thus obtained was evaluated for adhesiveness, water vapor barrier property (“WVTR” in Table 1 below), bending resistance (“flexibility” in Table 1 below) and transparency. The results are shown in Table 1 below.

Examples 8-10
[Production of gas barrier film]
(Formation of barrier layer)
A barrier layer was formed in the same manner as in Examples 5-7.

(Formation of curable resin layer)
Subsequently, on the barrier layer formed as described above, an ultraviolet curable adhesive (manufactured by Kyoritsu Kagaku Sangyo Co., Ltd., WORK ROCK 8723L2) is formed so as to have the film thickness (when dry) described in Table 1. It apply | coated using the dispenser, it irradiated and hardened only on the application | coating part on the following conditions, the curable resin layer was formed, and the gas barrier films 8-10 were obtained.

  The gas barrier film thus obtained was evaluated for adhesiveness, water vapor barrier property (“WVTR” in Table 1 below), bending resistance (“flexibility” in Table 1 below) and transparency. The results are shown in Table 1 below.

Comparative Example 1
In Example 1 above, a gas barrier film 11 was obtained according to the method described in Example 1 except that the curable resin layer was not formed.

  The gas barrier film thus obtained was evaluated for adhesiveness, water vapor barrier property (“WVTR” in Table 1 below), bending resistance (“flexibility” in Table 1 below) and transparency. The results are shown in Table 1 below.

Comparative Example 2
In Example 10 above, a gas barrier film 12 was obtained according to the method described in Example 10 except that the curable resin layer was not formed.

  The gas barrier film thus obtained was evaluated for adhesiveness, water vapor barrier property (“WVTR” in Table 1 below), bending resistance (“flexibility” in Table 1 below) and transparency. The results are shown in Table 1 below.

  As is clear from the results shown in Table 1 above, the gas barrier films 1 to 10 of the present invention have adhesiveness, gas barrier properties (WVTR), bending resistance (compared to the gas barrier films 11 and 12 of the comparative example). It can be seen that it has excellent flexibility and high visible light permeability.

Examples 11-12
[Production of gas barrier film]
(Formation of barrier layer)
A barrier layer was formed in the same manner as in Example 1.

(Formation of organosilicon compound layer)
Subsequently, 30 parts by weight of silica sol (trade name: Glasca HPC7002, manufactured by JSR Corporation) and 10 parts by weight of alkylalkoxysilane (trade name: Glasca HPC402H, manufactured by JSR Corporation) were stirred and mixed for 30 minutes. A coating solution for forming an organosilicon compound layer was obtained. This coating solution was applied onto the barrier layer formed above using a spin coater. The film was heated at 100 ° C. for 10 minutes and further subjected to a modification treatment under the following conditions to form an organosilicon compound layer (film density: 0.5) having a thickness of 1 μm.

(Formation of curable resin layer)
Subsequently, a thermosetting epoxy resin (manufactured by ThreeBond Co., two-pack epoxy resin; 20X-325) is formed on the organic silicon compound layer formed as described above, and the film thickness (when dried) ) Was applied using a dispenser and cured at 80 ° C. for 1 hour to form a curable resin layer to obtain gas barrier films 13 to 14.

  The gas barrier film thus obtained was evaluated for adhesiveness, water vapor barrier property (“WVTR” in Table 2 below), bending resistance (“flexibility” in Table 2 below) and transparency. The results are shown in Table 2 below.

Examples 13-14
[Production of gas barrier film]
(Formation of barrier layer)
A barrier layer was formed in the same manner as in Example 1.

(Formation of organosilicon compound layer)
Subsequently, 30 parts by weight of silica sol (trade name: Glasca HPC7002, manufactured by JSR Corporation) and 10 parts by weight of alkylalkoxysilane (trade name: Glasca HPC402H, manufactured by JSR Corporation) were stirred and mixed for 30 minutes. A coating solution for forming an organosilicon compound layer was obtained. This coating solution was applied onto the barrier layer formed above using a spin coater. The film was heated at 100 ° C. for 10 minutes and further subjected to a modification treatment under the following conditions to form an organosilicon compound layer (film density: 0.5) having a thickness of 1 μm.

(Formation of curable resin layer)
Subsequently, an ultraviolet curable adhesive (manufactured by Kyoritsu Kagaku Sangyo Co., Ltd., WORK ROCK 8723L2) is formed on the organic silicon compound layer formed as described above so as to have a film thickness (when dried) described in Table 2. Then, it was applied using a dispenser, and only the application part was irradiated and cured under the following conditions to form a curable resin layer, and gas barrier films 15 to 16 were obtained.

  The gas barrier film thus obtained was evaluated for adhesiveness, water vapor barrier property (“WVTR” in Table 2 below), bending resistance (“flexibility” in Table 2 below) and transparency. The results are shown in Table 2 below.

  As is clear from the results shown in Table 2 above, the gas barrier films 13 to 16 of the present invention are excellent in adhesion, gas barrier properties (WVTR), bending resistance (flexibility), and have high visible light permeability. I understand that

Examples 15-17
[Production of gas barrier film]
(Formation of polysilazane layer)
As a base film, a polyethylene naphthalate resin film having a glass transition temperature of 155 ° C., a thermal expansion coefficient of 8 ppm, a humidity expansion coefficient of 0.5 ppm, and a thickness of 200 μm (manufactured by Teijin DuPont Co., Ltd., trade name: “Teonex” Registered trademark))), and a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) is applied on one side by gravure printing, and 120 After drying with hot air at a temperature of 0 ° C., UV curing was performed to form a primer layer having a thickness of 0.1 μm. A polysilazane layer was formed on the primer layer according to the following method.

  A 10 wt% dibutyl ether solution of perhydropolysilazane (AQUAMICA (registered trademark) NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was used as a coating solution for forming a polysilazane layer.

  The polysilazane layer-forming coating solution is applied with a wireless bar so that the (average) film thickness after drying is 150 nm, and is dried by treatment for 1 minute in an atmosphere of temperature 85 ° C. and humidity 55% RH. Furthermore, it was kept for 10 minutes in an atmosphere of temperature 25 ° C. and humidity 10% RH (dew point temperature −8 ° C.) to perform dehumidification treatment, thereby forming a polysilazane layer.

(Barrier layer formation: Silica conversion of polysilazane layer by low-pressure mercury lamp)
Subsequently, the polysilazane layer formed above was subjected to silica conversion treatment under the condition of a dew point temperature of −8 ° C. or lower according to the following method using a low pressure mercury lamp.

With respect to the barrier layer thus formed, _{x and y} in SiO _x N _y were measured by XPS method using ESCALAB-200R manufactured by VG Scientific, and the results are shown in Table 3 below. Further, the film density of the barrier layer thus formed was measured, and the results are shown in Table 3 below.

(Formation of curable resin layer)
Subsequently, a thermosetting epoxy resin (manufactured by Three Bond, two-pack epoxy resin; 20X-325) on the barrier layer formed as described above, and the film thickness (when dried) described in Table 3 Thus, it applied using a dispenser, it was made to harden | cure at 80 degreeC for 1 hour, the curable resin layer was formed, and the gas barrier films 17-19 were obtained.

  The gas barrier film thus obtained was evaluated for adhesiveness, water vapor barrier property (“WVTR” in Table 3 below), bending resistance (“flexibility” in Table 3 below) and transparency. The results are shown in Table 3 below.

Examples 18-20
[Production of gas barrier film]
(Formation of barrier layer)
A barrier layer was formed in the same manner as in Examples 15-17.

(Formation of organosilicon compound layer)
Subsequently, 30 parts by weight of silica sol (trade name: Glasca HPC7002, manufactured by JSR Corporation) and 10 parts by weight of alkylalkoxysilane (trade name: Glasca HPC402H, manufactured by JSR Corporation) were stirred and mixed for 30 minutes. A coating solution for forming an organosilicon compound layer was obtained. This coating solution was applied onto the barrier layer formed above using a spin coater. The film was heated at 100 ° C. for 10 minutes and further subjected to a modification treatment under the following conditions to form an organosilicon compound layer (film density: 0.5) having a thickness of 1 μm.

(Formation of curable resin layer)
Subsequently, a thermosetting epoxy resin (manufactured by ThreeBond Co., two-pack epoxy resin; 20X-325) is formed on the organic silicon compound layer formed as described above, and the film thicknesses (when dried) are listed. ) Was applied using a dispenser and cured at 80 ° C. for 1 hour to form a curable resin layer, and gas barrier films 20 to 22 were obtained.

  The gas barrier film thus obtained was evaluated for adhesiveness, water vapor barrier property (“WVTR” in Table 3 below), bending resistance (“flexibility” in Table 3 below) and transparency. The results are shown in Table 3 below.

Comparative Example 3
A gas barrier film 23 was obtained according to the method described in Example 16 except that the curable resin layer was not formed in Example 16.

  The gas barrier film thus obtained was evaluated for adhesiveness, water vapor barrier property (“WVTR” in Table 3 below), bending resistance (“flexibility” in Table 3 below) and transparency. The results are shown in Table 3 below.

Comparative Example 4
A gas barrier film 24 was obtained according to the method described in Example 19 except that the curable resin layer was not formed in Example 19.

  The gas barrier film thus obtained was evaluated for adhesiveness, water vapor barrier property (“WVTR” in Table 3 below), bending resistance (“flexibility” in Table 3 below) and transparency. The results are shown in Table 3 below.

  As is clear from the results shown in Table 3 above, the gas barrier films 17 to 19 of the present invention are compared with the gas barrier film 23 of the comparative example, and the gas barrier films 20 to 22 of the present invention are comparative. As compared with the gas barrier film 24 of the example, it can be seen that the film has excellent adhesive ability, gas barrier property (WVTR), bending resistance (flexibility), and high visible light transmittance.

Examples 21-27, Comparative Examples 5-7
[Production of organic EL elements]
(1) Preparation of organic EL element substrate A conductive glass substrate (surface resistance value 10Ω / □, 0.6 mm thickness) having an ITO film as an organic EL substrate was washed with 2-propanol, and then UV-ozone for 10 minutes. Processed. The following first hole transport layer, second hole transport layer, and light emitting layer / electron transport layer were sequentially deposited on the substrate (anode) by vacuum deposition.

(First hole transport layer)
Copper phthalocyanine: film thickness 10nm
(Second hole transport layer)
N, N′-diphenyl-N, N′-dinaphthylbenzidine: film thickness 40 nm
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum: film thickness 60nm
Finally, lithium fluoride is sequentially deposited to a thickness of 1 nm and metal aluminum to a thickness of 100 nm to form a cathode, and a 5 μm thick silicon nitride film is formed thereon by a parallel plate CVD method to form an organic EL element. Produced.

(2) Installation of gas barrier film Gas barrier films 1 to 3, 13, 14, 18, and 21 prepared in Examples 1 to 3, 11, 12, 16, and 19 and Comparative Examples 1 to 3 as sealing films. The organic EL element was sealed using the gas barrier films 11, 12 and 23 produced in the above.

  Specifically, in the gas barrier films 1 to 3, 13, 14, 18, and 21 prepared in Examples 1 to 3, 11, 12, 16, and 19, the curable resin layer was prepared in the above (1). Each gas barrier film was laminated with an organic EL element and a vacuum muraminator installed in a nitrogen purge glove box so as to be in contact with the element surface of the organic EL element, and heated at 100 ° C. for 1 hour to obtain the organic EL element. Sealed.

  Moreover, in the gas barrier films 11, 12, and 23 produced in Comparative Examples 1 to 3, an adhesive sheet (manufactured by Three Bond Co., Ltd., thermosetting sheet-like adhesive, trade name: 1655) and each gas barrier film Then, the adhesive sheet and the barrier layer of the gas barrier film were successively stacked and heated at 100 ° C. for 1 hour to seal the organic EL element.

(3) Evaluation of organic EL element About the organic EL element produced above, durability was evaluated in accordance with the following method.

(Accelerated deterioration processing)
Each of the produced organic EL elements is allowed to stand for 750 hours in an environment of 60 ° C. and 90% RH and subjected to accelerated deterioration treatment. Then, together with the organic EL elements not subjected to accelerated deterioration treatment, darkness is performed as follows. The number of spots (non-light emitting parts) was counted.

That is, 1 mA / cm ^{2 for} each of the organic EL elements subjected to the accelerated deterioration treatment (“after 750 hours” in Table 4) and the organic EL elements not subjected to the accelerated deterioration treatment (“initial” in Table 4). Then, a portion of the panel was enlarged with a 100 × microscope (MS-804 manufactured by Moritex Co., Ltd., lens MP-ZE25-200) and photographed. The photographed image was cut out in a 2 mm square, and the number of dark spots (non-light emitting portions) was counted. The results are shown in Table 4 below. In Table 4, it was determined as “OK” if the change in the number of dark spots was 2 or less, and “NG” if it increased beyond that.

  As is clear from the results shown in Table 4 above, the organic EL device having the gas barrier films 1 to 3, 13, 14, 18, and 21 of the present invention has the gas barrier films 11, 12, and 23 of the comparative example. It can be seen that the change in the number of dark spots is small and the durability is excellent as compared with the organic EL element.

11 ... gas barrier film,
12 ... base material,
13 ... Barrier layer,
14 ... curable resin layer,
15: Organosilicon compound layer.

Claims (9)

A barrier layer containing SiO _x N _y (where x is 0.5 to 2.3 and y is 0.1 to 3.0) and curable resin layer on at least one of the substrates A gas barrier film comprising:   The gas barrier film according to claim 1, wherein the barrier layer is formed from polysilazane.   The gas barrier film according to claim 1 or 2, wherein the barrier layer is formed by ultraviolet irradiation using light energy having a wavelength of 300 nm or less.   The gas barrier film according to any one of claims 1 to 3, wherein the barrier layer has a thickness of 300 nm or less.   The gas barrier film according to claim 1, further comprising an organosilicon compound layer between the barrier layer and the curable resin layer.   The gas barrier film according to claim 5, wherein the organosilicon compound layer is formed from a compound having a siloxane bond.   The gas barrier film according to claim 5 or 6, wherein the organosilicon compound layer is formed by ultraviolet irradiation using light energy having a wavelength of 300 nm or less.   The electronic device which uses the gas-barrier film of any one of Claims 1-7 for a display element.   The electronic device of Claim 8 installed so that the said curable resin layer may contact | connect a display element.

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