JP2014223578A - Gas barrier film manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a gas barrier film having a high gas barrier property and excellent in storage stability under a high temperature condition.SOLUTION: A method for manufacturing a gas barrier film having at least one layer of a gas barrier film on a film base material, comprising; (1) a step of forming a coating film by applying a solution containing a silicon oxide precursor or silicon oxynitride precursor to the film base material; (2) a step of irradiating the coating film with an ultraviolet light containing a wavelength component less than 200 nm; and (3) a step of irradiating the coating film with an ultraviolet light having a wavelength not less than 200 nm but less than 230 nm.

Description

  The present invention relates to a method for producing a gas barrier film.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging goods and foods that require blocking of various gases such as water vapor and oxygen. It is widely used for packaging and the like to prevent alteration of industrial products and pharmaceuticals. In addition to packaging applications, they are used in liquid crystal display elements, solar cells, organic electroluminescence (hereinafter abbreviated as organic EL) elements, and the like. In particular, liquid crystal display elements, organic EL elements, and the like are required to have high gas barrier properties (gas barrier properties) because internal penetration of water vapor or air causes deterioration in quality.

  The demand for such a high gas barrier property such as water vapor and air has become more severe in recent years, and in addition, there is a demand for a method for producing a gas barrier film by a lower cost and simple method. Various attempts have been made. As such a conventional technique, a technique for producing a transparent gas barrier film on a film substrate is known (see Patent Document 1). However, since this technique requires a vacuum process for producing the gas barrier film, there is a problem that the apparatus becomes large and the cost is high.

On the other hand, as a method for producing a gas barrier film, there has been proposed a method for producing a gas barrier film containing silicon oxide by applying vacuum ultraviolet light irradiation to a coating film coated with a polysilazane compound solution. This method uses light energy of 100 nm to 200 nm called vacuum ultraviolet light (hereinafter also referred to as “VUV” or “VUV light”), which is larger than the interatomic bonding force in the polysilazane compound. In this manufacturing method, a silicon oxide film that becomes a gas barrier film at a relatively low temperature can be produced by advancing an oxidation reaction with active oxygen or ozone while directly cutting atomic bonds by the action of only photons called photon processes. Can be done. For example, a method of converting a polysilazane compound coating film into a silicon oxide film by irradiating an excimer lamp of a VUV light source having an illuminance of 40 mW / cm ² for 3 to 10 minutes is disclosed (see Patent Document 2). ). However, there is a problem that this irradiation condition is not suitable for industrial continuous production of a gas barrier film.

  From the viewpoint of manufacturing a gas barrier film, it is preferable that it can be continuously produced industrially by so-called roll-to-roll. As a conventional technique related to a roll-to-roll manufacturing method, there is known a method of manufacturing a gas barrier film by conveying a film and irradiating a polysilazane compound coating film with vacuum ultraviolet light from an excimer lamp (Patent Literature). 3). According to this method, high gas barrier properties are obtained by combining vacuum ultraviolet light of 200 nm or less and 230 to 300 nm ultraviolet light.

JP 2009-196155 A JP 2009-255040 A Special table 2009-503157

  However, the gas barrier films described in Patent Documents 1 to 3 have a problem that the gas barrier properties deteriorate due to changes over time.

  Accordingly, an object of the present invention is to provide a method for producing a gas barrier film having high gas barrier properties and excellent storage stability, particularly storage stability under severe conditions (high temperature conditions).

  The present inventor has intensively studied to solve the above problems. As a result, the step of irradiating the coating film containing a silicon oxide precursor or silicon oxynitride precursor with ultraviolet light containing a wavelength component of less than 200 nm, and irradiating with ultraviolet light of 200 nm or more and less than 230 nm It has been found that a gas barrier film obtained by a production method having the above solves the above problems. Based on the above findings, the present invention has been completed.

  That is, the present invention is a method for producing a gas barrier film having at least one gas barrier film on a film substrate, and (1) a silicon oxide precursor or a silicon oxynitride precursor on the film substrate. A step of applying a solution containing a body to form a coating film; (2) a step of irradiating the coating film with ultraviolet light containing a wavelength component of less than 200 nm; and (3) a coating film having a thickness of 200 nm to less than 230 nm. And a step of irradiating with ultraviolet light having a wavelength.

  According to the present invention, a method for producing a gas barrier film having high gas barrier properties and excellent storage stability under high temperature conditions can be provided.

(A) is an external view which shows an example of an ultraviolet light irradiation unit, (b) is sectional drawing which shows an example of an ultraviolet light irradiation unit. It is a figure which shows the result of having measured the ultraviolet absorption spectrum of the coating film, after forming the coating film containing perhydropolysilazane on a quartz substrate, and irradiating the ultraviolet light of wavelength 172nm so that irradiation amount may differ. (A) shows the ultraviolet absorption spectrum when the irradiation amount is 0J (no irradiation), 1J, 3J, and 6J, respectively, and (b) shows the case where the irradiation amount is 1J, 3J, and 6J and the irradiation amount of 0J. It is the graph which took the difference with the case.

  The present invention is a method for producing a gas barrier film having at least one gas barrier film on a film substrate, wherein (1) a silicon oxide precursor or a silicon oxynitride precursor is formed on the film substrate. A step of forming a coating film by applying a solution containing, (2) a step of irradiating the coating film with ultraviolet light containing a wavelength component of less than 200 nm, and (3) a wavelength of 200 nm or more and less than 230 nm on the coating film. And a step of irradiating with ultraviolet light.

  The gas barrier film obtained by such a production method exhibits high gas barrier properties and is excellent in storage stability, particularly storage stability at high temperatures.

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

  In the present specification, “X to Y” indicating a range means “X or more and Y or less”, and “weight” and “mass”, “wt%” and “mass%”, “part by weight” and “ “Part by mass” is treated as a synonym. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

(1) Step of forming a coating film by applying a solution containing a silicon oxide precursor or silicon oxynitride precursor on a film substrate In this step, a silicon oxide precursor or silicon is formed on the film substrate. A solution containing the oxynitride precursor is applied to form a coating film.

(Film substrate)
Examples of the film substrate used in the gas barrier film according to the present invention include a metal substrate such as silicon, a glass substrate, a ceramic substrate, and a plastic film, and a plastic film is preferably used. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a gas barrier film, a hard coat layer and the like, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  When the gas barrier film according to the present invention is used as a substrate of an electronic device such as an organic EL element, the film base material is preferably made of a heat-resistant material. Specifically, a resin film substrate having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 ° C. or more and 300 ° C. or less is used. The resin film substrate satisfies the requirements for use as a laminated film for electronic parts and displays. That is, when the gas barrier film according to the present invention is used for these applications, the gas barrier film may be exposed to a process at 150 ° C. or higher. In this case, if the linear expansion coefficient of the film base material in the gas barrier film exceeds 100 ppm / K, the substrate dimensions are not stable when the gas barrier film is passed through the temperature process as described above, and the thermal expansion and contraction occur. Inconvenience that the shut-off performance is deteriorated or a problem that it cannot withstand the heat process is likely to occur. If it is less than 15 ppm / K, the film may break like glass and the flexibility may deteriorate.

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

  When the gas barrier film according to the present invention is used in combination with a polarizing plate, it is preferable that the gas barrier film of the gas barrier film is disposed on the inner side (adjacent to the element) so as to face the inside of the cell. At this time, since the gas barrier film is disposed inside the cell from the polarizing plate, the retardation value of the gas barrier film is important. The usage form of the gas barrier film in such an embodiment is as follows: a gas barrier film using a film substrate having a retardation value of 10 nm or less and a circularly polarizing plate (¼ wavelength plate + (1/2 wavelength plate) + straight line. The polarizing plate is preferably used in combination with a linear polarizing plate in combination with a gas barrier film using a film substrate having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate. .

  Examples of the film substrate having a retardation of 10 nm or less include cellulose triacetate (Fuji Film Co., Ltd .: Fujitac (registered trademark)), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace (registered trademark), Kaneka Corporation): Elmec (registered trademark)), cycloolefin polymer (manufactured by JSR Corporation: Arton (registered trademark), Nippon Zeon Corporation: ZEONOR (registered trademark)), cycloolefin copolymer (manufactured by Mitsui Chemicals, Inc .: APPEL (registered trademark)) (Pellets), manufactured by Polyplastics Co., Ltd .: Topas (registered trademark) (pellets)), polyarylate (manufactured by Unitika Co., Ltd .: U100 (pellets)), transparent polyimide (manufactured by Mitsubishi Gas Chemical Co., Ltd .: Neoprim (registered trademark)) Etc.

  Moreover, as a quarter wavelength plate, the film base material adjusted to the desired retardation value by extending | stretching said film base material suitably can be used.

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

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

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

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

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

  The film substrate 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 substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  It is preferable to perform various known treatments for improving adhesion, for example, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, etc., on at least the side of the film base on which the gas barrier film according to the present invention is provided, It is more preferable to combine the above treatments as necessary.

(Silicon oxide precursor, silicon oxynitride precursor)
Specific examples of silicon oxide precursors or silicon oxynitride precursors (hereinafter also simply referred to as precursors) include, for example, perhydropolysilazane, organopolysilazane, silsesquioxane, tetramethylsilane, and trimethylmethoxysilane. , Dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1- Silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldivinylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsila , Dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoropropyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilyl Acetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxy Vinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane, diaryldimethoxysilane, butyldimeth Sivinylsilane, trimethyl-3-vinylthiopropylsilane, phenyltrimethylsilane, dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethyphenylsilane, benzoy Loxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanate Topropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, dibutoxydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) Triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, diacetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethyl Phenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxypropylmethylsilane, octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxy Silane, dodecyltrimethylsilane, diarylmethylphenylsilane, diphenylmethylvinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1 , 3-Divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, , 3-bis (3-acetoxypropyl) tetramethyldisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-tris Fluoropropyl) -1,3 5-trimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3,5,7-tetraethoxy-1,3,5,7-tetramethyl cyclotetrasiloxane, may be mentioned decamethylcyclopentasiloxane like. These precursors can be used alone or in combination of two or more.

  As the silsesquioxanes such, Mayaterials made Q8 series of Octakis (tetramethylammonium) pentacyclo-octasiloxane-octakis (yloxide) hydrate; Octa (tetramethylammonium) silsesquioxane, Octakis (dimethylsiloxy) octasilsesquioxane, Octa [[3 - [(3- ethyl-3-oxyethyl) methyoxy] propyl] dimethylsiloxy] octasilsesquioxane; Octalyloxetanes silsesquioxane, Octa [(3-Propylglycidylethyl ) Dimethylsiloxy] silsesquioxane; Octakis [[3- (2,3-epoxypropoxy) propyl] dimethylsiloxy] octasilsesquioxane, Octakis [[2- (3,4-epoxycyclohexyl) ethyl] dimethylsiloxy] octasilsesquioxane, Octakis [2- (vinyl) dimethylsiloxy] silsesquioxane; Octakis (dimethylvinylsilyloxy) octasilesquioxane, Octakis [(3-hydroxypropyloyl) dimethylsiloxy] octasilsesquioxane ethacryloylpropyl) dimethylsilyloxy] silsesquioxane, Octakis [(3-methacryloxypropyl) dimethylsiloxysequioxane, and hydrogenated groups containing no organic groups such as oxysilenes.

  Among these precursors, polysilazanes such as perhydropolysilazane and organopolysilazane; polysiloxanes such as silsesquioxane, and the like are preferable in terms of film formation, fewer defects such as cracks, and less residual organic matter. Polysilazane is more preferable, and perhydropolysilazane is particularly preferable because the performance is high and the barrier performance is maintained even when bent and under high temperature and high humidity conditions.

Polysilazane is a polymer having a silicon-nitrogen bond, having a bond such as Si-N, Si-H, N-H, etc., and SiO ₂ , Si ₃ N ₄ , and intermediate solid solutions of both SiO _x N _y. It is an inorganic polymer to be a precursor such as.

  Specifically, the polysilazane preferably has the following structure.

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

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

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

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

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

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

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

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

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

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

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

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

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

(Coating solution for coating film formation)
The solvent used in the preparation of the coating liquid for forming a coating film in this step (hereinafter also simply referred to as a coating film-forming coating liquid) is not particularly limited as long as it can dissolve the precursor. An organic solvent that does not contain water and a reactive group (for example, a hydroxyl group or an amine group) that easily react with the precursor and is inert to the precursor is preferable, and an aprotic organic solvent is more preferable. Specifically, the solvent includes an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben. Hydrogen solvents; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. The solvent is selected according to purposes such as the solubility of the precursor and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of the precursor in the coating liquid for forming a coating film is not particularly limited and varies depending on the film thickness of the gas barrier film and the pot life of the coating liquid, but is preferably 1 to 80% by weight, more preferably 5 to 50% by weight. More preferably, it is 10 to 40% by weight.

  The coating liquid for forming a coating film preferably contains a catalyst in order to promote modification. Examples of the catalyst applicable to the present invention include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′—. Amine compounds such as tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, and Pd compounds such as propionic acid Pd Metal catalysts such as Rh compounds such as Rh acetylacetonate, N-heterocyclic compounds, pyridine compounds such as pyridine, α-picoline, β-picoline, γ-picoline, piperidine, lutidine, pyrimidine, pyridazine, DBU (1 , 8-diazabicyclo [5.4.0] -7-undecene), DBN (1,5-diazabicyclo [4.3. 0] -5-nonene), organic acids such as acetic acid, propionic acid, butyric acid, valeric acid, maleic acid and stearic acid, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and hydrogen peroxide. Among these, it is preferable to use an amine compound. The concentration of the catalyst added at this time is preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, 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, decrease in film density, increase in film defects, and the like.

  In the coating liquid for forming a coating film, the additives listed below can be used as necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

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

  The coating thickness can be appropriately set according to the purpose. For example, the coating thickness per gas barrier film is preferably about 5 to 500 nm, more preferably 10 to 400 nm after drying. If the film thickness is 5 nm or more, sufficient barrier properties can be obtained, and if it is 500 nm or less, stable coating properties can be obtained at the time of coating film formation, and high light transmittance can be realized.

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

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

  The coating film obtained by applying the coating solution for forming the upper coating film may include a step of removing water before or during the modification treatment. As a method for removing moisture, a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. A preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −5 ° C. (temperature 25 ° C./humidity 10%) or less, and the time to be maintained depends on the film thickness of the gas barrier film. It is preferable to set appropriately. Under the condition that the film thickness of the gas barrier film is 1.0 μm or less, it is preferable that the dew point temperature is −5 ° C. or less and the maintaining time is 1 minute or more. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher and preferably −40 ° C. or higher. This is a preferred form from the viewpoint of promoting the dehydration reaction of the gas barrier film by removing water before or during the reforming process.

  Polysilazane, which is a preferred precursor, is commercially available in a solution state dissolved in an organic solvent, and a commercially available product can be used as it is as a coating liquid for coating film formation. 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.

(2) The process of irradiating the coating film with ultraviolet light containing a wavelength component of less than 200 nm In this step, the coating film is irradiated with ultraviolet light containing a wavelength component of less than 200 nm. In this process, light energy having a wavelength component of less than 200 nm, which is greater than the interatomic bonding force in silicon oxide or silicon oxynitride, is used, and preferably ultraviolet light containing a wavelength component of 100 to 180 nm is used. The silicon oxide film and / or the silicon oxynitride at a relatively low temperature (about 200 ° C. or less) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of only a photon called photon process A film is formed.

  The ultraviolet light used in this step is not particularly limited as long as it is ultraviolet light containing a wavelength component of less than 200 nm.

  The ultraviolet light source in this step may be any light source that generates ultraviolet light including a wavelength component of less than 200 nm, but is preferably an excimer radiator (for example, a Xe excimer lamp having a maximum emission at about 172 nm or a maximum at about 193 nm). ArF excimer lamp having radiation, excimer lamp such as ArBr excimer lamp having maximum radiation at about 161 nm), low-pressure mercury lamp, amalgam lamp, deuterium lamp having emission lines at about 185 nm and 254 nm, strong emission lines at about 156 nm and about 165 nm A lamp using carbon monoxide having a wavelength (such as JP 2010-135162 A), an ArF excimer laser having a maximum emission at about 193 nm, an F2 excimer laser having a maximum emission at about 157 nm, and the like are used. As described above, as the ultraviolet light used in this step, (1) ultraviolet light having only a wavelength component of less than 200 nm or (2) ultraviolet light comprising a wavelength component of less than 200 nm and a wavelength component of 230 nm or more is used. Is desirable.

Among these ultraviolet light sources, a rare gas excimer lamp is particularly preferably used. Since noble gas atoms such as Xe, Kr, Ar, Ne, and the like are chemically bonded and do not form molecules, they are called inert gases. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. When the rare gas is xenon,
e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Then, 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 lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. When the micro discharge streamer reaches the tube wall (dielectric), the electric discharge accumulates on the surface of the dielectric 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 seen 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 those of the 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, so that the outer electrode covers the entire outer surface and transmits light to extract light to the outside in order to discharge in the entire discharge space. 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 create 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, usually made of an aluminum block, is 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. Therefore, a very inexpensive light source can be provided.

  Since the double cylindrical lamp is processed by closing both ends of the inner and outer tubes, it is more likely to be damaged during handling and transportation than a thin tube lamp. The outer diameter of the tube of the thin tube lamp is about 6 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.

  Among rare gas excimer lamps, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

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

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

  Oxygen is required for the reaction at the time of irradiation, but ultraviolet light containing a wavelength component of 200 nm or less is easily absorbed because it is absorbed by oxygen. Therefore, irradiation is performed with oxygen concentration and water vapor concentration as much as possible. It is preferable to carry out in a low state. That is, the oxygen concentration during irradiation in this step is preferably 0.01 to 5% by volume, more preferably 0.01 to 1% by volume, and 0.01 to 0.5% by volume. More preferably. If it is this range, since modification | reformation of a coating film will fully progress and absorption of the ultraviolet light by oxygen will also be suppressed, generation | occurrence | production of ozone will also be suppressed and damage to the gas barrier film obtained will also be suppressed.

  As the gas satisfying the irradiation atmosphere used at the time of ultraviolet light irradiation, a dry inert gas is preferable, and dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

  In the ultraviolet light irradiation in this step, any commonly used ultraviolet light irradiation apparatus can be used, but an ultraviolet light irradiation unit as shown in FIG. 1 can be given as an example.

  FIG. 1A is an external view showing an example of an ultraviolet light irradiation unit used in this process, and FIG. 1B is a cross-sectional view showing an example of an ultraviolet light irradiation unit used in this process. In FIG. 1A, the ultraviolet light irradiation unit 1 includes an excimer lamp holder 2, an excimer lamp 3, and a nitrogen gas pipe inlet 4.

  FIG.1 (b) is sectional drawing in the position of AA of the ultraviolet light irradiation unit 1 of Fig.1 (a). In the excimer lamp holder 2, dried nitrogen gas is supplied from the nitrogen gas pipe inlet 4, passes through the nitrogen gas pipe 5, and the nitrogen gas flows from both sides of the excimer lamp 3 toward the lower film substrate. 6 can be injected. Further, the excimer lamp 3 can irradiate the vacuum ultraviolet light 7 toward the lower film substrate.

In this step, it is preferable that the peak intensity of the該紫outside light at the coated surface of the coating film is subjected is ^{50mW / cm 2 ~500mW / cm 2} , and more preferably 80mW / cm ² ~300mW / cm ² . If it is this range, modification | reformation will be possible to the deep part of a coating film.

Irradiation energy amount of ultraviolet light in the coated surface (irradiation amount) is preferably 0.01~20J / cm ^2, more preferably 0.1~20J / cm ^2, 0.3~15J More preferably, it is / cm ² . If it is this range, reforming will progress sufficiently and productivity will improve. In addition, it is possible to prevent cracks due to excessive modification and thermal deformation of the film substrate. As will be described later, this step may be performed a plurality of times. In this case, the irradiation amount per time may be appropriately selected so that the total irradiation amount falls within the above range.

Furthermore, ultraviolet light used for reforming, CO, it may be generated by plasma formed in a gas containing at least one of CO ₂ and CH _4. Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), a carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as a main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.

  In this step, it is preferable to set the distance between the film substrate and the ultraviolet light source and the irradiation time within the range where the film substrate carrying the coating film to be irradiated is not damaged.

  Taking the case of using a plastic film as the film substrate, for example, the distance between the substrate and the ultraviolet irradiation lamp is preferably 0.01 to 10 mm from the viewpoint of suppressing light absorption by oxygen. Further, the irradiation time is preferably 0.05 to 300 seconds from the viewpoint of reforming efficiency and productivity.

  Irradiation with ultraviolet light in this step can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, a laminate having a coating film containing a precursor on the surface can be processed in an ultraviolet baking furnace equipped with the ultraviolet light source as described above. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. Moreover, when the laminated body which has the coating film containing a precursor on the surface is a elongate film form, it irradiates with an ultraviolet light continuously in the drying zone equipped with the above ultraviolet light sources, conveying this. Thus, the modification can be performed.

(3) Step of irradiating the coating film with ultraviolet light having a wavelength of 200 nm or more and less than 230 nm In this step, the coating film is irradiated with ultraviolet light having a wavelength of 200 nm or more and less than 230 nm. By performing this step, defects (E ′ center) that can occur in the step (2) can be repaired and reduced, and the gas barrier properties can be further improved.

  FIG. 2 is a diagram showing the results of measuring the ultraviolet absorption spectrum of a coating film after forming a coating film containing perhydropolysilazane on a quartz substrate, and then irradiating ultraviolet light with a wavelength of 172 nm so that the irradiation amount is different. is there. (A) of FIG. 2 shows the ultraviolet absorption spectrum when the irradiation dose is 0J (no irradiation), 1J, 3J, and 6J, respectively, and (b) shows the irradiation when the irradiation dose is 1J, 3J, and 6J. It is the graph which took the difference with the case of quantity 0J. As shown in FIG. 2 (b), after irradiation with ultraviolet light, absorption that appears to be caused by the E ′ center appears in the vicinity of a wavelength of 220 nm. By irradiating ultraviolet light containing a wavelength component of less than 200 nm, It can be seen that defects occur. By performing this step, this defect can be repaired.

  The ultraviolet light source used in this step is not particularly limited as long as it generates ultraviolet light having a wavelength of 200 nm or more and less than 230 nm. For example, a KrCl excimer lamp (single wavelength of 222 nm), a KrBr excimer lamp (207 nm), AlGaN, Although the LED element etc. which used AlN are mentioned, it is not specifically limited. In addition, a phosphor is provided inside the glass tube of the Xe excimer lamp (for example, Japanese Patent Application Laid-Open No. 2011-175823), or ultraviolet light having the wavelength is generated through a filter provided with a phosphor between the Xe excimer lamp and the coating film. Can do.

  Although oxygen is required for the reaction at the time of irradiation, the oxygen concentration at the time of irradiation in this step is preferably 0.01 to 21% by volume, more preferably 0.1 to 21% by volume. . If it is this range, the modification | reformation of a coating film will fully advance.

  As the gas satisfying the irradiation atmosphere used at the time of ultraviolet light irradiation, a dry inert gas is preferable, and dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

  In the ultraviolet light irradiation in this step, any commonly used ultraviolet light irradiation apparatus can be used, but an ultraviolet light irradiation unit as shown in FIG. 1 can be given as an example.

In this step, it is more preferably ^{preferably, 50mW / cm 2 ~300mW / cm} 2 peak irradiance of該紫outside light at the coated surface of the coating film is subjected is 10mW / cm ² ~500mW / cm ² . If it is this range, modification | reformation will be possible to the deep part of a coating film.

In this step, the irradiation energy of ultraviolet light in the coated surface (irradiation amount) is preferably 0.01~20J / cm ^2, more preferably 0.1~15J / cm ^2, 0 More preferably, it is ³ to 10 J / cm ² . If it is this range, reforming will progress sufficiently and productivity will improve. In addition, it is possible to prevent cracks due to excessive modification and thermal deformation of the film substrate. As will be described later, this step may be performed a plurality of times. In this case, the irradiation amount per time may be appropriately selected so that the total irradiation amount falls within the above range.

  In the irradiation with ultraviolet light in this step, it is preferable to set the distance between the film substrate and the ultraviolet light source and the irradiation time so long as the film substrate carrying the irradiated coating film is not damaged.

  Taking the case of using a plastic film as the film substrate, for example, the distance between the substrate and the ultraviolet irradiation lamp is preferably 0.01 to 100 mm from the viewpoint of suppressing light absorption by oxygen. Further, the irradiation time is preferably 0.05 to 300 seconds from the viewpoint of reforming efficiency and productivity.

  The order of the step (2) and the step (3) is not particularly limited. The mode in which the step (3) is performed after the step (2), the step (2) after the step (3). The form which performs the process of (2) and the process of (3) simultaneously, etc. are mentioned.

  In the embodiment in which the step (3) is performed after the step (2), the ultraviolet light irradiation unit in the step (2) and the ultraviolet light irradiation unit in the step (3) What is necessary is just to install with a fixed space | interval in the running direction of a film base material. Here, the ultraviolet light irradiation unit in step (2) refers to an ultraviolet light irradiation unit provided with a VUV light source (Xe excimer lamp) for step (2) as the ultraviolet light irradiation unit shown in FIG. The ultraviolet light irradiation unit in the step (3) refers to an ultraviolet light irradiation unit provided with an ultraviolet light source (KrCl excimer lamp) of 200 nm to less than 230 nm for the step (3) as the ultraviolet light irradiation unit shown in FIG. Moreover, an irradiated body means the coating film formed by apply | coating the said precursor solution on the said film base material. When the above process is repeated, a plurality of coating apparatuses in the above process (1), an ultraviolet light irradiation unit for the above process (2), and a plurality of ultraviolet light irradiation units for the process (3) may be provided. However, if the travel distance of the film becomes too long, the roll-to-roll method is carried out an appropriate number of times (1) to (3), and the roll that has been wound up once again is attached to the unwinding side. Step (1) to step (3) may be repeated.

  In the case where the step (2) is performed after the step (3), the installation order of each ultraviolet light irradiation unit in the form in which the step (2) and the step (3) are simultaneously performed is reversed. That's fine.

  In the case where the step (2) and the step (3) are performed simultaneously, for example, the ultraviolet light irradiation unit in the step (2) is installed approximately 5 mm above the surface of the irradiated body. By linking the ultraviolet light irradiation unit of step (3) with the ultraviolet light irradiation unit of step (2) and placing it at about 5 mm above the surface of the irradiated body, the irradiated body is located at a portion where both irradiation ranges overlap. It is also possible to irradiate the coating film on the irradiated object with the VUV in the step (2) and the ultraviolet rays in the step (3) at the same time.

  As another embodiment in which the step (2) and the step (3) are performed simultaneously, the ultraviolet light irradiation unit in the step (2) is installed about 5 mm above the surface of the irradiated body. The ultraviolet light irradiation unit in the step (3) is installed approximately 50 mm above the surface of the irradiated object at a position spaced apart from the ultraviolet light irradiation unit in the step (2) by a certain distance (for example, 5 to 200 mm) in the traveling direction. By doing so, the irradiated body travels in a portion where both irradiation ranges overlap, and the coating film of the irradiated body is irradiated with the VUV in the step (2) and the ultraviolet ray in the step (3) at the same time. (Applicable to Example 14).

  As still another embodiment in which the step (2) and the step (3) are performed simultaneously, the ultraviolet light irradiation unit in the step (2) is installed about 5 mm above the surface of the irradiated body. The ultraviolet light irradiation unit in the step (3) is installed approximately 50 mm above the surface of the irradiated object at a position spaced apart from the ultraviolet light irradiation unit in the step (2) by a certain distance (for example, 5 to 200 mm) in the traveling direction. At this time, in the ultraviolet light irradiation unit of step (3), the ultraviolet light from the light source of the irradiation unit is reflected by a reflector (mirror) provided above the ultraviolet light irradiation unit of step (2), and then the process ( By adjusting the angle of the reflecting plate (mirror) and applying it to the coating film of the object to be irradiated so as to cover the entire irradiation range of VUV of 2), the VUV of step (2) and the step You may make it irradiate with the ultraviolet-ray of (3) simultaneously.

As still another embodiment in which the step (2) and the step (3) are performed simultaneously, the ultraviolet light irradiation unit in the step (2) is installed about 5 mm above the surface of the irradiated body. At this time, a phosphor is provided in half of the lamp tube of the ultraviolet light irradiation unit in the step (2), and the portion provided with this phosphor is used as the step (3), and the VUV in the step (2) is applied to the coating film of the irradiated object. And the ultraviolet rays in the step (3) may be irradiated simultaneously. The form in which the steps (2) and (3) are simultaneously performed is not particularly limited, and is not limited to the above-described four forms. Is not to be done.

  Further, the step (2) and the step (3) may be repeated a plurality of times. The number of repetitions is not particularly limited, and is usually in the range of 2 to 100 times. From the point which is excellent in storage stability, especially the storage stability under severe conditions (high temperature and high humidity conditions), it is preferably 3 to 50 times (see Examples 1 to 12). In addition, the repetition interval between the step (2) and the step (3) is preferably within 5 minutes, and more preferably within 30 seconds.

Furthermore, it is preferable that the irradiation energy amount (irradiation amount) of ultraviolet light per step (2) in the case of repeating (2) is 10 mJ / cm ² or more. Similarly, the irradiation energy amount (irradiation amount) of ultraviolet light per step (3) is preferably 0.01 J / cm ² or more. This is because defects per se are reduced by repeated irradiation, and it can be said that it is better to apply a certain amount of energy from the viewpoints of ultraviolet light absorption efficiency, modification efficiency, and production efficiency.

  The steps (2) and (3) are preferably performed using an ultraviolet light irradiation apparatus including a plurality of ultraviolet light irradiation units shown in FIG. 1 from the viewpoint of improving productivity.

  The gas barrier film obtained by the production method of the present invention may include two or more gas barrier films. At this time, only the step (1) is repeated to obtain a coating film having a laminated structure, and then the step (2) and the step (3) may be performed, or each layer (1) to (3). A laminated structure of gas barrier films may be obtained by repeating the process. In consideration of the absorption efficiency of ultraviolet light, a method of repeating the steps (1) to (3) for each layer is preferable.

[Constituent layers other than gas barrier film of gas barrier film]
In the gas barrier film, in addition to the gas barrier film according to the present invention, various functional layers may be provided as necessary.

(Anchor coat layer)
On the surface of the film substrate according to the present invention, an anchor coat layer may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion). As the constituent material and forming method of the anchor coat layer, the materials and methods disclosed in paragraphs “0229” to “0232” of JP2013-52561A are appropriately employed.

(Smooth layer)
The gas barrier film according to the present invention may have a smooth layer between the surface of the film substrate having the gas barrier film, preferably between the film substrate and the gas barrier film. The smooth layer is provided to flatten the rough surface of the film base where protrusions and the like are present, or to fill the unevenness and pinholes generated in the gas barrier film by the protrusions existing on the film base. . The materials, methods, and the like disclosed in paragraphs “0233” to “0248” of JP2013-52561A are appropriately employed as the constituent material, forming method, surface roughness, film thickness, and the like of the smooth layer.

(Bleed-out prevention layer)
The gas barrier film according to the present invention may further have a bleed-out preventing layer. The bleed-out prevention layer is used for the purpose of suppressing a phenomenon that, when a film having a smooth layer is heated, unreacted oligomers migrate from the resin base material to the surface 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. As the constituent material, forming method, film thickness and the like of the bleed-out prevention layer, materials, methods and the like disclosed in paragraphs “0249” to “0262” of JP2013-52561A are appropriately employed.

(Dry gas barrier film)
In the gas barrier film according to the present invention, a dry gas barrier film may be provided in addition to the gas barrier film according to the present invention. For example, by providing the gas barrier film according to the present invention on the dry gas barrier film, further improvement of the gas barrier property can be expected due to a synergistic effect by repairing fine defects of the dry gas barrier film by a uniform film by coating.

  Dry gas barrier films include Si, Ta, Nb, Al, In, W, Sn, Zn, Ti, Cu, Ce, Ca, Na, B, Pb, Mg, P, Ba, Ga, Ge, Li, K, A film containing an oxide or nitride, nitride oxide, or carbide containing one or more metal atoms selected from Zr as a main component can be used. Silicon oxide, silicon nitride oxide, silicon nitride, aluminum oxide, silicon oxide Aluminum, silicon oxynitride aluminum, ZTO, ITO and ZnO are preferably used. These films may contain a certain proportion of carbon, or may be gradient films having a composition change in the film thickness direction.

  As a method for producing a dry gas barrier film, physical vapor deposition (vacuum vapor deposition, ion plating, sputtering, etc.) or chemical vapor deposition (PECVD, Cat-CVD, atmospheric pressure plasma, ALD, etc.) is used. it can.

[Electronic device]
The gas barrier film obtained by the production method of the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. Examples of the device include electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV), and an organic EL element or a solar cell is preferable. Organic EL elements are particularly preferred.

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

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

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

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

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

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

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

<Circularly polarizing plate>
A circularly polarizing plate can be produced by using the gas barrier film according to the present invention as a substrate and laminating a λ / 4 plate and a polarizing plate. In this case, the lamination is performed so that the angle formed by the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate is 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. .

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

Example 1
Step (1) Dibutyl ether solution containing 20% by weight of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20) and amine catalyst (N, N, N ′, N 20% by weight of a perhydropolysilazane solution (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) containing '-tetramethyl-1,6-diaminohexane (TMDAH)) In a solvent mixed so that the weight ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, the solid content of the coating solution is 5% by weight. The coating solution was diluted and prepared.

  The coating solution obtained above was formed on a PET base material (125 μm thick) with a clear hard coat manufactured by Kimoto Co., Ltd. with a spin coater so as to have a thickness of 250 nm and left for 2 minutes. Then, additional heat treatment was performed for 1 minute on a hot plate at 80 ° C. to form a polysilazane coating film.

After forming the polysilazane coating film, a vacuum ultraviolet ray irradiation treatment of 1.0 J / cm ² was performed in an atmosphere having an oxygen concentration of 0.1 vol% according to the following method.

Steps (2) and (3) Steps (2) and (3) were performed using an apparatus including a plurality of ultraviolet light irradiation units shown in FIG.

  The energy applied to the surface of the coating film in the steps (2) and (3) was measured using a UV integrated photometer: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics Co., Ltd. In the measurement, the sensor head is installed at the center of the sample stage so that the shortest distance between the light source tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber is (2) and (3). Nitrogen and oxygen were supplied so as to achieve the same oxygen concentration as in the above step, and measurement was performed by moving the sample stage at a speed of 0.5 m / min. Prior to the measurement, in order to stabilize the illuminance of the light source, an aging time of 10 minutes was provided after the light source was turned on, and then the measurement was started by moving the sample stage.

  Based on the irradiation energy obtained by this measurement, the moving speed of the sample stage was adjusted so that the irradiation energy (irradiation amount) described in Tables 1 and 2 was obtained. The ultraviolet light irradiation was performed after aging for 10 minutes, as in the case of irradiation energy measurement.

  In this way, a gas barrier film was produced.

(Examples 2-18, Comparative Examples 1-9)
A gas barrier film was produced in the same manner as in Example 1 except that the type of light source, oxygen concentration, irradiation amount, and steps (2) and (3) were changed to the conditions shown in Tables 1 and 2. .

  Example 14 is an example in which the steps (2) and (3) were performed simultaneously. Specifically, the ultraviolet light irradiation unit in the step (2) is installed 5 mm above the surface of the object to be irradiated, and the ultraviolet light irradiation unit in the step (3) is spaced from the ultraviolet light irradiation unit in the step (2) in a traveling direction (50 mm). It was installed 50 mm above the surface of the irradiated object at a separated position. By adopting such an apparatus configuration, the irradiated body travels through the portion where both irradiation ranges overlap, and the coating film of the irradiated body is simultaneously irradiated with the VUV of step (2) and the ultraviolet ray of step (3). By the method.

  The water vapor barrier property of the obtained gas barrier film was measured according to the following method.

<Evaluation of water vapor barrier properties>
(apparatus)
Vapor deposition apparatus: manufactured by JEOL Ltd., vacuum vapor deposition apparatus JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation sample)
Using a vacuum deposition apparatus (vacuum deposition apparatus JEE-400 manufactured by JEOL Ltd.), calcium metal was deposited in a size of 12 mm × 12 mm through the mask on the surface of the gas barrier film of the gas barrier film produced in Examples and Comparative Examples.

  Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet to perform temporary sealing. Next, the vacuum state is released, quickly transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum deposition surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX). A water vapor barrier property evaluation sample was produced by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.

(Evaluation method)
The obtained sample was stored under high temperature and high humidity of 40 ° C. and 90% RH, and the appearance of the metal calcium corroded with respect to the storage time was observed. Observation was performed every 5 hours, and the area where metal calcium corroded relative to the metal calcium vapor deposition area of 12 mm × 12 mm was calculated in%. The time when the area where metallic calcium corroded reached 100% was evaluated according to the following rank.

1: Less than 30 hours 2: 30 hours or more and less than 100 hours 3: 100 hours or more and less than 200 hours 4: 200 hours or more and less than 300 hours 5: 300 hours or more and less than 500 hours 6: 500 hours or more About each example and comparative example, The above-described water vapor barrier property evaluation was performed on each of the gas barrier film immediately after production and the gas barrier film after being stored at 85 ° C. and 85% RH for 7 days.

  The evaluation results are shown in Tables 1 and 2 below.

  As apparent from Table 1 and Table 2, the gas barrier film according to the present invention has high gas barrier properties and is excellent in storage stability under high temperature and high humidity.

1 UV light irradiation unit,
2 Excimer lamp holder 3 Excimer lamp,
4 Nitrogen gas piping inlet,
5 Nitrogen gas piping,
6 Nitrogen gas,
7 Ultraviolet light.

Claims (7)

A method for producing a gas barrier film having at least one gas barrier film on a film substrate,
(1) forming a coating film by applying a solution containing a silicon oxide precursor or a silicon oxynitride precursor on the film substrate;
(2) irradiating the coating film with ultraviolet light containing a wavelength component of less than 200 nm;
(3) irradiating the coating film with ultraviolet light having a wavelength of 200 nm or more and less than 230 nm;
A method for producing a gas barrier film, comprising:   The method for producing a gas barrier film according to claim 1, wherein, in the step (2), the coating film is irradiated with vacuum ultraviolet light having a wavelength of less than 200 nm.   The method for producing a gas barrier film according to claim 1 or 2, wherein the step (2) and the step (3) are repeated a plurality of times.   The method for producing a gas barrier film according to any one of claims 1 to 3, wherein the step (3) is performed after the step (2).   The method for producing a gas barrier film according to any one of claims 1 to 4, wherein the oxygen concentration in the step (2) is 0.01 to 1% by volume.   The method for producing a gas barrier film according to any one of claims 1 to 5, wherein the oxygen concentration in the step (3) is 0.01 to 21% by volume.   The method for producing a gas barrier film according to any one of claims 1 to 5, wherein the step (2) and the step (3) are performed simultaneously.