JP6056694B2 - Gas barrier film - Google Patents

Description

  The present invention relates to a gas barrier film having ultraviolet reflectivity, a method for producing the same, and an electronic device including the gas barrier film.

  Conventionally, a relatively simple structure in which an inorganic film such as a metal or metal oxide vapor deposition film is provided on the surface of a resin substrate in order to prevent permeation of gases such as water vapor and oxygen in the fields of food, packaging materials, pharmaceuticals, etc. Gas barrier films having the following have been used.

  In recent years, such gas barrier films that prevent permeation of water vapor, oxygen, and the like are being used in the field of electronic devices such as liquid crystal display (LCD) elements, solar cells (PV), and organic electroluminescence (EL). In order to give such an electronic device the property of being flexible and light and not easily broken, a gas barrier film having a high gas barrier property is required instead of a hard and easily broken glass substrate.

  As a measure for obtaining a gas barrier film applicable to an electronic device, a barrier layer is formed on a substrate such as a film by a plasma CVD method (Chemical Vapor Deposition) on a resin substrate. A method of forming is known.

  For example, Patent Document 1 discloses a technique for forming a high nitrogen concentration region in part of a polysilazane coating film by irradiating polysilazane with energy rays in an atmosphere substantially free of oxygen and water vapor in order to obtain high gas barrier properties. Has been.

  Patent Document 2 discloses an inorganic EL element sealing film in which an inorganic vapor deposition film is formed on the first layer on a transparent plastic substrate and a barrier layer is formed thereon to improve the gas barrier property. However, the opposite side of the barrier layer is an ultraviolet cut layer made of only metal oxide particles, and cannot block the ultraviolet light around 380 nm of the barrier layer.

  In Patent Document 3, a weathering layer 1 containing an organic compound ultraviolet absorber and a resin binder is provided on at least one surface of a resin substrate, and a weathering layer 2 containing metal oxide fine particles and a resin binder on the weathering layer 1. It is described that ultraviolet rays can be shielded by providing.

International Publication No. 2011/007543 JP 2004-338201 A JP 2012-076386 A

  However, when the laminate described in Patent Document 1 is exposed to UV light under high temperature and high humidity, the polysilazane region other than the nitrogen high-concentration region is gradually oxidized and modified, so that the unmodified layer Peeling easily from the interface in contact with the surface, and the barrier properties deteriorate. Even in the configuration described in Patent Document 3, when the nitrogen atom of the modified siloxane film exceeds a certain ratio, the ultraviolet absorber significantly deteriorates when stored under high temperature and high humidity for a long time. Have the same issues.

  Therefore, the present invention has been made in view of the above circumstances, and by effectively suppressing the incidence of ultraviolet rays on the barrier layer, high adhesion even under high humidity and high temperature, even under ultraviolet irradiation, It is an object of the present invention to provide a gas barrier film that can maintain transparency and gas barrier properties, and an optical reflector using the same.

  As a result of intensive studies to solve the above problem, the present inventors have found that the above problem can be solved by efficiently shielding ultraviolet rays having a specific wavelength among the deterioration factors of the barrier layer. The present invention has been completed.

That is, the above-mentioned subject of the present invention is a gas barrier film comprising a base material and a barrier layer formed by applying a solution containing a polysilazane compound on at least one surface of the base material. Gas barrier film characterized by satisfying the conditions:
i) The reflectance of light having a wavelength of 280 nm to 380 nm is 20% or more;
ii) The transmittance of light having a wavelength of 380 nm is 80% or more.

  The gas barrier film of the present invention is excellent in storage stability, adhesion and gas barrier properties under high temperature and high humidity conditions.

It is sectional drawing of the transparent gas barrier film in one Embodiment of this invention. It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of the CVD layer in one Embodiment of this invention. It is a schematic diagram which shows an example of the other manufacturing apparatus used for formation of the CVD layer in one Embodiment of this invention.

The present invention is a gas barrier film comprising a base material and a barrier layer formed by applying a solution containing a polysilazane compound to at least one surface of the base material,
Gas barrier film characterized by satisfying the following conditions:
i) The reflectance of light having a wavelength of 280 nm to 380 nm is 20% or more;
ii) The transmittance of light having a wavelength of 380 nm is 80% or more.

  The ultraviolet reflective gas barrier film of the present invention is excellent in storage stability, adhesion and gas barrier properties under high temperature and high humidity conditions. Here, the mechanism for exerting the above-described effects by the configuration of the present invention is presumed as follows. The present invention is not limited to the following. That is, a modified polysilazane film that imparts gas barrier properties to a gas barrier film is denatured by the reaction with water, particularly the remaining unmodified portion of the polysilazane layer, when irradiated with ultraviolet rays at high temperature and high humidity, causing peeling. It is possible. However, it is considered that a gas barrier film capable of maintaining adhesion and gas barrier properties even under high temperature and high humidity and ultraviolet irradiation while maintaining transparency can be obtained by selectively blocking ultraviolet rays that cause deterioration.

  However, the above mechanism is merely an estimation, and the technical scope of the present invention is not limited by the above mechanism.

  Embodiments of the present invention will be described below. 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%.

<Gas barrier film>
The optical properties of the gas barrier film according to the present application are such that the light transmittance at a wavelength of 380 nm is 80% or more, preferably 85% or more, more preferably 90% or more, and reflection at a wavelength of 280 nm to 380 nm. The rate is 20% or more, preferably 25% or more, more preferably 30% or more. If the light transmittance at 380 nm is 80% or more, it is preferable because sufficient transparency can be secured. In addition, when the reflectance at a wavelength of 280 nm to 380 nm is 20% or more, deterioration of the barrier layer under high temperature and high humidity and ultraviolet irradiation is sufficiently suppressed, and the deterioration of adhesion and the occurrence of cracks can be remarkably suppressed. In addition, the reflectance of wavelength 280nm-380nm means the average reflectance in wavelength 280nm-380nm, and it is not required that a reflectance is 20% or less in the whole area | region of this wavelength.

  The method for imparting the above-described function to the gas barrier film according to the present invention is not particularly limited, but in one embodiment, it may be imparted by providing an ultraviolet absorbing layer in the gas barrier film. The structure of the layer of the gas barrier film which concerns on one Embodiment of this invention is demonstrated using FIG.

  In FIG. 1, a gas barrier film 11 according to an embodiment of the present invention includes a base material 12, a barrier layer 13 and an ultraviolet reflective film 14 formed on the base material 12. The ultraviolet reflective film 14 in the barrier film of the present invention may have a laminated structure of units composed of the high refractive index layer 15 and the low refractive index layer 16. When it has a laminated structure, it is sufficient that at least one unit is composed of the high refractive index layer 15 and the low refractive index layer 16. In addition, the layer order of the base material, the barrier layer, and the ultraviolet reflective film is not limited as long as the layer configuration can be used with the ultraviolet reflective film facing the incident light side of the barrier layer, but the layer is covered with the barrier layer. It is preferable to have at least one ultraviolet reflective film having no surface. Further, another intermediate layer (for example, an organic layer, a moisture absorbing layer, an antistatic layer, between the high refractive index layer and the low refractive index layer or between the two units composed of the high refractive index layer and the low refractive index layer, A smooth layer, a bleed-out layer), and another control layer (for example, a unit composed of a high refractive index layer and a low refractive index layer first formed on the base material). , An organic layer, a hygroscopic layer, an antistatic layer, a smooth layer, a bleed-out layer), and another protective layer (for example, an organic layer, a hygroscopic layer, an antistatic layer, a smooth layer, a bleed layer) on the outermost layer. Out layer) may be provided, and another functional layer (for example, an organic layer, a hygroscopic layer, an antistatic layer, a smooth layer, a bleed-out layer) may be provided on the substrate.

[Base material]
The substrate used in the present invention is not particularly limited as long as it is a long support and can hold the barrier layer.

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

  The Tg and the linear expansion coefficient of the substrate can be adjusted with an additive or the like. More preferable specific examples of the thermoplastic resin that can be used as the substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polybutylene terephthalate, polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.). , Cycloaliphatic polyolefins such as polyethylene (PE) and polypropylene (PP) (for example, ZEONOR (registered trademark) 1600: 160 ° C. manufactured by ZEON CORPORATION), polyarylate (PAr: 210 ° C.), polyether sulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: compound described in JP 2001-150584 A: 162 ° C.), polyimide (for example, manufactured by Mitsubishi Gas Chemical Company, Neoprim (registered trademark)): 260 ° C), Fluo Ring-modified polycarbonate (BCF-PC: compound described in JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP 2000-227603 A: 205 ° C.), Acryloyl compound (compound described in JP-A-2002-80616: 300 ° C. or higher), acrylic ester, methacrylic ester, polyvinyl chloride (PVC), polystyrene (PS), nylon (Ny), aromatic polyamide, poly Examples include ether ether ketone, polysulfone, polyether imide and the like (in parentheses indicate Tg). Or heat-resistant transparent film (Sila-DEC: manufactured by Chisso Corporation, Silplus: manufactured by Nippon Steel Chemical Co., Ltd.) having silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton; transparent polyimide film (transparent polyimide film) Type HM: manufactured by Toyobo Co., Ltd., transparent polyimide film Neoprim L L-3430: manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like may be used as the base material.

  Of these, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used from the viewpoint of cost and availability.

  In addition, from the viewpoint of properties such as optical transparency and heat resistance, and adhesion to inorganic layers and barrier layers, it is possible to use a heat-resistant transparent film or the like based on silsesquioxane having an organic-inorganic hybrid structure. preferable.

  Furthermore, from the viewpoint of the manufacturing process, the heat-resistant transparency is particularly high in heat resistance, specifically, a polyimide or polyetherimide having a glass transition point of 150 ° C. or higher, or a silsesquioxane having an organic-inorganic hybrid structure. It is preferable to use a film. For example, when a gas barrier film is used for an electronic device, the process temperature may exceed 200 ° C. in the array manufacturing process. Particularly in roll-to-roll manufacturing, a certain amount of tension is always applied to the substrate. Therefore, when a substrate having a glass transition point of 150 ° C. or higher is used, even if the substrate is placed at a high temperature and the substrate temperature is increased, the substrate It is preferable because elongation can be suppressed and damage to the barrier layer can be prevented. However, since the heat-resistant resin as described above is usually non-crystalline, the water absorption rate is larger than that of crystalline PET or PEN. As a result, the degree of dimensional change of the substrate due to humidity is increased, and the barrier layer can be damaged. However, by forming barrier layers on both surfaces of these substrates, dimensional changes due to moisture absorption and desorption of the substrates can be suppressed under severe conditions of high temperature and high humidity. Therefore, a heat-resistant substrate and a gas barrier film in which a barrier layer is disposed on both surfaces of the heat-resistant substrate are a preferred embodiment.

  Furthermore, when 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 of visible light (400 to 700 nm) 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.

  These base materials may be used alone or in combination of two or more.

  Moreover, the base material using the resin film may be an unstretched film or a stretched film.

  The base material using the above resin film can be produced by a conventionally known general production method. For example, an unstretched film that is substantially amorphous and not oriented can be produced by melting the resin with an extruder, extruding it with an annular die or T-die, and quenching. In addition, the unstretched film is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like in the flow (vertical axis) direction of the substrate or the base. A stretched film can be produced by stretching in the direction perpendicular to the flow direction of the material (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, respectively. In order to improve the dimensional stability of the base material, the stretched film may be subjected to relaxation treatment after stretching.

  The thickness of the base material used in the gas barrier film according to the present invention is appropriately selected depending on the application and is not particularly limited, but is typically preferably 5 to 500 μm, and preferably 25 to 250 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. As 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.

  Furthermore, the base material used in the present invention preferably has a 10-point average surface roughness Rz defined by JIS B 0601 (2001) of 1 to 1500 nm, more preferably 5 to 400 nm, More preferably, it is 350 nm. The center line average roughness Ra specified by JIS B 0601 (2001) is preferably 0.5 to 12 nm, and more preferably 1 to 8 nm. It is preferable that Rz and Ra are within the above ranges since the coating property of the coating liquid is improved. If necessary, the substrate may be polished on one side or both sides, preferably the side on which the barrier layer is provided, to improve smoothness.

  Various known treatments for improving adhesion, such as excimer treatment, corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and a primer described later are provided on at least the side of the base material on which the barrier layer according to the present invention is provided. It is preferable to stack layers, and it is more preferable to combine the above treatments as necessary.

[Barrier layer (PHPS layer)]
The barrier layer is formed by applying a solution containing a polysilazane compound to at least one surface of the substrate.

<Solution containing polysilazane compound>
The solution containing a polysilazane compound contains a polysilazane compound.

(Polysilazane compound)
The polysilazane compound is a polymer having a bond such as Si—N, Si—H, or N—H in its structure, and an inorganic precursor such as SiO ₂ , Si ₃ N ₄ , or an intermediate solid solution thereof such as SiO _x N _y. Functions as a body.

  The polysilazane compound is not particularly limited, but it is preferable that the polysilazane compound is a compound that is converted to silica by being converted to silica at a relatively low temperature in consideration of performing the modification treatment described later, for example, in JP-A-8-112879. It is preferable that it is a compound which has the main skeleton which consists of a unit represented by the following general formula (1) of description.

In the general formula (1), R ¹ , R ² and R ³ represent 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, 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. Particularly preferred is perhydropolysilazane (PHPS) in which all of R ¹ , R ² and R ³ are hydrogen atoms. A barrier layer (gas barrier film) formed from such polysilazane exhibits high density.

  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 can be a liquid or solid substance (depending on the molecular weight). As the perhydropolysilazane, a commercially available product may be used. Examples of the commercially available product include AQUAMICA NN120, NN120-10, NN120-20, NN110, NAX120, NAX120-20, NAX110, NL120A, NL120-20, NL110A, NL150A, NP110, NP140 (all are made by AZ Electronic Materials Co., Ltd.) and the like. These may be used alone or in combination of two or more.

  As another example of the polysilazane compound that becomes ceramic at low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with the polysilazane compound represented by the above general formula (for example, JP-A-5-23827), glycidol can be used. A glycidol-added polysilazane obtained by reaction (for example, JP-A-6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (for example, JP-A-6-240208), and a metal carboxylate are reacted. Metal carboxylate-added polysilazane obtained (for example, JP-A-6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (for example, JP-A-6-306329) Metal fines Obtained by adding the metal particles added polysilazane (e.g., JP-A-7-196986 JP), and the like.

  The content of the polysilazane compound in the solution containing the polysilazane compound varies depending on the film thickness of the desired barrier layer, the pot life of the coating solution, etc., but is 0.1 mass relative to the total amount of the solution containing the polysilazane compound. It is preferable that it is% -35 mass%.

  The solution containing the polysilazane compound may further contain an amine catalyst, a metal, and a solvent.

(Amine catalyst and metal)
The amine catalyst and the metal can promote the conversion of the polysilazane compound to the silicon oxide compound in the modification treatment described later.

  The amine catalyst that can be used is not particularly limited, but N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N ′. -Tetramethyl-1,3-diaminopropane, N, N, N ', N'-tetramethyl-1,6-diaminohexane.

  In addition, the metal that can be used is not particularly limited, and examples thereof include platinum compounds such as platinum acetylacetonate, palladium compounds such as palladium propionate, and rhodium compounds such as rhodium acetylacetonate.

  The amine catalyst and the metal are preferably contained in an amount of 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.5 to 2% by mass with respect to the polysilazane compound. When the amount of the catalyst added is within the above range, it is preferable because excessive silanol formation, film density reduction, and film defect increase due to rapid progress of the reaction can be prevented.

(solvent)
The solvent that can be contained in the solution containing the polysilazane compound is not particularly limited as long as it does not react with the polysilazane compound, and a known solvent can be used. Specific examples include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons; ether solvents such as aliphatic ethers and alicyclic ethers. More specifically, examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, toluene, xylene, solvesso, turben, methylene chloride, trichloroethane, and the like. Examples of ether solvents include dibutyl ether, dioxane, and tetrahydrofuran. These solvents can be used alone or in admixture of two or more. These solvents can be appropriately selected according to the purpose in consideration of the solubility of the polysilazane compound and the evaporation rate of the solvent.

<Formation of coating film>
A coating film is obtained by apply | coating the solution containing the said polysilazane compound on a base material.

  As a method for applying the solution containing the polysilazane compound, a known method can be appropriately employed. Examples of coating methods include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, casting film formation, bar coating, wireless bar coating, and gravure printing. Law.

  The coating amount of the solution containing the polysilazane compound is not particularly limited, but can be appropriately adjusted in consideration of the thickness of the barrier layer after drying.

  After coating the solution containing the polysilazane compound, 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 barrier layer can be obtained. The remaining solvent can be removed later.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 20-200 degreeC. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate 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. or lower, the drying time is preferably set to 1 to 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.

  Moreover, you may anneal from a viewpoint of obtaining a uniform coating film. The annealing temperature is not particularly limited, but is preferably 60 to 200 ° C, and more preferably 70 to 160 ° C. The annealing temperature may be constant, may be changed stepwise, or may be continuously changed (temperature increase and / or temperature decrease). The annealing time is not particularly limited, but is preferably 5 seconds to 24 hours, and more preferably 10 seconds to 2 hours.

<Coating film modification treatment>
The modification treatment of the coating film formed by the coating method in the present invention refers to the conversion reaction of polysilazane to silicon oxide or silicon oxynitride, and specifically contributes to the upper barrier layer exhibiting gas barrier properties. This is a treatment that forms an inorganic thin film at a possible level.

  The conversion reaction of polysilazane to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method. As the modification treatment, from the viewpoint of adapting to a plastic substrate, vacuum ultraviolet irradiation by plasma treatment capable of conversion reaction at a lower temperature or conversion reaction by ultraviolet irradiation treatment is preferable.

(Vacuum plasma treatment)
The vacuum plasma treatment is preferably performed in an atmosphere substantially free of oxygen or water vapor. Examples of the method carried out in an atmosphere substantially free of oxygen or water vapor include a method of reducing the pressure in the apparatus and a method of gas flow. The method of reducing the pressure is preferred. The pressure in the apparatus is reduced from atmospheric pressure to preferably 100 Pa or less, more preferably 20 Pa or less using a vacuum pump, and then a predetermined gas is introduced to obtain a predetermined pressure, thereby creating an atmosphere excited by plasma. to make.

  The oxygen concentration and water vapor concentration under vacuum are generally evaluated by the oxygen partial pressure and the water vapor partial pressure.

  The vacuum plasma treatment is performed under the above-described vacuum under an oxygen partial pressure of 10 Pa or less (oxygen concentration 0.001% (10 ppm)) or less, preferably an oxygen partial pressure of 2 Pa or less (oxygen concentration 0.0002% (2 ppm)) or less. The concentration is 10 ppm or less, preferably 1 ppm or less.

  Alternatively, the plasma treatment is preferably performed at normal pressure in the absence of oxygen and / or water vapor. Alternatively, the atmospheric pressure plasma treatment is performed with an oxygen concentration of 10% (100,000 ppm) or less, preferably an oxygen concentration of 5% (50000 ppm) or less, more preferably an oxygen concentration of 1% (10000 ppm) or less, more preferably an oxygen concentration of 0.1 % (1000 ppm) or less, more preferably 0.01% (100 ppm) or less, or a relative humidity of 10% or less, preferably a relative humidity of 5% or less, more preferably a relative humidity of 1% or less, more preferably An atmosphere having a relative humidity of 0.1% or less. Further, the water vapor concentration (water vapor partial pressure / atmospheric pressure at room temperature 23 ° C.) can be carried out in a low oxygen / low water vapor concentration atmosphere of 2800 ppm or less, more preferably 1400 ppm, and even more preferably 280 ppm.

  The plasma treatment is also preferably performed in an inert gas or noble gas or reducing gas atmosphere (normal pressure).

  The atmospheric gas excited by the plasma emits energy and deactivates. At that time, depending on the type and pressure of the gas, vacuum ultraviolet light having various wavelengths is emitted.

  Note that a method using plasma may be used as the vapor deposition method, but the vapor deposition method cannot substantially serve as a step of irradiating light with a wavelength of 150 nm or less. The reason for this is that there is a gas that is the material of the vapor deposition film in the space where the plasma is formed and between the plasma and the vapor deposition film, and they absorb the vacuum ultraviolet light generated from the plasma. This is because it cannot be performed efficiently.

  The vacuum plasma treatment is performed by introducing a gas into the apparatus after reducing the pressure to make the atmosphere substantially free of oxygen or water vapor. In the low-pressure plasma treatment, vacuum ultraviolet emission is used when atoms and molecules excited by low-pressure plasma fall to the ground state or the lower level. The wavelength of the vacuum ultraviolet light generated by the low-pressure plasma depends on the gas species that generates the plasma. A shorter wavelength is better, and it is more preferable to use vacuum ultraviolet light having a wavelength of 125 nm or less. However, if the wavelength is too short, the frequency of excitation to a high energy level is low, and the emission intensity is significantly reduced. The wavelength of relatively high-intensity vacuum ultraviolet light that can be used substantially in the low-pressure plasma treatment is 50 nm or more. That is, the range of 50 to 125 nm is more preferable as the wavelength of light used in the low-pressure plasma treatment.

The vacuum ultraviolet light emitted by the excited atoms formed in the plasma is absorbed by another ground state atom, which has the effect of self-absorption used to excite that atom. Therefore, if the pressure is too high, the generated vacuum ultraviolet light is absorbed by the atoms and molecules of the atmospheric gas, and the deposited film may not be efficiently irradiated. Therefore, the pressure is preferably 100 Pa or less. On the other hand, if the pressure is too low, the generation of plasma may be difficult. Therefore, the lower limit of the pressure varies depending on the plasma generation method, but is preferably about 0.1 Pa or more.

The gas species of the low-pressure plasma used in the present invention is mainly helium (He), neon (N
e) and one or more rare gases selected from argon (Ar) are used. The wavelength of the main vacuum ultraviolet light emitted by these excited rare gas atoms is 5 in the case of helium (He).
8.4 nm, 73.6 nm and 74.4 nm for Neon (Ne), Argon (Ar
) Is known to be 104.8 nm and 106.7 nm.

Further, the plasma of these rare gas atoms not only emits vacuum ultraviolet light when excited by plasma, but also forms a large amount of metastable excited atoms that do not emit light. In order to effectively use the energy of the metastable excited atoms, at least one of H ₂ and N ₂ may be added to the rare gas. When the above gas is added to the rare gas, the excitation energy of the rare gas atoms in the metastable excited state is efficiently used to excite the additive gas. With the addition of vacuum ultraviolet light emission, the irradiation intensity of vacuum ultraviolet light having a wavelength of 150 nm or less can be increased. The additive gas has a case where dissociated / excited atoms emit vacuum ultraviolet light, and an excited molecule emits vacuum ultraviolet light, but the emission of the molecule is in a band shape, and its central wavelength is Longer than the emission wavelength of atoms. For the modification of the deposited film, the emission of atoms with a short wavelength is more important. It is known that the wavelength of the main vacuum ultraviolet light emitted by the excited H atoms is 121 nm, and in the case of N atoms, it is 120 nm. As the additive gas species, H ₂ having no metastable excited state is more preferable.

  The ratio of the additive gas is preferably in the range of 0.1 to 20% by volume. If it is within this range, the effect of the additive gas appears remarkably, the plasma density is hardly reduced, and the density of the metastable rare gas atoms used for exciting the additive gas increases. . The ratio of the additive gas is more preferably in the range of 0.5 to 10% by volume.

Furthermore, in order to efficiently irradiate the deposited film with light having a wavelength of 150 nm or less, a gas species of polyatomic molecules that absorbs light having a wavelength of 150 nm or less and decomposes itself (for example, CO, CO ₂ , CH ₄ Si -H ₄ etc.) is more preferably not substantially contained.

  The frequency of the power source necessary for generating the low-pressure plasma is preferably 1 MHz to 100 GHz. Within this range, energy can be efficiently given to electrons that directly contribute to the plasma generation reaction, and the electron density, that is, the plasma density increases. Along with this, the intensity of the vacuum ultraviolet light generated by the plasma also increases. In addition, energy transmission efficiency is improved. The frequency of the power source is more preferably 4 MHz to 15 GHz.

  As a method for generating plasma that emits light having a wavelength of 150 nm or less, a conventionally known method can be used. Preferably, a method that can deal with the processing of a deposited film formed on a wide substrate is good. For example, capacitively coupled plasma (CCP), inductively coupled plasma (ICP), surface wave plasma, electron cyclotron resonance (ECR) plasma, helicon Wave plasma etc. are mentioned.

The input power density normalized by the area occupied by the plasma source reflecting the plasma magnitude is defined as an index of the magnitude of the input power to the plasma facing the deposited film. This is a parameter that correlates with the irradiation intensity of vacuum ultraviolet light applied to the deposited film per unit area. In particular,
In the case of electroded plasma such as capacitively coupled plasma, the electrode area on the side to which the high frequency is applied substantially defines the size of the plasma, and this is the area occupied by the plasma source.

The applied power per unit area is preferably 0.1 to 20 W / cm ² , more preferably 0.3 to 10 W / cm ² . If it is this range, irradiation with sufficient intensity | strength can be performed and the thermal deformation by the temperature rise of a base material, the nonuniformity of a plasma, damage to the members which comprise plasma sources, such as an electrode, etc. can be prevented.

  The time of the vacuum plasma treatment varies depending on the base material used, the composition of the barrier layer, the concentration, and the like, and is preferably determined as appropriate in consideration of damage to the material.

(Vacuum ultraviolet light irradiation)
When the coating film is irradiated with vacuum ultraviolet light as described above, the polysilazane compound constituting the coating film is modified to form a barrier layer. Here, the modification of the polysilazane compound means that the polysilazane compound is converted into a silicon oxide compound and / or a silicon oxynitride compound. In the present specification, the “vacuum ultraviolet light” means ultraviolet light including electromagnetic waves having a wavelength of 10 to 200 nm, preferably 100 to 200 nm, more preferably 100 to 180 nm.

  The reaction mechanism when perhydropolysilazane is converted by irradiation with vacuum ultraviolet light is described below, but this reaction mechanism is presumed, and the actual reaction proceeds along a different route from the reaction mechanism described. However, it is included in the technical scope of the present invention.

(I) Dehydrogenation and accompanying Si-N bond formation Si-H bonds and N-H bonds in perhydropolysilazane are relatively easily cleaved by excitation with vacuum ultraviolet light irradiation, etc., and an inert atmosphere Below, it is thought that it recombines as Si-N (the unbonded hand of Si may be formed). That is, it is cured as a SiN _y composition without being oxidized. 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. When two Si—OH are dehydrated and condensed, a Si—O—Si bond is formed and cured. This is a reaction that can occur in the air, but in the case of irradiation with vacuum ultraviolet light in an inert atmosphere, it is considered that water vapor generated as outgas from the base material by the heat of irradiation becomes the main moisture source. If 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 SiO _2.1 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 during irradiation with vacuum ultraviolet light, singlet oxygen having a very strong oxidizing power is formed. H or N in perhydropolysilazane is replaced with O to form a Si—O—Si bond and is cured. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

(IV) Oxidation accompanied by Si-N bond cleavage by vacuum ultraviolet light 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 broken, It is considered that when an oxygen source (oxygen, ozone, water, etc.) is present, it is oxidized to form a Si—O—Si bond (in some cases, 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 that has been subjected to vacuum ultraviolet light irradiation on the layer containing the polysilazane compound is performed by appropriately controlling the oxidation state by appropriately combining the oxidation mechanisms (I) to (IV) described above. Can do. As described above, since the oxidation mechanism is directly oxidized without passing through silanol (the action of a photon called a photon process), the silicon oxide film has a small volume change, a high density and a small number of defects in the oxidation process. And / or a silicon oxynitride film can be obtained. As a result, a denser silicon oxide film and / or silicon oxynitride film can be obtained. Therefore, the barrier layer obtained by modifying the polysilazane compound by irradiation with vacuum ultraviolet light can have high barrier properties.

  The light source of the vacuum ultraviolet light is not particularly limited, and a known light source can be used. For example, a low pressure mercury lamp, an excimer lamp, etc. are mentioned. Of these, it is preferable to use an excimer lamp, particularly a xenon (Xe) excimer lamp.

A rare gas excimer lamp such as the xenon excimer lamp can irradiate vacuum ultraviolet light. A rare gas atom such as Xe, Kr, Ar, Ne or the like is called an inert gas because the outermost electrons are closed and are chemically very inert. However, noble gases (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. For example, when the rare gas is xenon,
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
It becomes. At this time, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light (vacuum ultraviolet light) of 172 nm emits light. The excimer lamp uses the excimer light. Examples of the method for generating the excimer light include a method using dielectric barrier discharge and a method using electrodeless field discharge.

  A dielectric barrier discharge is a lightning generated in a gas space when a gas space is arranged between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and a high frequency high voltage of several tens of kHz is applied to the electrode. This is a very thin discharge called micro discharge. When the micro discharge streamer reaches the tube wall (dielectric), the electric charge accumulates on the dielectric surface, and the micro discharge disappears. In the dielectric barrier discharge, this micro discharge spreads over the entire tube wall and repeats generation and extinction, thereby causing flickering of light that can be seen with the naked eye. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall is accelerated.

  The electrodeless field discharge is an electrodeless field discharge due to capacitive coupling, and is also called an RF discharge. Specifically, a lamp, an electrode, and the like are arranged in the same manner as the dielectric barrier discharge, and the high frequency applied between the electrodes is uniform in space and time when a high frequency voltage of several MHz is applied. Discharge. In the method using the electrodeless electric field discharge, there is no flicker and a long-life lamp can be obtained.

  In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes, so the outer electrode covers the entire outer surface and transmits light to extract the light to the outside in order to discharge in the entire discharge space. Must be something to do. As the external electrode, a net-like electrode using a thin metal wire so as not to block light can be used. However, the external electrode can be damaged by ozone generated by irradiation with vacuum ultraviolet light. Therefore, in order to prevent damage to the electrodes, 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. Since the outer diameter of the double cylindrical lamp is about 25 mm, the difference in the distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp. sell. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution is not always 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. However, the synthetic quartz window is not only an expensive consumable, but can also cause light loss.

  On the other hand, in the case of electrodeless electric field discharge, it is not necessary to make the external electrode mesh, and glow discharge can spread over the entire discharge space only by providing the 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, can be 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 preferably 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

  The form of discharge may be dielectric barrier discharge or electrodeless field discharge. The electrode may have a flat surface in contact with the lamp, but the lamp can be firmly fixed by making the shape in accordance with the curved surface of the lamp, and the discharge can be more stable when the electrode is in close contact with the lamp. . Also, if the curved surface is made of aluminum, it can function as a light reflector.

  Such an excimer light (vacuum ultraviolet light) irradiation apparatus can use a commercially available lamp (for example, manufactured by USHIO INC., Manufactured by M.D.Com Co., Ltd.).

  The excimer lamp is characterized in that the excimer light is concentrated at one wavelength, and only the necessary light is hardly emitted, and is highly efficient. Moreover, since excess light is not radiated | emitted, the temperature of a target object can be kept low. Further, since no time is required for starting and restarting, lighting and blinking can be performed instantaneously. In particular, the Xe excimer lamp is excellent in luminous efficiency because it emits short wavelength 172 nm vacuum ultraviolet light at a single wavelength. Since the Xe excimer lamp has a short wavelength of 172 nm and a high energy, it is known that the bond breaking ability of organic compounds is high. In addition, since the Xe excimer lamp has a large oxygen absorption coefficient, it can efficiently generate active oxygen and ozone even with a very small amount of oxygen. Therefore, for example, in contrast to a low-pressure mercury lamp that emits vacuum ultraviolet light having a wavelength of 185 nm, the Xe excimer lamp has a high bond breaking ability of organic compounds, can efficiently generate active oxygen and ozone, and has a low temperature. In addition, the polysilazane compound can be modified in a short time. In addition, the Xe excimer lamp has high light generation efficiency, so it can be turned on and off instantaneously with low power, and can emit a single wavelength, thereby shortening process time and equipment area associated with high throughput. It is also preferable from the viewpoints of the economic viewpoint and application to a gas barrier film using a base material that is easily damaged by heat.

  Thus, since the excimer lamp has high light generation efficiency, it can be turned on with low power, and an increase in the surface temperature of the irradiation object can be suppressed. In addition, since the number of photons penetrating into the interior increases, the modified film thickness can be increased and / or the film quality can be increased.

  The conditions of vacuum ultraviolet light irradiation are generally examined for the conversion reaction using the integrated light amount represented by the product of irradiation intensity and irradiation time as an index, but there are various conditions even if the composition is the same as in silicon oxide. When using a material having a structural form, the absolute value of the irradiation intensity may be important.

  What is necessary is just to select the irradiation intensity | strength of vacuum ultraviolet light irradiation suitably according to a base material to be used, a composition, density | concentration, etc. of a barrier layer.

  Although the time of vacuum ultraviolet light irradiation changes also with a base material used, the composition of a barrier layer, a density | concentration, etc., it is preferable that it is 0.1 second-10 minutes, and it is more preferable that it is 0.5 second-7 minutes. preferable.

Integrated light quantity of vacuum ultraviolet light is not particularly limited, is preferably from 200~5000mJ / cm ^2, more preferably 500~3000mJ / cm ^2. It is preferable that the accumulated amount of vacuum ultraviolet light is 200 mJ / cm ² or more because high barrier properties can be obtained by sufficient modification. On the other hand, when the cumulative amount of vacuum ultraviolet light is 5000 mJ / cm ² or less, it is preferable because a barrier layer having high smoothness can be formed without deformation of the substrate.

  Moreover, the irradiation temperature of vacuum ultraviolet light changes with base materials to apply, and can be suitably determined by those skilled in the art. The irradiation temperature of the vacuum ultraviolet light is preferably 50 to 200 ° C, and more preferably 80 to 150 ° C. It is preferable for the irradiation temperature to be within the above-mentioned range since deformation of the base material, deterioration of strength, etc. are unlikely to occur and the characteristics of the base material are not impaired.

  Furthermore, the irradiation atmosphere of the vacuum ultraviolet light is not particularly limited, but it is preferably performed in an atmosphere containing oxygen from the viewpoint of generating active oxygen and ozone and efficiently modifying. The oxygen concentration in the vacuum ultraviolet irradiation is preferably 10 to 10000 volume ppm (0.001 to 1 volume%), more preferably 30 to 5000 volume ppm. It is preferable that the oxygen concentration is 10 ppm by volume or more because the reforming efficiency is increased. On the other hand, when the oxygen concentration is 10,000 ppm by volume or less, the substitution time between the atmosphere and oxygen can be shortened, which is preferable.

  The coating film to be irradiated with ultraviolet rays is mixed with oxygen and a small amount of moisture at the time of application, and adsorbed oxygen and adsorbed water may also exist in the base material and adjacent layers. If oxygen or the like is used, the oxygen source required for generation of active oxygen or ozone for performing the reforming process may be sufficient without newly introducing oxygen into the irradiation chamber. In addition, since the vacuum ultraviolet light of 172 nm like the Xe excimer lamp is absorbed by oxygen, the amount of vacuum ultraviolet light reaching the coating film may be decreased. Therefore, the oxygen concentration is set low when the vacuum ultraviolet light is irradiated. In addition, it is preferable that the vacuum ultraviolet light be able to efficiently reach the coating film.

  The gas other than oxygen in the atmosphere irradiated with vacuum ultraviolet light is preferably a dry inert gas, and more preferably a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas, inert gas, or the like introduced into the irradiation chamber and changing the flow rate ratio.

  From the viewpoint of improving irradiation efficiency and achieving uniform irradiation, the generated vacuum ultraviolet light may be applied to the barrier layer before modification after reflecting the vacuum ultraviolet light from the generation source with a reflector. Moreover, the irradiation of vacuum ultraviolet light 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, when the substrate is in the form of a long film, it is preferable to perform the modification by continuously irradiating the vacuum ultraviolet light while transporting the substrate.

  The film thickness, density, and the like of the barrier layer obtained by the above-described modification treatment can be controlled by appropriately selecting application conditions, vacuum ultraviolet light irradiation conditions, and the like. For example, the film thickness and density of the barrier layer can be controlled by appropriately selecting the irradiation method of vacuum ultraviolet light from continuous irradiation, irradiation divided into a plurality of times, and so-called pulse irradiation, etc. in which the plurality of times of irradiation is short. Can be done.

  The thickness of the barrier layer (application thickness) can be appropriately set according to the purpose. For example, the thickness of the barrier layer (coating thickness) is preferably about 1 nm to 100 μm, more preferably about 10 nm to 10 μm, and more preferably 50 nm to 1 μm as the thickness after drying. More preferably, it is 20 nm-2 micrometers especially preferable. If the thickness of the barrier layer is 1 nm or more, sufficient barrier properties can be obtained, and if it is 100 μm or less, stable coating properties can be obtained when forming the barrier layer, and high light transmittance can be realized.

  The barrier layer preferably has an appropriate surface smoothness. Specifically, as the smoothness of the surface of the barrier layer, the center line average roughness (Ra) of the barrier layer is preferably 50 nm or less, and more preferably 10 nm or less. The lower limit of the center line average roughness (Ra) of such a barrier layer is not particularly limited, but is practically 0.01 nm or more and preferably 0.1 nm or more. In the case of such a barrier layer having Ra, the second barrier layer is closely formed on the barrier layer corresponding to the unevenness in the barrier layer. For this reason, the second barrier layer more efficiently covers defects such as cracks and dangling bonds generated in the barrier layer, thereby forming a dense surface. Therefore, it is possible to more effectively suppress and prevent a decrease in gas barrier properties (for example, low oxygen permeability and low water vapor permeability) under high temperature and high humidity conditions. In the present specification, the center line average roughness (Ra) of the barrier layer is a value measured by the method described in the following examples.

  The method for forming the barrier layer having the center line average roughness (Ra) is not particularly limited. For example, a method of providing a control layer (especially the following CVD layer) between the substrate and the barrier layer; a method of providing an intermediate layer (especially the following CVD layer) between the barrier layer and the second barrier layer A method of controlling the surface roughness by selecting a substrate; a method of controlling the surface roughness of the underlayer; a method of performing a surface treatment before applying the PHPS layer; ) Can be controlled within the above range.

[Ultraviolet reflective film]
The ultraviolet reflecting performance of the gas barrier film according to the present invention can be achieved by, for example, an ultraviolet reflecting film. The ultraviolet reflecting film selectively reflects ultraviolet light which causes deterioration of the barrier film, so that only light except the ultraviolet light can enter the gas barrier film. For this reason, it is preferable that at least one of the ultraviolet reflecting films is provided on the incident light side with respect to the barrier film, and at least one of the ultraviolet reflecting films is preferably not covered with the barrier layer.

  Although the ultraviolet reflective film of the present invention is not particularly limited, a film including at least one optical interference film formed by alternately laminating a high refractive index layer and a low refractive index layer on a substrate can be used. . From the viewpoint of ultraviolet reflectivity and productivity, the range of the total number of the high refractive index layer and the low refractive index layer is preferably 100 layers or less, 5 layers or more, more preferably 40 layers or less, 5 layers or more, and further preferably. Is 20 layers or less and 5 layers or more.

  In general, in an ultraviolet shielding film, it is preferable to design a large difference in refractive index between a high refractive index layer and a low refractive index layer from the viewpoint that the reflectance for a desired light beam can be increased with a small number of layers. . In the present invention, the difference in refractive index between at least two adjacent layers (high refractive index layer and low refractive index layer) is preferably 0.1 or more, more preferably 0.25 or more, and further preferably 0. .3 or more, more preferably 0.35 or more, and most preferably 0.4 or more. The upper limit is not particularly limited, but is usually 1.4 or less.

  The refractive index difference between the refractive index layers in the ultraviolet shielding film and the necessary number of layers can be calculated using commercially available optical design software.

  When the high refractive index layer and the low refractive index layer are alternately laminated in the ultraviolet shielding film, the refractive index difference between the high refractive index layer and the low refractive index layer is within the range of the preferred refractive index difference. Is preferred. However, for example, when the outermost layer is formed as a layer for protecting the film or when the lowermost layer is formed as an adhesion improving layer with the substrate, the above-mentioned preferable refraction is performed with respect to the outermost layer and the lowermost layer. A configuration outside the range of the rate difference may be used.

  Since reflection at the interface between adjacent layers depends on the refractive index ratio between the layers, the larger the refractive index ratio, the higher the reflectance. In addition, when the optical path difference between the reflected light on the surface of the layer and the reflected light on the bottom of the layer is a relationship expressed by n · d = wavelength / 4 when viewed as a single layer film, the reflected light is controlled to be strengthened by the phase difference. And reflectivity can be increased. Here, n is the refractive index, d is the physical film thickness of the layer, and n · d is the optical film thickness. By using this optical path difference, reflection can be controlled. Using this relationship, the refractive index and film thickness of each layer are controlled to control the transmission of visible light and the reflection of ultraviolet light.

  Moreover, it is preferable that the relationship between the average thickness dH of the high refractive index layer and the average thickness dL of the low refractive index layer satisfies the following expressions (1) and (2).

| DH−dL | <40 nm Formula (1)
| DH + dL | <150 nm Formula (2)
By satisfying the above formulas (1) and (2), the reflectance in the ultraviolet region can be increased. | DH−dL | is more preferably 25 nm or less. The lower limit of | dH−dL | is not particularly limited, but is preferably 5 nm or more in order to ensure an optical path difference. Further, | dH + dL | is more preferably 130 nm or less. The lower limit of | dH + dL | is usually 100 nm or more.

  The wavelength having the maximum reflectance in the spectrum of the ultraviolet shielding film of the present invention is not particularly limited as long as it is in the ultraviolet shielding wavelength region, but it is preferably designed to be 350 to 380 nm. This is because light with a wavelength shorter than 340 nm out of 280 nm to 380 nm, which is ultraviolet light harmful to the resin support, is absorbed by a metal oxide having a high refractive index such as titanium oxide or zirconium oxide contained in the high refractive index layer. In addition, since the film can be shielded by an ultraviolet absorber, it is preferable to design the film so that a region of 350 to 380 nm which is difficult to cut with a metal oxide or an ultraviolet absorber can be reflected.

  The ultraviolet shielding film of the present invention preferably has a high visible light transmittance. A formed body in which an ultraviolet shielding laminated portion is formed on a resin support is prepared, and the average transmittance of the formed body at 400 to 2500 nm is preferably 60% or more, more preferably 70% or more, and 80 % Or more is more preferable. Moreover, it is preferable that the average reflectance of an ultraviolet region (280-400 nm) is 10% or more, and it is more preferable that it is 20% or more.

  The low refractive index layer preferably has a refractive index of 1.10 to 1.60, more preferably 1.30 to 1.55. The high refractive index layer preferably has a refractive index of 1.80 to 2.50, more preferably 1.80 to 2.20.

  The thickness per layer of the low refractive index layer (thickness after drying) is preferably 20 to 80 nm, more preferably 30 to 70 nm, and more preferably 40 to 60 nm.

  Here, when measuring the thickness per layer, the high refractive index layer and the low refractive index layer may have a clear interface between them or may be gradually changed. When the interface is gradually changing, the maximum refractive index-minimum refractive index = Δn in the region where the layers are mixed and the refractive index continuously changes, the minimum refractive index between two layers + Δn The point of / 2 is regarded as the layer interface.

  The total thickness of the ultraviolet reflective film of the present invention is preferably 3 μm to 5 μm, more preferably 3 μm to 4 μm.

  In the present invention, the first metal oxide particles included in the one or more high refractive index layers constituting the optical interference film in which the high refractive index layers and the low refractive index layers are alternately stacked include core-shell particles. . Therefore, when the ultraviolet reflective film of the present invention has a plurality of high refractive index layers, it is sufficient that at least one layer of the plurality of high refractive index layers contains core-shell particles, and the ultraviolet reflective film of the present invention has a high refractive index. In the case of having one refractive index layer, the single high refractive index layer may contain core-shell particles. It is particularly preferred that all high refractive index layers contain core-shell particles.

In the ultraviolet reflecting film according to the present invention, at least one of the high refractive index layers is coated with a first water-soluble binder resin and a silicon-containing hydrated oxide as a first metal oxide particle. Core-shell particles. Therefore, due to the structure of the present invention, due to the interaction between the silicon-containing hydrated oxide on the surface of the core-shell particles and the first water-soluble binder resin, the core-shell particles and the first water-soluble binder resin Therefore, it is considered that intermixing between the high refractive index layer and the low refractive index layer is suppressed, and preferable ultraviolet reflection characteristics are achieved. In particular, when polyvinyl alcohol is used as the first water-soluble binder resin, the core-shell particles and the polyvinyl alcohol form a strong hydrogen bonding network between the OH groups, thereby providing a high refractive index layer and a low refractive index layer. The interlayer mixing is suppressed, and preferable near-infrared blocking characteristics are achieved. The effect of the interaction and the titanium oxide particles used as the material for increasing the refractive index are suppressed by the photocatalytic activity by using the core-shell particles coated with the silicon-containing hydrated oxide. It is considered that an ultraviolet reflecting film having excellent durability can be provided even when the temperature changes. In the refractive index control of the high refractive index layer, it is considered that the refractive index difference between the high refractive index layer and the low refractive index layer can be effectively controlled by controlling the silica coating amount. The components contained in the high refractive index layer and the low refractive index layer, which are components of the ultraviolet reflective film of the present invention, will be described in detail.

(Water-soluble binder resin)
In the present invention, examples of the water-soluble binder resin that can be contained in the high refractive index layer and the low refractive index layer include polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymers, acrylic acid. Acrylic resins such as potassium-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, or acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, Styrene acrylic acid resin such as styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, or styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene -Sodium styrenesulfonate copolymer, Styrene-2-hydroxyethyl acrylate copolymer, styrene-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer Vinyl acetate copolymers such as polymers, vinyl naphthalene-maleic acid copolymers, vinyl acetate-maleic acid ester copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-acrylic acid copolymers, and the like Synthetic water-soluble resins such as salts; natural water-soluble resins such as gelatin and thickening polysaccharides. Among these, particularly preferred examples include polyvinyl alcohol, polyvinylpyrrolidones and copolymers containing them, gelatin, thickening polysaccharides (particularly celluloses) from the viewpoint of handling during production and film flexibility. Among these, polyvinyl alcohol is more preferable from the viewpoint of optical properties. These water-soluble resins may be used alone or in combination of two or more.

  The polyvinyl alcohol preferably used in the present invention includes modified polyvinyl alcohol in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate. Examples of the modified polyvinyl alcohol include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonion-modified polyvinyl alcohol, and vinyl alcohol polymers.

  The polyvinyl alcohol obtained by hydrolyzing vinyl acetate preferably has an average degree of polymerization of 1,000 or more, and particularly preferably has an average degree of polymerization of 1,500 to 5,000. The degree of saponification is preferably 70 to 100 mol%, particularly preferably 80 to 99.5 mol%.

  Here, the degree of polymerization refers to the viscosity average degree of polymerization, and is measured according to JIS-K6726 (1994). After the PVA is completely re-saponified and purified, the intrinsic viscosity [η] measured in water at 30 ° C. It can be obtained from (dl / g) by the following equation.

  Examples of the cation-modified polyvinyl alcohol have primary to tertiary amino groups and quaternary ammonium groups in the main chain or side chain of the polyvinyl alcohol as described in JP-A-61-110483. Polyvinyl alcohol, which is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.

  Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride. N-vinylimidazole, N-vinyl-2-methylimidazole, N- (3-dimethylaminopropyl) tacrylamido, hydroxylethyltrimethylammonium chloride, trimethyl- (2-methacrylamidopropyl) ammonium chloride, N- (1,1 -Dimethyl-3-dimethylaminopropyl) acrylamide and the like. The ratio of the cation-modified group-containing monomer of the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.

  Anion-modified polyvinyl alcohol is, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-2060888, as described in JP-A-61-237681 and JP-A-63-330779, Examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.

  Nonionic modified polyvinyl alcohol is, for example, a polyvinyl alcohol derivative obtained by adding a polyalkylene oxide group to a part of vinyl alcohol as described in JP-A-7-9758, and described in JP-A-8-25595. Block copolymer of vinyl compound having hydrophobic group and vinyl alcohol, silanol modified polyvinyl alcohol having silanol group, reactive group modified polyvinyl alcohol having reactive group such as acetoacetyl group, carbonyl group, carboxyl group Etc. Examples of the vinyl alcohol polymer include Exeval (trade name: manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (trade name: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). Polyvinyl alcohol can be used in combination of two or more, such as the degree of polymerization and the type of modification.

  In addition to lime-processed gelatin, acid-processed gelatin may be used as gelatin applicable to the present invention, and gelatin hydrolyzate and gelatin enzyme-decomposed product can also be used.

  Examples of thickening polysaccharides that can be used in the present invention include generally known natural polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides and synthetic complex polysaccharides. For details, reference can be made to “Biochemical Encyclopedia (2nd edition), Tokyo Chemical Doujinshi”, “Food Industry”, Vol. 31 (1988), p. 21.

  The thickening polysaccharide referred to in the present invention is a polymer of saccharides and has many hydrogen bonding groups in the molecule, and the viscosity at low temperature and the viscosity at high temperature due to the difference in hydrogen bonding force between molecules depending on the temperature. It is a polysaccharide with a large difference in characteristics, and when adding metal oxide fine particles, it causes a viscosity increase that seems to be due to hydrogen bonding with the metal oxide fine particles at a low temperature. When added, it is a polysaccharide that causes an increase in viscosity at 40 ° C. of 1.0 mPa · s or more, preferably 5.0 mPa · s or more, more preferably 10.0 mPa · s or more. Polysaccharides.

  Examples of the thickening polysaccharide applicable to the present invention include β1-4 glucan (eg, carboxymethylcellulose, carboxyethylcellulose, etc.), galactan (eg, agarose, agaropectin, etc.), galactomannoglycan (eg, locust bean gum). , Guaran, etc.), xyloglucan (eg, tamarind gum, etc.), glucomannoglycan (eg, salmon mannan, wood-derived glucomannan, xanthan gum, etc.), galactoglucomannoglycan (eg, softwood-derived glycan), arabino Galactoglycan (for example, soybean-derived glycan, microorganism-derived glycan, etc.), Glucarnoglycan (for example, gellan gum), glycosaminoglycan (for example, hyaluronic acid, keratan sulfate, etc.), alginic acid and alginate, agar, κ -Natural polymer polysaccharides derived from red algae such as -carrageenan, λ-carrageenan, ι-carrageenan, furseleran and the like.

  The weight average molecular weight of the water-soluble resin is preferably 1,000 or more and 200,000 or less. Furthermore, 3,000 or more and 40,000 or less are more preferable. In this specification, the value measured on the following measurement conditions using gel permeation chromatography (GPC) is employ | adopted for a weight average molecular weight.

Solvent: 0.2M NaNOH ₃ , NaH ₂ P0 ₄ , pH 7
Column: Combination of Shodex Column Ohpak SB-802.5 HQ, 8 × 300 mm and Shodex Column Ohpak SB-805 HQ, 8 × 300 mm Column temperature: 45 ° C.
Sample concentration: 0.1% by mass
Detector: RID-10A (manufactured by Shimadzu Corporation)
Pump: LC-20AD (manufactured by Shimadzu Corporation)
Flow rate: 1 ml / min
Calibration curve: Standard P-82 for Shodex Standard GFC (aqueous GPC) column Use of calibration curve with standard substance pullulan Among them, it is preferable to use polyvinyl alcohol because of its good optical reflection characteristics.

  The water-soluble resin may be cured using a curing agent.

  The curing agent applicable to the present invention is not particularly limited as long as it causes a curing reaction with a water-soluble resin.

  When the water-soluble resin is polyvinyl alcohol, the curing agent that can be used is not particularly limited as long as it causes a curing reaction with polyvinyl alcohol, but a group consisting of boric acid, borate, and borax. Is preferably selected from. Known compounds other than boric acid, borate, and borax can be used, and generally compounds having a group capable of reacting with polyvinyl alcohol or compounds that promote the reaction between different groups possessed by polyvinyl alcohol These are appropriately selected and used. Specific examples of the curing agent include, for example, epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl- 4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde curing agents (formaldehyde, glioxal, etc.), active halogen curing agents (2,4-dichloro-4-hydroxy-1,3,5) , -S-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum and the like.

  Boric acid or borate refers to oxyacids and salts thereof having a boron atom as a central atom, and specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octaborate. Boric acid and their salts.

Borax is a mineral represented by Na ₂ B ₄ O ₅ (OH) ₄ .8H ₂ O (decahydrate of sodium tetraborate Na ₂ B ₄ O ₇ ).

  Boric acid having a boron atom as a curing agent, borate, and borax may be used as a single aqueous solution or in combination of two or more. An aqueous solution of boric acid or a mixed aqueous solution of boric acid and borax is preferred. The aqueous solutions of boric acid and borax can be added only as relatively dilute aqueous solutions, respectively, but by mixing them both can be made into a concentrated aqueous solution and the coating solution can be concentrated. Further, the pH of the aqueous solution to be added can be controlled relatively freely.

  In the present invention, it is preferable to use boric acid and a salt thereof and / or borax in order to obtain the effects of the present invention. When boric acid and its salts and / or borax are used, preferable ultraviolet shielding properties can be achieved more. In particular, when a multilayer coating of a high refractive index layer and a low refractive index layer is applied with a coater, the film surface temperature of the coating film is once cooled to about 15 ° C., and then the set surface coating process is used to dry the film surface. Can express an effect more preferably.

  1-600 mg is preferable per 1 g of polyvinyl alcohol-type resin, and, as for the total usage-amount of the said hardening | curing agent, 100-500 mg is more preferable.

  When the water-soluble resin is gelatin, for example, an organic hardener such as a vinyl sulfone compound, a urea-formalin condensate, a melanin-formalin condensate, an epoxy compound, an aziridine compound, an active olefin, an isocyanate compound, Examples thereof include inorganic polyvalent metal salts such as chromium, aluminum and zirconium.

  Further, when both the high refractive index layer and the low refractive index layer contain polyvinyl alcohol, the average saponification degree of polyvinyl alcohol contained in the high refractive index layer and the average saponification degree of polyvinyl alcohol contained in the low refractive index layer. And are preferably different.

  By making the average saponification degree of the polyvinyl alcohol contained in the high refractive index layer different from the average saponification degree of the polyvinyl alcohol contained in the low refractive index layer, interlayer mixing can be suppressed and reflection characteristics can be improved. . Moreover, since interlayer mixing is suppressed, the haze of the film can also be reduced.

  The average degree of saponification of polyvinyl alcohol in each refractive index layer is determined in consideration of the content ratio in the refractive index layer. That is, the average degree of saponification = Σ (degree of saponification of each polyvinyl alcohol (mol%) × content of each polyvinyl alcohol in each refractive index layer (%) / 100 mass (%)). For example, the refractive index layer is polyvinyl alcohol A (the mass ratio in the refractive index layer (the mass content (%) of each polyvinyl alcohol in each refractive index layer / 100 mass (%)): Wa, the saponification degree: Sa (mol %)), Polyvinyl alcohol B (mass ratio in the refractive index layer: Wb, saponification degree: Sb (mol%)), polyvinyl alcohol C (mass ratio in the refractive index layer: Wc, saponification degree: Sc (mol) %)), The average degree of saponification = (Wa × Sa + Wb × Sb + Wc × Sc / (Wa + Wb + Wc)).

  The difference (absolute value) between the average saponification degree of polyvinyl alcohol contained in the high refractive index layer and the average saponification degree of polyvinyl alcohol contained in the low refractive index layer is preferably 1 mol% or more, and is 3 mol% or more. Preferably, it is 5 mol% or more, more preferably 8 mol% or more. If it is such a range, the effect of this invention will increase further and film characteristics (a reflection characteristic, visible light transmittance, etc.) will improve more. The difference between the average saponification degree of polyvinyl alcohol contained in the high refractive index layer and the average saponification degree of polyvinyl alcohol contained in the low refractive index layer is preferably as far as possible, but the dissolution of polyvinyl alcohol in water is preferable. From the viewpoint of properties, it is preferably 20 mol% or less.

  The content of the water-soluble resin in the refractive index layer is not particularly limited, but is preferably 1 to 50 mass%, more preferably, based on the total mass (solid content) of each refractive index layer. It is 5-30 mass%.

  In order to adjust the refractive index difference, a fluorine-containing polymer may be used for the low refractive index layer. Examples of the fluorine-containing polymer include a polymer mainly containing a fluorine-containing unsaturated ethylenic monomer component.

  Examples of the fluorine-containing unsaturated ethylenic monomer include a fluorine-containing alkene, a fluorine-containing acrylic ester, a fluorine-containing methacrylate, a fluorine-containing vinyl ester, a fluorine-containing vinyl ether, and the like. And fluorine-containing unsaturated ethylenic monomers described in paragraph “0181” of the No.

  Examples of monomers that can be copolymerized with fluorine-containing monomers include, for example, ethylene, propylene, butene, vinyl acetate, vinyl ethyl ether, vinyl ethyl ketone, methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl-α-fluoroacrylate, ethyl-α-fluoroacrylate, propyl-α-fluoroacrylate, butyl-α-fluoroacrylate, cyclohexyl-α-fluoroacrylate, hexyl-α-fluoroacrylate , Benzyl-α-fluoroacrylate, acrylic acid, methacrylic acid, α-fluoroacrylic acid, styrene, styrene sulfonic acid, methoxypolyethylene glycol And methacrylate.

  Refractive index of single resin of fluorine-containing ethylenically unsaturated monomer is in the range of about 1.33 to 1.42, and refractive index of single resin polymer of monomer not containing fluorine that can be copolymerized. Can be used as a fluorine-containing polymer having a desired refractive index by copolymerizing these at an arbitrary ratio of 1.44 or more, and having a desired refractive index by mixing with the polyvinyl alcohol at an arbitrary ratio. Can be used. The mass ratio (in terms of solid content) in the refractive index layer of such a fluoropolymer and polyvinyl alcohol is preferably polyvinyl alcohol: fluoropolymer = 1: 0.1-5.

(Metal oxide)
At least one of the high refractive index layer and the low refractive index layer preferably contains a metal oxide (particle) together with the water-soluble resin. By containing metal oxide particles, the refractive index difference between the refractive index layers can be increased, and the reflection characteristics are improved. In particular, metal oxides such as titanium oxide and zirconium oxide absorb ultraviolet rays and improve ultraviolet shielding properties. Therefore, at least the high refractive index layer preferably contains metal oxide particles, and the refractive index difference is further increased. Therefore, it is more preferable that both the high refractive index layer and the low refractive index layer contain metal oxide particles.

  The metal oxide particles preferably have an average particle size of 100 nm or less. When the average particle diameter of the metal oxide particles to be used is 100 nm or less, light scattering can be suppressed and the accuracy in controlling the film thickness of each refractive index layer in the ultraviolet shielding film can be improved. Here, in this specification, an average particle diameter refers to a primary average particle diameter. As used herein, the primary average particle size refers to a method of observing the particle itself using a laser diffraction scattering method, a dynamic light scattering method, or an electron microscope, and a particle image appearing on the cross section or surface of the refractive index layer. The average particle size is a value obtained by measuring the particle size of 1,000 arbitrary particles by a method of observing with an electron microscope. When the metal oxide particles are coated (for example, silica-attached titanium dioxide described later), the average particle diameter of the metal oxide particles is the base (the silica-attached titanium dioxide). In this case, it means the average particle diameter of titanium dioxide before treatment).

(Metal oxide in the low refractive index layer)
Silica (silicon dioxide) is preferably used as the metal oxide for the low refractive index layer, and specific examples include synthetic amorphous silica and colloidal silica. Among these, it is more preferable to use acidic colloidal silica sol, and it is particularly preferable to use colloidal silica dispersed in an organic solvent. In order to further reduce the refractive index, hollow fine particles having pores inside the particles may be used as the metal oxide fine particles of the low refractive index layer, and hollow fine particles of silica (silicon dioxide) are particularly preferable. Moreover, well-known metal oxide particles other than a silica can also be used.

  The metal oxide particles (preferably silicon dioxide) contained in the low refractive index layer preferably have an average particle size of 3 to 100 nm. The average particle size of primary particles of silicon dioxide dispersed in a primary particle state (particle size in a dispersion state before coating) is more preferably 3 to 50 nm, and further preferably 3 to 40 nm. 3 to 20 nm is particularly preferable, and 4 to 10 nm is most preferable. Moreover, as an average particle diameter of secondary particle | grains, it is preferable from a viewpoint with few hazes and excellent visible light transmittance | permeability that it is 30 nm or less.

  When obtained from a transmission electron microscope, the primary average particle diameter of the particles is observed with an electron microscope on the particles themselves or the cross section or surface of the refractive index layer, and the particle diameter of 1000 arbitrary particles is measured. It is obtained as its simple average value (number average). Here, the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.

  Further, the particle diameter of the metal oxide particles of the low refractive index layer can be determined by a volume average particle diameter in addition to the primary average particle diameter.

  The colloidal silica used in the present invention is obtained by heating and aging a silica sol obtained by metathesis with an acid of sodium silicate or the like and passing through an ion exchange resin layer. For example, JP-A-57-14091, JP-A-60-219083, JP-A-60-219084, JP-A-61-20792, JP-A-61-188183, JP-A-63-17807, JP-A-4-93284 No. 5, JP-A-5-278324, JP-A-6-92011, JP-A-6-183134, JP-A-6-297830, JP-A-7-81214, JP-A-7-101142. JP-A-7-179029, JP-A-7-137431, and International Publication No. 94/26530. Than is.

  Such colloidal silica may be a synthetic product or a commercially available product. Examples of commercially available products include the Snowtex series (Snowtex OS, OXS, S, OS, 20, 30, 40, O, N, C, etc.) sold by Nissan Chemical Industries.

  The surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.

  Moreover, hollow particles can also be used as the metal oxide particles of the low refractive index layer. When hollow fine particles are used, the average particle pore size is preferably 3 to 70 nm, more preferably 5 to 50 nm, and even more preferably 5 to 45 nm. The average particle pore size of the hollow fine particles is an average value of the inner diameters of the hollow fine particles. If the average particle pore diameter of the hollow fine particles is within the above range, the refractive index of the low refractive index layer is sufficiently lowered. The average particle diameter is 50 or more at random, which can be observed as an ellipse in a circular, elliptical or substantially circular shape by electron microscope observation, and obtains the pore diameter of each particle. Is obtained. The average particle hole diameter means the minimum distance among the distances between the two parallel lines that surround the outer edge of the hole diameter that can be observed as a circle, an ellipse, or a substantially circle or ellipse.

  The content of the metal oxide particles in the low refractive index layer is preferably 20 to 90% by mass, and more preferably 30 to 85% by mass with respect to 100% by mass of the solid content of the low refractive index layer. More preferably, it is 40-70 mass%. When it is 20% by mass or more, a desired refractive index is obtained, and when it is 90% by mass or less, the coatability is good, which is preferable.

(Metal oxide in the high refractive index layer)
As the metal oxide particles of the high refractive index layer according to the present invention, for example, titanium dioxide, zirconium oxide, zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, oxidized oxide Examples thereof include ferric iron, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide. Among these, metal oxide particles such as titanium dioxide and zirconium oxide are preferable because they can absorb light in the ultraviolet region.

  In the present invention, in order to form a transparent and higher refractive index layer having a higher refractive index, the high refractive index layer is made of high refractive index metal oxide fine particles such as titanium dioxide and zirconium oxide, that is, fine particles of titanium oxide and fine particles of zirconium oxide. It is preferable to contain. In that case, it is preferable to contain rutile (tetragonal) titanium oxide particles.

  The primary average particle diameter of the metal oxide particles used for the metal oxide particles used in the high refractive index layer is preferably 30 nm or less, more preferably 1 to 30 nm, and more preferably 5 to 15 nm. Further preferred. A primary average particle diameter of 1 nm or more and 30 nm or less is preferable from the viewpoint of low haze and excellent visible light transmittance.

  As the titanium oxide particles of the present invention, it is preferable to use particles in which the surface of an aqueous titanium oxide sol is modified to stabilize the dispersion state.

  As a method for preparing the aqueous titanium oxide sol, any conventionally known method can be used. For example, JP-A-63-17221, JP-A-7-819, JP-A-9-165218, See the matters described in Kaihei 11-43327, JP-A 63-17221, JP-A 7-819, JP-A 9-165218, JP-A 11-43327, etc. Can do.

  As for other methods for producing titanium oxide particles, for example, “Titanium oxide—physical properties and applied technology”, Kiyoshi Manabu, p. 255-258 (2000), Gihodo Publishing Co., Ltd., or WO 2007/039953, paragraph numbers 0011- The method of the step (2) described in 0023 can be referred to.

  In the production method according to the above step (2), titanium dioxide hydrate is treated with at least one basic compound selected from the group consisting of alkali metal hydroxides or alkaline earth metal hydroxides. After the step (1), the titanium dioxide dispersion obtained comprises a step (2) of treating with a carboxylic acid group-containing compound and an inorganic acid.

Furthermore, another method for producing metal oxide particles including titanium oxide particles is disclosed in JP-A-2000-053421 (comprising alkyl silicate as a dispersion stabilizer, and silicon in the alkyl silicate can be converted to SiO _2. Weight ratio (SiO ₂ / TiO ₂ ) of the amount converted to TiO ₂ and the amount converted to TiO ₂ in the titanium oxide is 0.7 to 10), JP 2000-063119 A (TiO ₂ -ZrO ₂ -SnO ₂ composite colloidal particles as the core, and the surface thereof coated with the composite oxide colloidal particles of WO ₃ -SnO ₂ -SiO ₂ ) can be referred to. .

  Further, the titanium oxide particles may be coated with a silicon-containing hydrated oxide. Here, the “coating” means a state in which a silicon-containing hydrated oxide is attached to at least a part of the surface of the titanium oxide particles. That is, the surface of the titanium oxide particles used as the metal oxide particles may be completely covered with a silicon-containing hydrated oxide, and a part of the surface of the titanium oxide particles is a silicon-containing hydrated oxide. It may be coated. From the viewpoint that the refractive index of the coated titanium oxide particles is controlled by the coating amount of the silicon-containing hydrated oxide, it is preferable that a part of the surface of the titanium oxide particles is coated with the silicon-containing hydrated oxide. .

  The titanium oxide of the titanium oxide particles coated with the silicon-containing hydrated oxide may be a rutile type or an anatase type. The titanium oxide particles coated with a silicon-containing hydrated oxide are more preferably rutile-type titanium oxide particles coated with a silicon-containing hydrated oxide. This is because the rutile type titanium oxide particles have lower photocatalytic activity than the anatase type titanium oxide particles, and therefore the weather resistance of the high refractive index layer and the adjacent low refractive index layer is increased, and the refractive index is further increased. Because.

  The “silicon-containing hydrated oxide” in the present specification may be any of a hydrate of an inorganic silicon compound, a hydrolyzate and / or a condensate of an organosilicon compound, and in order to obtain the effects of the present invention. More preferably has a silanol group.

  The coating amount of the silicon-containing hydrated oxide is 3 to 30% by mass, preferably 3 to 10% by mass, and more preferably 3 to 8% by mass. This is because when the coating amount is 30% by mass or less, the desired refractive index of the high refractive index layer can be obtained, and when the coating amount is 3% or more, particles can be stably formed.

As a method of coating titanium oxide particles with a silicon-containing hydrated oxide, it can be produced by a conventionally known method. For example, JP-A-10-158015 (Si / Al hydration to rutile titanium oxide) Oxide treatment; a method for producing a titanium oxide sol in which a hydrous oxide of silicon and / or aluminum is deposited on the surface of titanium oxide after peptization in the alkaline region of the titanate cake), JP 2000-204301 A (A sol in which a rutile titanium oxide is coated with a complex oxide of Si and Zr and / or Al. Hydrothermal treatment), JP 2007-246351 (Oxidation obtained by peptizing hydrous titanium oxide) titanium to hydrosol, wherein ^R 1 ^nSiX ₄ -n (wherein ^{R 1} as stabilizer _C 1 -C ₈ alkyl group, glycidyl-substituted C1-C8 A compound having a complexing action with respect to an organoalkoxysilane or titanium oxide of an alkyl group or a C2-C8 alkenyl group, X is an alkoxy group, and n is 1 or 2. Sodium silicate or silica sol in an alkali region is added. The method described in, for example, a method for producing a titanium oxide hydrosol coated with a hydrous oxide of silicon by adding, pH adjusting, and aging to the above solution can be referred to.

In addition, as the metal oxide particles contained in the high refractive index layer, core-shell particles produced by a known method can be used. For example, the following (i) to (iv); (i) An aqueous solution containing titanium oxide particles is hydrolyzed by heating, or an aqueous solution containing titanium oxide particles is neutralized by adding an alkali, so that the average particle size is After obtaining 1 to 30 nm of titanium oxide, the titanium oxide particles and the mineral acid were mixed so that the titanium oxide particles / mineral acid in a molar ratio ranged from 1 / 0.5 to 1/2. The slurry is heat-treated at a temperature not lower than the boiling point of the slurry and not higher than the boiling point of the slurry, and then a silicon compound (for example, an aqueous sodium silicate solution) is added to the obtained slurry containing the titanium oxide particles. (Ii) Hydrous Titanium Hydroxide: a method of precipitating silicon hydrated oxide on the surface and then treating the surface, and then removing impurities from the resulting slurry of the surface treated titanium oxide particles (Japanese Patent Laid-Open No. 10-158015); A method of neutralizing by mixing a titanium oxide sol stabilized at a pH in an acidic range obtained by peptizing a monobasic acid or a salt thereof with an alkyl silicate as a dispersion stabilizer by a conventional method ( (Iii) Hydrogen peroxide and tin metal are simultaneously or alternately kept in a mixed aqueous solution of a titanium salt (for example, titanium tetrachloride) while maintaining a molar ratio of H2O2 / Sn of 2 to 3 And a basic salt aqueous solution containing titanium is produced, and the basic salt aqueous solution is held at a temperature of 50 to 100 ° C. for 0.1 to 100 hours to form aggregates of complex colloid containing titanium oxide. Then, the electrolyte in the aggregate slurry is removed to produce a stable aqueous sol of composite colloidal particles containing titanium oxide; silicate (eg, sodium silicate aqueous solution), etc. A stable aqueous sol of composite colloidal particles containing silicon dioxide is produced by preparing an aqueous solution containing and removing cations present in the aqueous solution; the resulting composite aqueous sol containing titanium oxide is metal 100 parts by weight in terms of oxide TiO _2, and ₂ to 100 parts by weight in terms of metal oxide SiO ₂ in which the composite aqueous sol containing silicon dioxide obtained was mixed,
A method of heating and aging at 80 ° C. for 1 hour after removing the anion (Japanese Patent Laid-Open No. 2000-063119); (iv) Hydrogen peroxide is added to a hydrous titanic acid gel or sol to dissolve the hydrous titanic acid. A silicon compound or the like is added to the peroxotitanic acid aqueous solution and heated to obtain a dispersion of core particles composed of a complex solid solution oxide having a rutile structure, and then the silicon compound or the like is added to the dispersion of the core particles. Then, heating is performed to form a coating layer on the surface of the core particles to obtain a sol in which the composite oxide particles are dispersed, and further heating (Japanese Patent Laid-Open No. 2000-204301); Titanium oxide hydrosol obtained by glueing, organoalkoxysilane (R ¹ nSiX ₄ -n) or hydrogen peroxide and aliphatic or aromatic hydroxycarboxylic acid as stabilizer The core-shell particles produced by the method of adding a compound selected from the above, adjusting the pH of the solution to 3 or more and less than 9 and performing aging after desalting (Japanese Patent No. 4550753);

  The core-shell particles may be those in which the entire surface of the titanium oxide particles as a core is coated with a silicon-containing hydrated oxide, and a part of the surface of the titanium oxide particles as a core is covered with a silicon-containing hydrated oxide. It may be coated with.

  Furthermore, the metal oxide particles used in the present invention are preferably monodispersed. The monodispersion here means that the monodispersity obtained by the following formula is 40% or less. This monodispersity is more preferably 30% or less, and particularly preferably 0.1 to 20%.

  As content of the metal oxide particle in a high refractive index layer, it is preferable that it is 15-90 mass% with respect to 100 mass% of solid content of a high refractive index layer, and it is more preferable that it is 20-85 mass%. Preferably, it is 30-85 mass% from a viewpoint of a reflectance improvement, and is further more preferable.

[Surfactant]
Each refractive index layer preferably contains a surfactant from the viewpoint of coatability.

Anionic surfactants, nonionic surfactants, amphoteric surfactants and the like can be used as the surfactant used for adjusting the surface tension at the time of coating, but anionic surfactants are more preferable. Preferred compounds include those containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. Anionic surfactants include alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkane or olefin sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl or alkyl aryl ether sulfate ester, alkyl phosphate, alkyl diphenyl ether It is possible to use a surfactant selected from the group consisting of disulfonates, ether carboxylates, alkylsulfosuccinates, α-sulfo fatty acid esters and fatty acid salts, condensates of higher fatty acids and amino acids, naphthenates, and the like. it can. Preferred anionic surfactants are alkylbenzene sulfonates (especially those of linear alkyls), alkanes or olefin sulfonates (especially secondary alkane sulfonates, α-olefin sulfonates), alkyl sulfates Salts, polyoxyethylene alkyl or alkyl aryl ether sulfates (especially polyoxyethylene alkyl ether sulfates), alkyl phosphates (especially monoalkyl type), ether carboxylates, alkyl sulfosuccinates, α-sulfo fatty acid esters and A surfactant selected from the group consisting of fatty acid salts, and alkylsulfosuccinate is particularly preferable.

  The content of the surfactant in each refractive index layer is preferably 0.001 to 0.5% by weight, preferably 0.005 to 0.3% by weight, as the solid content of the refractive index layer is 100% by mass. It is more preferable.

(Polymer dispersant)
Each refractive index layer preferably contains a polymer dispersant from the viewpoint of dispersion stability of the coating solution. The polymer dispersant refers to a polymer dispersant having a weight average molecular weight of 10,000 or more. Preferred is a polymer having a hydroxyl group substituted at the side chain or terminal, for example, an acrylic polymer such as poly (sodium acrylate) or polyacrylamide and 2-ethylhexyl acrylate copolymerized, polyethylene glycol or the like. Examples include polyethers such as polypropylene glycol, polyvinyl alcohol, and the like. Commercially available polymer dispersants may be used, and examples of such polymer dispersants include Marialim AKM-0531 (manufactured by NOF Corporation). The content of the polymer dispersant is preferably 0.1 to 10% by mass in terms of solid content with respect to the refractive index layer.

[Emulsion resin]
The high refractive index layer or the low refractive index layer may further contain an emulsion resin. By including the emulsion resin, the flexibility of the film is increased and the workability such as sticking to glass is improved.

  The emulsion resin is a resin in which fine resin particles having an average particle diameter of about 0.01 to 2.0 μm, for example, are dispersed in an emulsion state in an aqueous medium, and an oil-soluble monomer having a high hydroxyl group. Obtained by emulsion polymerization using a molecular dispersant. There is no fundamental difference in the polymer component of the resulting emulsion resin depending on the type of dispersant used. Examples of the dispersant used in the polymerization of the emulsion include polyoxyethylene nonylphenyl ether in addition to low molecular weight dispersants such as alkylsulfonate, alkylbenzenesulfonate, diethylamine, ethylenediamine, and quaternary ammonium salt. , Polymer dispersing agents such as polyoxyethylene lauryl ether, hydroxyethyl cellulose, and polyvinylpyrrolidone. When emulsion polymerization is performed using a polymer dispersant having a hydroxyl group, the presence of hydroxyl groups is estimated on at least the surface of fine particles, and the emulsion resin polymerized using other dispersants has chemical and physical properties of the emulsion. Different.

  The polymer dispersant containing a hydroxyl group is a polymer dispersant having a weight average molecular weight of 10,000 or more, and has a hydroxyl group substituted at the side chain or terminal. For example, an acrylic polymer such as sodium polyacrylate or polyacrylamide is used. Examples of such a polymer include those obtained by copolymerization of 2-ethylhexyl acrylate, polyethers such as polyethylene glycol and polypropylene glycol, and polyvinyl alcohol. Polyvinyl alcohol is particularly preferable.

  Polyvinyl alcohol used as a polymer dispersant is an anion-modified polyvinyl alcohol having an anionic group such as a cation-modified polyvinyl alcohol or a carboxyl group in addition to ordinary polyvinyl alcohol obtained by hydrolysis of polyvinyl acetate. Further, modified polyvinyl alcohol such as silyl-modified polyvinyl alcohol having a silyl group is also included. Polyvinyl alcohol has a higher effect of suppressing the occurrence of cracks when forming the ink absorbing layer when the average degree of polymerization is higher, but when the average degree of polymerization is within 5000, the viscosity of the emulsion resin is not high, and at the time of production Easy to handle. Accordingly, the average degree of polymerization is preferably 300 to 5000, more preferably 1500 to 5000, and particularly preferably 3000 to 4500. The saponification degree of polyvinyl alcohol is preferably 70 to 100 mol%, more preferably 80 to 99.5 mol%.

  Examples of the resin that is emulsion-polymerized with the above polymer dispersant include homopolymers or copolymers of ethylene monomers such as acrylic acid esters, methacrylic acid esters, vinyl compounds, and styrene compounds, and diene compounds such as butadiene and isoprene. Examples of the polymer include acrylic resins, styrene-butadiene resins, and ethylene-vinyl acetate resins.

[Other additives for refractive index layer]
The high refractive index layer and the low refractive index layer according to the present invention can contain various additives as required.

  For example, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57-74192, JP-A-57-87989, JP-A-60- No. 72785, 61-146591, JP-A-1-95091, JP-A-3-13376, etc., and JP-A-59-42993 and 59-52689. Fluorescent brighteners, sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide described in JP-A-62-280069, JP-A-61-228771 and JP-A-4-219266 Various known additives such as pH adjusters such as potassium carbonate, antifoaming agents, lubricants such as diethylene glycol, preservatives, antistatic agents and matting agents. It may have.

[Control layer / intermediate layer / protective layer / functional layer]
The gas barrier film according to the present invention may further have a control layer / intermediate layer / protective layer / functional layer as required. When providing a control layer, it is normally provided between a base material and a barrier layer.

<CVD layer>
The control layer / intermediate layer / protective layer / functional layer may be a CVD layer, and preferably the control layer is a CVD layer. Here, the CVD layer includes at least one oxide, nitride, oxynitride, or oxycarbide selected from the group consisting of silicon, aluminum, and titanium.

When the gas barrier property of the CVD layer is calculated using a laminate in which a CVD layer is formed on a substrate, the permeated water amount measured by the method described in Examples below is 0.1 g / (m ² · 24 h. ) Or less, more preferably 0.01 g / (m ² · 24 h) or less.

  The CVD layer is an oxide, nitride, oxynitride, or oxycarbide such as silicon, titanium, and aluminum formed by a chemical vapor deposition method (CVD method). Chemical vapor deposition (Chemical Vapor Deposition) is a method of depositing a film on a substrate by a chemical reaction in the surface of the substrate or in the gas phase by supplying a raw material gas containing the components of the target thin film onto the substrate. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of film forming speed and processing area. Forming a CVD layer by chemical vapor deposition is advantageous in terms of gas barrier properties.

  Hereinafter, the plasma CVD method which is a preferable form among the CVD methods will be specifically described.

  FIG. 2 is a schematic view showing an example of a vacuum plasma CVD apparatus used for forming a CVD layer according to the present invention.

  In FIG. 2, the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface inside the vacuum chamber 102. Further, a cathode electrode 103 is disposed on the ceiling side inside the vacuum chamber 102 at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102. A heat medium is disposed in the heat medium circulation system 106. The heat medium circulation system 106 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 160 having a storage device is provided.

  The heating / cooling device 160 is configured to measure the temperature of the heat medium, heat or cool the heat medium to a stored set temperature, and supply the heat medium to the susceptor 105. The supplied heat medium flows inside the susceptor 105, heats or cools the susceptor 105, and returns to the heating / cooling device 160. At this time, the temperature of the heat medium is higher or lower than the set temperature, and the heating and cooling device 160 heats or cools the heat medium to the set temperature and supplies the heat medium to the susceptor 105. Thus, the cooling medium circulates between the susceptor and the heating / cooling device 160, and the susceptor 105 is heated or cooled by the supplied heating medium having the set temperature.

  The vacuum chamber 102 is connected to an evacuation system 107, and before the film formation process is started by the vacuum plasma CVD apparatus 101, the inside of the vacuum chamber 102 is evacuated in advance and the heat medium is heated from room temperature. The temperature is raised to a set temperature, and a heat medium having the set temperature is supplied to the susceptor 105. The susceptor 105 is at room temperature at the start of use, and when a heat medium having a set temperature is supplied, the susceptor 105 is heated.

  After circulating the heat medium at a set temperature for a certain time, the substrate 110 to be deposited is carried into the vacuum chamber 102 and placed on the susceptor 105 while maintaining the vacuum atmosphere in the vacuum chamber 102.

  A number of nozzles (holes) are formed on the surface of the cathode electrode 103 facing the susceptor 105.

  The cathode electrode 103 is connected to a gas introduction system 108. When a CVD gas is introduced from the gas introduction system 108 to the cathode electrode 103, the CVD gas is ejected from the nozzle of the cathode electrode 103 into the vacuum chamber 102 in a vacuum atmosphere.

  The cathode electrode 103 is connected to a high frequency power source 109, and the susceptor 105 and the vacuum chamber 102 are connected to a ground potential.

  When a CVD gas is supplied from the gas introduction system 108 into the vacuum chamber 102, a high-frequency power source 109 is activated while a heating medium having a constant temperature is supplied from the heating / cooling device 160 to the susceptor 105, and a high-frequency voltage is applied to the cathode electrode 103, Plasma of the introduced CVD gas is formed. When the CVD gas activated in the plasma reaches the surface of the substrate 110 on the susceptor 105, a CVD layer as a thin film grows on the surface of the substrate 110.

  At this time, the distance between the susceptor 105 and the cathode electrode 103 is set as appropriate.

  The flow rates of the raw material gas and the cracked gas are appropriately set in consideration of the raw material gas, the cracked gas type, and the like. In one embodiment, the flow rate of the source gas is 30 to 300 sccm, and the flow rate of the decomposition gas is 100 to 1000 sccm.

  During the growth of the thin film, a heating medium having a constant temperature is supplied from the heating / cooling device 160 to the susceptor 105, and the susceptor 105 is heated or cooled by the heating medium, and a thin film is formed while being maintained at the constant temperature. Generally, the lower limit temperature of the growth temperature when forming a thin film is determined by the film quality of the thin film, and the upper limit temperature is determined by the allowable range of damage to the thin film already formed on the substrate 110. The lower limit temperature and upper limit temperature vary depending on the material of the thin film to be formed, the material of the thin film already formed, etc., but the lower limit temperature is 50 ° C. or more in order to ensure the film quality with high gas barrier properties, and the upper limit temperature is the base material. It is preferable that it is below the heat-resistant temperature.

  The correlation between the film quality of the thin film formed by the vacuum plasma CVD method and the film formation temperature and the correlation between the damage to the film formation target (substrate 110) and the film formation temperature are obtained in advance, and the lower limit temperature and the upper limit temperature are determined. Is done. For example, the temperature of the substrate 110 during the vacuum plasma CVD process is preferably 50 to 250 ° C.

  Furthermore, the relationship between the temperature of the heat medium supplied to the susceptor 105 and the temperature of the substrate 110 when plasma is formed by applying a high frequency voltage of 13.56 MHz or more to the cathode electrode 103 is measured in advance, and vacuum plasma CVD is performed. In order to maintain the temperature of the substrate 110 between the lower limit temperature and the upper limit temperature during the process, the temperature of the heat medium supplied to the susceptor 105 is required.

  For example, a lower limit temperature (here, 50 ° C.) is stored, and a heat medium whose temperature is controlled to a temperature equal to or higher than the lower limit temperature is set to be supplied to the susceptor 105. The heat medium refluxed from the susceptor 105 is heated or cooled, and a heat medium having a set temperature of 50 ° C. is supplied to the susceptor 105. For example, as a CVD gas, a mixed gas of silane gas, ammonia gas, and nitrogen gas is supplied, and the SiN film is formed in a state where the substrate 110 is maintained at a temperature condition not lower than the lower limit temperature and not higher than the upper limit temperature.

  Immediately after startup of the vacuum plasma CVD apparatus 101, the susceptor 105 is at room temperature, and the temperature of the heat medium returned from the susceptor 105 to the heating / cooling apparatus 160 is lower than the set temperature. Therefore, immediately after the activation, the heating / cooling device 160 heats the refluxed heat medium to raise the temperature to the set temperature, and supplies it to the susceptor 105. In this case, the susceptor 105 and the substrate 110 are heated and heated by the heat medium, and the substrate 110 is maintained in a range between the lower limit temperature and the upper limit temperature.

  When a thin film is continuously formed on the plurality of substrates 110, the susceptor 105 is heated by heat flowing from the plasma. In this case, since the heat medium recirculated from the susceptor 105 to the heating / cooling device 160 is higher than the lower limit temperature (50 ° C.), the heating / cooling device 160 cools the heat medium and converts the heat medium at the set temperature into the susceptor. It supplies to 105. Thereby, it is possible to form a thin film while maintaining the substrate 110 in a range between the lower limit temperature and the upper limit temperature.

  Thus, the heating / cooling device 160 heats the heating medium when the temperature of the refluxed heating medium is lower than the set temperature, and cools the heating medium when the temperature is higher than the set temperature. In addition, a heat medium having a set temperature is supplied to the susceptor, and as a result, the substrate 110 is maintained in a temperature range between the lower limit temperature and the upper limit temperature.

  Once the thin film has been formed to a predetermined thickness, the substrate 110 is unloaded from the vacuum chamber 102, the undeposited substrate 110 is loaded into the vacuum chamber 102, and a heating medium having a set temperature is supplied as described above. A thin film is formed.

(Polysiloxane layer)
The control layer / intermediate layer / protective layer / functional layer may be a polysiloxane-based layer.

  The polysiloxane-based layer contains a product obtained by modifying polysiloxane and / or polysiloxane.

Polysiloxane The polysiloxane is not particularly limited, and known ones can be used. Among these, it is preferable to use an organopolysiloxane represented by the following general formula (2).

In the said General formula (2), R < ³ > -R < ⁸ > represents a C1-C8 organic group each independently. At this time, at least one of R ^{3 to} R ⁸ is an alkoxy group or a hydroxyl group, and m is an integer of 1 or more. The C1-C8 organic group is not particularly limited, but is a halogenated alkyl group such as a γ-chloropropyl group or 3,3,3-trifluoropropyl group; an alkenyl group such as a vinyl group; an aryl group such as a phenyl group. A (meth) acrylic acid ester group such as γ-methacryloxypropyl group; an epoxy-containing alkyl group such as γ-glycidoxypropyl group; a mercapto-containing alkyl group such as γ-mercaptopropyl group; a γ-aminopropyl group; Aminoalkyl group; isocyanate-containing alkyl group such as γ-isocyanatopropyl group; linear or branched alkyl group such as methyl group, ethyl group, propyl group and isopropyl group; alicyclic alkyl group such as cyclohexyl group and cyclopentyl group; Linear or branched group such as ethoxy group, propyloxy group, isopropyloxy group, etc. Jo alkoxy group; an acetyl group, a propionyl group, a butyryl group, valeryl group, and an acyl group such as caproyl.

  Of the organopolysiloxanes represented by the general formula (2), it is more preferable to use an organopolysiloxane having m of 1 or more and a weight average molecular weight (polystyrene conversion) of 1000 to 20000. It is preferable that the weight average molecular weight of the organopolysiloxane is 1000 or more because cracks are unlikely to occur in the formed polysiloxane layer and the gas barrier property can be maintained. On the other hand, when the weight average molecular weight of the organopolysiloxane is 20000 or less, the polysiloxane-based layer to be formed is sufficiently cured and a sufficient hardness as a layer can be obtained.

Product formed by modifying polysiloxane A product formed by modifying polysiloxane can be formed by modifying the above-described polysiloxane with vacuum ultraviolet light or the like. The specific composition of the product obtained by modifying the polysiloxane is not clear.

  The polysiloxane-based layer may be a single layer or a laminate of two or more layers. When two or more layers are laminated, each layer may be composed of the same component or different components.

  The thickness of the polysiloxane-based layer can be appropriately set according to desired performance. For example, the thickness of the polysiloxane-based layer is preferably 100 nm to 10 μm, and more preferably 50 nm to 1 μm. It is preferable that the thickness of the polysiloxane-based layer is 100 nm or more because sufficient barrier properties can be obtained. On the other hand, when the thickness of the polysiloxane-based layer is 10 μm or less, it is preferable because high light transmittance can be realized and stable coating can be performed when the polysiloxane-based layer is formed.

The film density of the polysiloxane-based layer is usually 0.35 to 1.2 g / cm ³ , preferably 0.4 to 1.1 g / cm ³ , more preferably 0.5 to 1.0 g / cm ^3. cm ³ . A film density of 0.35 g / cm ³ or more is preferable because sufficient mechanical strength of the coating film can be obtained. On the other hand, when the film density is 1.2 g / cm ³ or less, cracks in the polysiloxane layer are less likely to occur.

Formation of polysiloxane-based layer The polysiloxane-based layer can be formed by applying a polysiloxane-based layer coating solution.

  The polysiloxane-based layer coating solution contains polysiloxane.

  Since polysiloxanes similar to those described above can be used, description thereof is omitted here.

  Further, the polysiloxane layer coating solution may further contain a solvent and appropriately known components.

  The solvent that can be contained in the polysiloxane layer coating solution is not particularly limited, and examples thereof include water, alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, and the like. Examples of alcohol solvents include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, and triethylene. Examples include glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, diacetone alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of ether solvents include tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like. Examples of the ketone solvent include cyclohexanone, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvent include methyl acetate, ethyl acetate, ethoxyethyl acetate and the like. In addition to these, solvents such as dichloroethane and acetic acid may be used. These solvents can be used alone or in admixture of two or more.

  Known components include aminosilane compounds, epoxysilane compounds, colloidal silica, and curing catalysts.

  As the coating method of the second coating solution, a conventionally known appropriate wet coating method can be employed. Specific examples include spin coating, dipping, roller blades, and spraying methods.

  The coating amount of the polysiloxane layer coating solution is not particularly limited, but can be appropriately adjusted in consideration of the thickness of the dried polysiloxane layer.

  After applying the polysiloxane-based layer 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 polysiloxane-based layer can be obtained. As a drying method, a method similar to “formation of a coating film” in the barrier layer can be applied.

  The coating film obtained in this way may be further irradiated with vacuum ultraviolet light to modify the polysiloxane to form a polysiloxane-based layer. For the vacuum ultraviolet light irradiation, a method similar to “vacuum ultraviolet light irradiation” in the barrier layer is applied, and the irradiation conditions can be appropriately set according to the desired performance. The specific composition of the polysiloxane obtained by modification is not clear.

(Other control layer / intermediate layer / protective layer / functional layer)
Other layers other than the polysiloxane layer may be used as the control layer / intermediate layer / protective layer / functional layer.

  Examples of other layers include curable resin-based layers.

  The curable resin-based layer can be formed by applying an organic resin composition coating solution to form a coating film and curing it by heat treatment or light irradiation treatment.

Organic resin composition coating liquid The organic resin composition coating liquid usually contains a thermosetting resin and / or a photocurable resin, a photopolymerization initiator, and a solvent.

  The thermosetting resin is not particularly limited as long as it is cured by heat treatment, but phenol resin (PF), epoxy resin (EP), melamine resin (MF), urea resin (UF), unsaturated polyester resin (UP ), Alkyd resin, polyurethane (PUR), thermosetting polyimide (PI), and the like.

  The photocurable resin is not particularly limited as long as it is cured by light treatment, but a resin containing an acrylate compound having a radical reactive unsaturated bond, a resin containing an acrylate compound and a mercapto compound having a thiol group, Examples thereof include resins containing polyfunctional acrylate monomers such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate. Specifically, “ORMOCER” described in US Pat. No. 6,503,634, UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation (with polymerizable unsaturated groups on silica fine particles) And a compound formed by bonding an organic compound having an organic compound). It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no restriction in particular.

  Moreover, you may use the monomer which has one or more photopolymerizable unsaturated groups in a molecule | numerator. The monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 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, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylic 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 tri Chryrate, 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-trimethyl-1, 3-pentadiol diacryl , Diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and those obtained by replacing the above acrylates with methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, etc. Can be mentioned.

  The thermosetting resin and / or photocurable resin preferably contains a polymerizable group and / or a crosslinkable group. The polymerizable group and the crosslinkable group are not particularly limited as long as a polymerization reaction or a crosslinking reaction is caused by heat treatment or light irradiation, and include known functional groups. Specific examples include polymerizable groups such as an ethylenically unsaturated group, an epoxy group, and a cyclic ether group such as an oxetanyl group; a crosslinking group such as a thiol group, a halogen atom, and an onium salt structure. Among these, it is preferable to have an ethylenically unsaturated group, and examples of the ethylenically unsaturated group include functional groups described in JP-A No. 2007-17948.

  The above-mentioned thermosetting resin and / or photocurable resin can be used alone or in admixture of two or more.

  The photopolymerization initiator is not particularly limited, but benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4 , 4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropio Phenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetate Benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (P-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propane Dione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-be Zoyl) oxime, 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 carbon, tribromophenyl sulfone, Examples include a combination of a photoreductive dye such as benzoin peroxide, eosin, methylene blue and a reducing agent (ascorbic acid, triethanolamine, etc.). These photopolymerization initiators may be used alone or in combination of two or more.

  The solvent is not particularly limited, but alcohols such as methanol, ethanol, propanol, isopropyl alcohol, ethylene glycol and propylene glycol; terpenes such as α- or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, N-methyl- Ketones such as 2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methylcarbitol, ethyl Carbitol, butyl carbitol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl Glycol ethers such as ether; ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl Esters such as acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate and methyl benzoate; amides such as N, N-dimethylacetamide and N, N-dimethylformamide Can be mentioned. These solvents may be used alone or in combination of two or more.

  The organic resin composition coating liquid may further contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, inorganic particles, a coupling material, and a resin other than the photosensitive resin as necessary.

  Of these, preferred additives are inorganic particles and coupling materials.

  By adding the inorganic particles, the elastic modulus of the curable resin-based layer can be adjusted.

The inorganic particles are not particularly _{limited, SiO 2, Al 2 O 3} , TiO 2, ZrO 2, ZnO, SnO 2, In 2 O 3, BaO, SrO, CaO, MgO, VO 2, V 2 O 5, _{CrO 2, MoO 2, MoO 3} , MnO 2, Mn 2 O 3, WO 3, LiMn 2 O 4, Cd 2 SnO4, CdIn 2 O 4, Zn 2 SnO 4, ZnSnO 3, Zn 2 In 2 O 5, Cd ₂ SnO ₄ , CdIn ₂ O ₄ , Zn ₂ SnO ₄ , ZnSnO ₃ , Zn ₂ In ₂ O _{5 and the} like can be mentioned. Further, as inorganic particles, mica groups such as natural mica and synthetic mica, and tabular particles such as talc, teniolite, montmorillonite, saponite, hectorite, synthetic smectite, zirconium phosphate represented by the formula 3MgO · 4SiO · H ₂ O May be used. Examples of the natural mica include muscovite, soda mica, phlogopite, biotite, sericite, and the like. Further, as the synthetic mica, non-swelling mica such as fluorine phlogopite mica ₃ (AlSi ₃ O ₁₀ ) F ₂ , potassium tetrasilicon mica KMg _2.5 (Si ₄ O ₁₀ ) F ₂ ; and Na tetrasilicic mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li Teniolite (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , Montmorillonite Na or Li Hectorite (Na, Li) _1/8 Mg _2/5 Examples thereof include swelling mica such as Li _1/8 (Si ₄ O ₁₀ ) F ₂ . These inorganic particles may be used alone or in combination of two or more.

  The number average particle diameter of the inorganic particles is preferably 1 to 200 nm, and more preferably 3 to 100 nm.

  The inorganic particles may be subjected to a surface treatment.

  Inorganic particles may be prepared by themselves according to methods described in recent academic papers, but commercially available products may also be used. Examples of the commercially available products include the Snowtex series, organosilica sol (manufactured by Nissan Chemical Industries, Ltd.), NANOBYK series (manufactured by Big Chemie Japan Co., Ltd.), NanoDur (manufactured by Nanophase Technologies), and the like.

  The content of the inorganic particles in the curable resin-based layer is preferably 10 to 95% by mass and more preferably 20 to 90% by mass with respect to the mass of the curable resin-based layer.

  Moreover, another material can be mixed by adding the said coupling material.

  Although it does not restrict | limit especially as a coupling agent, A silane coupling agent, a titanate coupling agent, an aluminate coupling agent, etc. are mentioned. Among these, it is preferable to use a silane coupling agent from the viewpoint of the stability of the coating solution.

  Examples of the silane coupling agent include halogen-containing silane coupling agents such as 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, and 3-chloropropyltriethoxysilane; (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxy Epoxy group-containing silane coupling agents such as silane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane; 2-aminoethyltrimethoxy Lan, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyl Amino group-containing silane coupling agents such as trimethoxysilane, 3- (2-aminoethyl) amino] propyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propylmethyldimethoxysilane; 2-mercaptoethyl Mercapto group-containing silane coupling agents such as trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, etc.), (meth) acryloyl group-containing silane coupling Agent (2-methacryloyl Oxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane Examples thereof include vinyl group-containing silane coupling agents, etc. These silane coupling agents may be used alone or in admixture of two or more.

Formation of curable resin-based layer The coating method of the organic resin composition coating solution is not particularly limited, but is a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method such as a vapor deposition method. Law. A curable resin-based layer can be formed by drying and removing the solvent and the like contained in the coated organic resin composition coating solution.

  When a thermosetting resin is used as the organic resin, the curing is usually performed by heating. Although heating temperature changes also with the thermosetting resins to be used, it is preferable that it is 60-150 degreeC. On the other hand, when a photocurable resin is used as the organic resin, the curing is usually performed by ionizing radiation. Examples of the ionizing radiation include ultra high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, metal halide lamps, and the like that emit 100 to 400 nm, preferably 200 to 400 nm of vacuum ultraviolet light, or scanning or curtain type electrons. An electron beam having a wavelength region of 100 nm or less emitted from a line accelerator can be used. The light irradiation may be performed by vacuum ultraviolet light irradiation. When the curable resin layer is formed by vacuum ultraviolet light, the barrier layer and the curable resin layer can be applied and formed on the same line. In addition, although it may heat suitably at the time of light irradiation, and it changes also with curable resin, it is preferable that it is 60-150 degreeC.

The amount of irradiation energy (irradiation amount) is preferably 0.01~20J / cm ^2, more preferably 0.01~20J / cm ^2, to be 0.01~20J / cm ² Further preferred. If it is this range, hardening will fully advance and productivity will improve. Further, it is possible to prevent generation of cracks due to excessive curing and thermal deformation of the film substrate. In addition, although this process may be performed in multiple times, what is necessary is just to select the irradiation amount per time suitably so that the sum total of irradiation amount may become the said range.

[Intermediate layer / Protective layer / Functional layer]
An intermediate layer / protective layer separately between the above-mentioned base material, barrier layer, and any two layers of the high refractive index layer and the low refractive index layer, or on the surface of any of the above layers, as long as the effects of the present invention are not impaired. / A functional layer may be provided. For example, the surface of the substrate opposite to the surface on which the barrier layer is disposed (substrate surface) (functional layer), the outermost layer (farthest from the substrate) on the UV reflective film (protective layer), high refractive index An intermediate layer such as an anchor coat layer, a smooth layer, and a bleed out prevention layer is formed between the layer and the low refractive index layer or between the units composed of the high refractive index layer and the low refractive index layer (intermediate layer). Can be done. The intermediate layer is preferably formed on the substrate surface.

(Anchor coat layer)
An anchor coat layer has the function to improve the adhesiveness of a base material and a barrier layer, and to provide high smoothness. The anchor coat layer can be formed, for example, by applying an anchor coat agent on a substrate.

  The anchor coating agent that can be used is not particularly limited, but polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, alkyl titanate, etc. Is mentioned. These anchor coating agents can be used alone or in combination of two or more. A known additive such as a solvent or a diluent may be further added to the anchor coating agent.

  The method for coating the base material with the anchor coating agent is not particularly limited, and examples thereof include roll coating, gravure coating, knife coating, dip coating, and spray coating. An anchor coat layer can be formed by drying and removing a solvent, a diluent or the like that can be contained in an anchor coat agent coated on a substrate.

The anchor coating agent is preferably applied at a coating amount of 0.1 to 5 g / m ^{2 in} a dry state.

(Smooth layer)
The smooth layer is usually formed on one surface of the substrate, flattenes the rough surface of the substrate where there are minute protrusions etc., and generates irregularities and pinholes in the barrier layer etc. deposited on the substrate It has the function to prevent. The smooth layer is formed by applying a coating solution containing the above organic resin composition, that is, a thermosetting resin and / or a photocurable resin, a photopolymerization initiator, and a solvent, and then curing the coating solution. It is preferable to contain a photocurable resin.

  As for the smoothness of the smooth layer, the 10-point average roughness Rz defined by JIS B 0601 (2001) is preferably 100 nm or less, and more preferably 50 nm or less. More preferably, it is 30 nm or less.

  Further, on the surface of the film substrate, the center line average roughness Ra defined by JIS B 0601 (2001) is preferably 10 nm or less, and more preferably 5 nm or less. In order to achieve such surface roughness, a known smoothing method can be used. For example, a method may be used in which a coating film is provided between the film substrate and the barrier layer and the surface is smoothed by leveling and then cured and a smoothing layer is disposed.

  Although it does not restrict | limit especially as thickness of a smooth layer, It is preferable that it is 0.5-10 micrometers, and it is more preferable that it is 1-7 micrometers. It is preferable that the thickness of the smooth layer is 0.5 μm or more because the function as the smooth layer can be sufficiently exhibited. On the other hand, when the thickness of the smooth layer is 10 μm or less, the balance of the optical properties of the gas barrier film can be adjusted, and curling of the gas barrier film can be suppressed.

(Bleed-out prevention layer)
In the base material having a smooth layer, unreacted oligomers or the like may migrate from the base material to the surface during heating, and the base material surface may be contaminated. The bleed-out prevention layer has a function of suppressing contamination of the substrate surface. The bleed-out prevention layer is usually provided on the surface opposite to the smooth layer of the substrate having the smooth layer.

  The bleed-out prevention layer may have the same configuration as the smooth layer as long as it has the above function. That is, the bleed-out prevention layer can be formed by applying a photosensitive resin composition on a substrate and then curing it.

  The photosensitive resin composition includes a photosensitive resin, a photopolymerization initiator, and a solvent. As the photosensitive resin, the photopolymerization initiator, and the solvent, the same ones as those described in the smooth layer can be used. In addition, the photosensitive resin composition may further contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, inorganic particles, and a resin other than the photosensitive resin, as in the above-described smooth layer. .

  Therefore, for example, various components are appropriately blended, a predetermined dilution solvent is added to prepare a coating solution, and the coating solution is applied onto a substrate by a known coating method. Thereafter, the bleed-out preventing layer can be formed by irradiating with ionizing radiation and curing.

  The thickness of the bleed-out prevention layer is preferably 0.5 to 10 μm, and more preferably 1 to 7 μm. It is preferable that the thickness of the bleed-out preventing layer is 0.5 μm or more because the heat resistance of the gas barrier film can be improved. On the other hand, when the thickness of the bleed-out prevention layer is 10 μm or less, the optical characteristics of the gas barrier film are preferably adjusted, and curling of the gas barrier film can be suppressed.

  When at least one intermediate layer selected from the group consisting of the above-mentioned anchor coat layer, smooth layer, and bleed-out layer is formed on the base material, the total film thickness of the base material and the intermediate layer is 30 It is preferable that it is -300 micrometers, and it is more preferable that it is 50-200 micrometers.

[Method for producing gas barrier film]
There is no restriction | limiting in particular about the manufacturing method of the gas barrier film of this invention, As long as at least 1 unit comprised from a high-refractive-index layer and a low-refractive-index layer can be formed on a base material, what kind of thing The method can also be used.

  In the method for producing a gas barrier film of the present invention, a unit composed of a high refractive index layer and a low refractive index layer is laminated on a substrate.

  Specifically, it is preferable to form a laminate by alternately applying and drying a high refractive index layer and a low refractive index layer. Specific examples include: (1) A high refractive index layer coating solution is applied and dried on a substrate to form a high refractive index layer, and then a low refractive index layer coating solution is applied and dried. (2) A low refractive index layer coating liquid is applied on a substrate and dried to form a low refractive index layer, and then a high refractive index layer is applied. A method of forming a gas barrier film by applying a liquid and drying to form a gas barrier film; (3) A high refractive index layer coating liquid and a low refractive index layer coating liquid are alternately and successively formed on a substrate. A method of forming a gas barrier film including a high refractive index layer and a low refractive index layer by applying multiple layers and then drying; (4) a high refractive index layer coating solution and a low refractive index layer coating solution on a substrate; A gas barrier film including a high refractive index layer and a low refractive index layer; It is. Among these, the method (4), which is a simpler manufacturing process, is preferable. That is, the method for producing a gas barrier film of the present invention preferably includes laminating the high refractive index layer and the low refractive index layer by a simultaneous multilayer coating method.

  When the simultaneous multilayer coating is applied, the layers are stacked in an undried liquid state, so that inter-layer mixing or the like is more likely to occur. However, particularly when the saponification degree of the ethylene-modified polyvinyl alcohol contained in the high refractive index layer and the saponification degree of the polyvinyl alcohol contained in the low refractive index layer are different, the compatibility of polyvinyl alcohol resins having different saponification degrees may be low. Are known. Therefore, even when the high refractive index layer and the low refractive index layer are stacked in an undried liquid state, even if the layers are mixed somewhat, if the solvent water is volatilized and concentrated in the drying process, the saponification degree Polyvinyl alcohol resins having different values cause phase separation, and a force to minimize the area of the interface of each layer is exerted, so interphase mixing is suppressed and interface disturbance is reduced. Therefore, a gas barrier film having excellent light reflection characteristics in a desired wavelength region and less haze can be obtained.

  Moreover, high water resistance can be provided to the coating film by using ethylene-modified polyvinyl alcohol as a binder. For this reason, especially this invention can exhibit a remarkable effect, when manufacturing a gas-barrier film by aqueous | water-based simultaneous multilayer coating. During simultaneous multi-layer coating, multiple coating solutions are layered on the coater, applied to the substrate, and dried, so the coating time is short and fewer defects on the coated surface compared to sequential coating where each layer is coated and dried. By applying the present invention, a gas barrier film having excellent performance and appearance can be produced with high productivity.

  Examples of the coating method include a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, or US Pat. Nos. 2,761,419 and 2,761,791. A slide bead coating method using an hopper, an extrusion coating method, or the like is preferably used.

  The solvent for preparing the high refractive index layer coating solution and the low refractive index layer coating solution is not particularly limited, but water, an organic solvent, or a mixed solvent thereof is preferable. In the present invention, an aqueous solvent can be used to mainly use ethylene-modified polyvinyl alcohol / polyvinyl alcohol as a binder. Compared to the case where an organic solvent is used, the aqueous solvent does not require a large-scale production facility, so that it is preferable in terms of productivity and also in terms of environmental conservation.

  Examples of the organic solvent include alcohols such as methanol, ethanol, 2-propanol and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, diethyl ether, Examples thereof include ethers such as propylene glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone. These organic solvents may be used alone or in combination of two or more. From the viewpoint of environment and simplicity of operation, the solvent of the coating solution is preferably an aqueous solvent, more preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate, and water is particularly preferable.

  When using a mixed solvent of water and a small amount of an organic solvent, the content of water in the mixed solvent is preferably 80 to 99.9% by weight, based on 100% by weight of the entire mixed solvent, and 90 to 99%. More preferably, it is 5% by weight. Here, when it is 80% by weight or more, volume fluctuation due to volatilization of the solvent can be reduced, handling is improved, and when it is 99.9% by weight or less, homogeneity at the time of liquid addition is increased and stable. This is because the obtained liquid properties can be obtained.

  The concentration of the first water-soluble binder in the high refractive index layer coating solution is preferably 0.5 to 10% by weight. Moreover, it is preferable that the density | concentration of the inorganic oxide particle in a high refractive index layer coating liquid is 1 to 50 weight%.

  The concentration of the second water-soluble binder in the low refractive index layer coating solution is preferably 0.5 to 10% by weight. Moreover, it is preferable that the density | concentration of the inorganic oxide particle in a low refractive index layer coating liquid is 1 to 50 weight%.

  The method for preparing the high refractive index layer coating solution and the low refractive index layer coating solution is not particularly limited, and examples thereof include inorganic oxide particles, polyvinyl alcohol (polyvinyl alcohol resin), chelate compounds having higher refractive index than polyvinyl alcohol, and acylates. Examples thereof include a method of adding a compound, a salt thereof, and other additives that are added as necessary, followed by stirring and mixing. At this time, the addition of each component is not particularly limited, and each component may be added and mixed sequentially while stirring, or may be added and mixed all at once while stirring.

  In the present invention, when simultaneous multilayer coating is performed, it is preferable that the saponification degrees of polyvinyl alcohol (polyvinyl alcohol resin) used in the high refractive index layer coating solution and the low refractive index layer coating solution are different. Here, the degree of saponification is the ratio of hydroxyl groups to the total number of acetyloxy groups (derived from the starting vinyl acetate) and hydroxyl groups in polyvinyl alcohol, and is common to ethylene-modified polyvinyl alcohol and other polyvinyl alcohols. is there. Due to the different saponification degrees, mixing of layers can be suppressed in each step of coating and drying. Thereby, a gas barrier film having a high reflectance can be produced. Although this mechanism is not yet clear, it is thought that mixing is suppressed by the difference in surface tension derived from the difference in saponification degree. Furthermore, increasing the degree of polymerization further increases this function. This mechanism is not yet clear, but increasing the degree of polymerization reduces the number of molecules in the unit volume, suppresses physical mixing, and causes a difference in solubility parameter due to the difference in the proportion of hydrophobic acetyloxy groups. Emphasized and speculated to suppress binder mixing.

  In the present invention, the difference in saponification degree between polyvinyl alcohol (polyvinyl alcohol resin) used in the high refractive index layer coating solution and the low refractive index layer coating solution is preferably 3 mol% or more, more preferably 8 mol% or more. That is, the difference between the saponification degree of the ethylene-modified polyvinyl alcohol contained in the high refractive index layer and the saponification degree of the polyvinyl alcohol contained in the low refractive index layer is preferably 3 mol% or more, and 8 mol% or more. Is more preferable. The upper limit of the difference between the degree of saponification of ethylene-modified polyvinyl alcohol in the high refractive index layer and the degree of saponification of polyvinyl alcohol in the low refractive index layer takes into account the effect of suppressing / preventing interlayer mixing between the high refractive index layer and the low refractive index layer. Then, since it is so preferable that it is high, it is not particularly limited, but it is preferably 15 mol% or less, more preferably 10 mol% or less.

  The polyvinyl alcohol for comparing the difference in the degree of saponification in each refractive index layer has the highest content in the refractive index layer when each refractive index layer contains a plurality of polyvinyl alcohols (different in saponification degree and polymerization degree). High polyvinyl alcohol. Here, when the term “polyvinyl alcohol having the highest content in the refractive index layer” is used, it is assumed that a polyvinyl alcohol having a difference in saponification degree of 3 mol% or less is one polyvinyl alcohol, and the saponification degree or polymerization degree is defined as calculate. Specifically, when polyvinyl alcohol having a saponification degree of 90 mol%, a saponification degree of 91 mol%, and a saponification degree of 93 mol% is contained in the same layer by 10 wt%, 40 wt%, and 50 wt%, respectively. These three polyvinyl alcohols are the same polyvinyl alcohol, and the mixture of these three is polyvinyl alcohol (A) or (B). The saponification degree of this polyvinyl alcohol (A) / (B) is (90 × 0 1 + 91 × 0.4 + 93 × 0.5) /1=91.9 mol%. The “polyvinyl alcohol having a saponification degree difference of 3 mol% or less” is not more than 3 mol% when attention is paid to any polyvinyl alcohol. For example, 90, 91, 92, 94 mol% In the case where the vinyl alcohol is included, since all the polyvinyl alcohols are within 3 mol% when focusing on 91 mol% vinyl alcohol, the same polyvinyl alcohol is obtained.

  When polyvinyl alcohol having a saponification degree different by 3 mol% or more is contained in the same layer, it is regarded as a mixture of different polyvinyl alcohols, and the polymerization degree and the saponification degree are respectively calculated.

  For example, PVA-203: 5 wt%, PVA-117: 25 wt%, PVA-217: 10 wt%, PVA-220: 10 wt%, PVA-224: 10 wt%, PVA-235: 20 wt%, PVA-245: When 20% by weight is included, the PVA with the highest content is a mixture of PVA-217 to 245 (the difference in saponification degree of PVA-217 to 245 is within 3 mol%, so the same polyvinyl alcohol The mixture becomes polyvinyl alcohol (A) or (B). In the mixture of PVA-217 to 245 (polyvinyl alcohol (A) / (B)), the degree of polymerization is (1700 × 0.1 + 2000 × 0.1 + 2400 × 0.1 + 3500 × 0.2 + 4500 × 0.2) /0.7=3200, and the degree of saponification is 88%.

  When the slide bead coating method is used, the temperature of the high refractive index layer coating solution and the low refractive index layer coating solution in simultaneous multilayer coating is preferably a temperature range of 25 to 60 ° C, and a temperature range of 30 to 45 ° C. Is more preferable. Moreover, when using a curtain application | coating system, the temperature range of 25-60 degreeC is preferable, and the temperature range of 30-45 degreeC is more preferable.

  The viscosities of the high refractive index layer coating solution and the low refractive index layer coating solution when performing simultaneous multilayer coating are not particularly limited. However, when the slide bead coating method is used, the preferable temperature range of the coating liquid is preferably in the range of 5 to 160 mPa · s, more preferably in the range of 60 to 140 mPa · s. Moreover, when using a curtain application | coating system, in the preferable temperature range of said coating liquid, the range of 5-1200 mPa * s is preferable, More preferably, it is the range of 25-500 mPa * s. If it is the range of such a viscosity, simultaneous multilayer coating can be performed efficiently.

  Moreover, as a viscosity at 15 degreeC of a coating liquid, 100 mPa * s or more is preferable, 100-30,000 mPa * s is more preferable, More preferably, it is 2,500-30,000 mPa * s.

  The conditions for the coating and drying method are not particularly limited. For example, in the case of a sequential coating method, first, either one of a high refractive index layer coating solution and a low refractive index layer coating solution heated to 30 to 60 ° C. is used. After coating and drying on a substrate to form a layer, the other coating solution is coated on this layer and dried to form a laminated film precursor (unit). Next, the number of units necessary for expressing the desired shielding performance is successively applied and dried by the above method to obtain a laminated film precursor. When drying, it is preferable to dry the formed coating film at 30 ° C. or higher. For example, it is preferable to dry in the range of 5-50 ° C. wet bulb temperature and 5-100 ° C. (preferably 10-50 ° C.) film surface temperature. For example, warm air of 40-60 ° C. is blown for 1-5 seconds. dry. As a drying method, warm air drying, infrared drying, and microwave drying are used. Further, drying in a multi-stage process is preferable to drying in a single process, and it is more preferable to set the temperature of the constant rate drying section <the temperature of the rate-decreasing drying section. In this case, the temperature range of the constant rate drying part is preferably 30 to 60 ° C., and the temperature range of the decreasing rate drying part is preferably 50 to 100 ° C.

  Moreover, the conditions of the coating and drying method when performing simultaneous multilayer coating are as follows: the high refractive index layer coating solution and the low refractive index layer coating solution are heated to 30 to 60 ° C., and the high refractive index layer coating is applied on the substrate. After the simultaneous multi-layer coating of the liquid and the low refractive index layer coating liquid, the temperature of the formed coating film is preferably cooled (set) preferably to 1 to 15 ° C. and then dried at 10 ° C. or higher. More preferable drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C. For example, 40-80 degreeC warm air is sprayed for 1 to 5 seconds, and it dries. Moreover, as a cooling method immediately after application | coating, it is preferable to carry out by a horizontal set system from a viewpoint of the uniformity improvement of the formed coating film.

  Here, the set means that the viscosity of the coating composition is increased by means such as lowering the temperature by applying cold air or the like to the coating film, the fluidity of the substances in each layer and in each layer is reduced, or the gel It means the process of converting. A state in which the cold air is applied to the coating film from the surface and the finger is pressed against the surface of the coating film is defined as a set completion state.

  The time (setting time) from the time of application to the completion of setting by applying cold air is preferably within 5 minutes, and more preferably within 2 minutes. Further, the lower limit time is not particularly limited, but it is preferable to take 45 seconds or more. If the set time is too short, mixing of the components in the layer may be insufficient. On the other hand, if the set time is too long, the interlayer diffusion of the inorganic oxide particles proceeds, and the refractive index difference between the high refractive index layer and the low refractive index layer may be insufficient. If the intermediate layer between the high-refractive index layer and the low-refractive index layer is highly elastic, the setting step may not be provided.

  The set time is adjusted by adjusting the concentration of polyvinyl alcohol and inorganic oxide particles, or adding other components such as various known gelling agents such as gelatin, pectin, agar, carrageenan, and gellan gum. Can be adjusted.

  The temperature of the cold air is preferably 0 to 25 ° C, and more preferably 5 to 10 ° C. The time for which the coating film is exposed to cold air is preferably 10 to 360 seconds, more preferably 10 to 300 seconds, and still more preferably 10 to 120 seconds, although it depends on the transport speed of the coating film.

  What is necessary is just to apply | coat so that the coating thickness of a high refractive index layer coating liquid and a low refractive index layer coating liquid may become the thickness at the time of preferable drying as shown above.

[Membrane design]
The gas barrier film of the present invention preferably includes an ultraviolet reflecting film including at least one unit in which a high refractive index layer and a low refractive index layer are laminated. Preferably, it has a multilayer optical interference film in which a high refractive index layer and a low refractive index layer are alternately laminated on one side or both sides of a substrate. From the viewpoint of productivity, the range of the total number of high refractive index layers and low refractive index layers per side of the substrate is preferably 100 layers or less, more preferably 20 layers or less. The lower limit of the range of the total number of high refractive index layers and low refractive index layers per side of the substrate is not particularly limited, but is preferably 5 layers or more. In the gas barrier film of the present invention, the lowermost layer (layer contacting the substrate) and the outermost layer may be either a high refractive index layer or a low refractive index layer. However, by adopting a layer structure in which the low refractive index layer is located in the lowermost layer and the outermost layer, the adhesion to the base material of the lowermost layer, the blowing resistance of the uppermost layer, and the hard coat layer to the outermost layer, etc. From the viewpoint of excellent applicability and adhesion, the gas barrier film of the present invention preferably has a layer structure in which the lowermost layer and the outermost layer are low refractive index layers.

  In general, in a gas barrier film, it is preferable to design a large difference in refractive index between a high refractive index layer and a low refractive index layer from the viewpoint that the reflectance for a desired light beam can be increased with a small number of layers. . In the present invention, the difference in refractive index between at least two adjacent layers (high refractive index layer and low refractive index layer) is preferably 0.1 or more, more preferably 0.35 or more, and most preferably 0. .4 or more. The upper limit is not particularly limited, but is usually 1.4 or less.

  The refractive index difference and the required number of layers can be calculated using commercially available optical design software. For example, in order to obtain an ultraviolet reflectance of 20% or more, if the refractive index difference is smaller than 0.1, it is necessary to laminate 200 layers or more, which not only lowers productivity but also causes large scattering at the lamination interface. Therefore, transparency may be lowered, and it may be very difficult to manufacture without failure.

  In the gas barrier film, when the high refractive index layer and the low refractive index layer are alternately laminated, the refractive index difference between the high refractive index layer and the low refractive index layer is within the range of the preferred refractive index difference. Is preferred. However, for example, when the outermost layer is formed as a layer for protecting the film or when the lowermost layer is formed as an adhesion improving layer with the substrate, the above-mentioned preferable refraction is performed with respect to the outermost layer and the lowermost layer. A configuration outside the range of the rate difference may be used.

  In this specification, the terms “high refractive index layer” and “low refractive index layer” refer to the refractive index layer having a higher refractive index when the refractive index difference between two adjacent layers is compared. This means that the lower refractive index layer is the lower refractive index layer. Therefore, the terms “high refractive index layer” and “low refractive index layer” are the same when each refractive index layer constituting the gas barrier film is focused on two adjacent refractive index layers. All forms other than those having a refractive index are included.

  Since reflection at the interface between adjacent layers depends on the refractive index ratio between the layers, the larger the refractive index ratio, the higher the reflectance. In addition, when the optical path difference between the reflected light on the surface of the layer and the reflected light on the bottom of the layer is a relationship expressed by n · d = wavelength / 4 when viewed as a single layer film, the reflected light is controlled to be strengthened by the phase difference. And reflectivity can be increased. Here, n is the refractive index, d is the physical film thickness of the layer, and n · d is the optical film thickness. By using this optical path difference, reflection can be controlled. Using this relationship, the refractive index and film thickness of each layer are controlled to control the reflection of visible light and near infrared light. That is, the reflectance in a specific wavelength region can be increased by the refractive index of each layer, the film thickness of each layer, and the way of stacking each layer.

[Layer structure of gas barrier film]
The gas barrier film includes at least one unit in which a high refractive index layer and a low refractive index layer are laminated on a base material. The unit may be formed only on one side of the substrate, or may be formed on both sides. Since the reflectance of a specific wavelength improves, it is preferable that this unit is formed on both surfaces of a base material.

  The ultraviolet reflectance and visible light transmittance of the gas barrier film can be determined by a method based on JIS R5759.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

(Examples 1 to 3, Comparative Example 1)
<Formation of intermediate layer on substrate>
As a base material, ultra-low heat yield PET Q83 (manufactured by Teijin DuPont Films Ltd.), which is a polyester film having a thickness of 125 μm and easily bonded to both surfaces, was used. A UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7535 (manufactured by JSR Corporation), which is a photosensitive resin, is applied to one surface of the substrate so that the film thickness after drying becomes 4.0 μm It was applied to. The resulting coating film was irradiated with a high-pressure mercury lamp and cured to form a bleed-out prevention layer. Irradiation was performed at 80 ° C. for 3 minutes in an air atmosphere at an irradiation energy amount of 1.0 J / cm ² .

On the surface opposite to the bleed-out prevention layer of the base material, a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 (manufactured by JSR Corporation), which is a photosensitive resin, is dried. Was applied so as to be 4.0 μm. The resulting coating film was irradiated with a high-pressure mercury lamp and cured to form a smooth layer. Irradiation was performed at 80 ° C. for 3 minutes in an air atmosphere at an irradiation energy amount of 1.0 J / cm ² .

  The 10-point average surface roughness (Rz) and the centerline average roughness (Ra) were measured for the smooth layer of the substrate 1 having the intermediate layer (bleedout prevention layer and smooth layer) thus obtained. The Rz and Ra were measured according to the method defined in JIS B 0601: 2001. Specifically, using an AFM (Atomic Force Microscope) SPI3800N DFM (manufactured by SII Nano Technology Co., Ltd.) as an apparatus, the measurement range for one time is set to 80 μm × 80 μm, and the measurement location is changed three times. Measurements were made. As a result, Rz was 20 nm and Ra was 1 nm.

<Formation of barrier layer>
(Preparation of solution containing polysilazane compound)
Dibutyl ether solution containing 20% by mass of perhydropolysilazane (Aquamica (registered trademark) NN120-20: manufactured by AZ Electronic Materials), 1% by mass of amine catalyst (N, N, N ′, N′-tetramethyl) -1,6-diaminohexane) and a 19% by mass perhydropolysilazane dibutyl ether solution (AQUAMICA (registered trademark) NAX120-20: manufactured by AZ Electronic Materials Co., Ltd.) is mixed at a volume ratio of 4: 1 to obtain a coating solution. Was prepared.

(Formation of coating film)
On the smooth layer of the substrate, the solution containing the polysilazane compound prepared above is diluted with dibutyl ether and applied using a spin coater (10 s, 3000 rpm) so that the film thickness after drying is 250 nm. And dried at 100 ° C. for 2 minutes to obtain a coating film. Drying was performed in an atmosphere having a water vapor concentration of about 300 ppm.

(Coating film modification treatment)
The coating film was subjected to vacuum plasma treatment under the following conditions to modify polysilazane (barrier species 1).
Vacuum plasma processing apparatus: Utec Co., Ltd. gas: Ar,
Gas flow rate: 55 mL / min,
Pressure: 16Pa,
Temperature: 30 ° C
Applied power per unit electrode area: 1.4 W / cm ²
Frequency: 13.56 MHz,
Processing time: 10 min,
Oxygen concentration 100 ppm,
Water vapor concentration 100 ppm (25 ° C.).

<Formation of UV reflective film>
An ultraviolet reflective film was formed by the following method on the base material on which the barrier layer was not formed.

[Preparation of coating solution]
(Preparation of coating solution for low refractive index layer)
680 parts of a 10% by mass colloidal silica (Nissan Chemical Co., Snowtex OXS) aqueous solution, 4.0 parts by mass of a 4.0% by mass aqueous polyvinyl alcohol (Kuraray Co., PVA103: average polymerization degree 300), 3.0 mass 150 parts of an aqueous boric acid solution of 150% were mixed and dispersed. Pure water was added to prepare 1000 parts of colloidal silica dispersion as a whole.

  Next, the obtained coating solution for a low refractive index layer was heated to 45 ° C., and 605 parts of a 4.0% by weight aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA235: average polymerization degree 3500) and 4.0 155 parts of an aqueous solution of mass% polyvinyl alcohol (manufactured by Nihon Vinegar Bipovar, JP45: average polymerization degree 4500) in water were sequentially added with stirring. Thereafter, 40 parts of an aqueous 1% by weight anionic surfactant (Nippon Rapisol A30) aqueous solution was added to prepare a coating solution for a low refractive index layer.

(Preparation of coating solution for high refractive index layer)
Preparation of Rutile Type Titanium Oxide as Core of Core-Shell Particles An aqueous suspension of titanium dioxide is prepared so that titanium dioxide hydrate is suspended in water and the concentration when converted to TiO ₂ is 100 g / L. Prepared. To 10 L of the suspension, 30 L of an aqueous sodium hydroxide solution (concentration: 10 mol / L) was added with stirring, then heated to 90 ° C. and aged for 5 hours. Next, the mixture was neutralized with hydrochloric acid, washed with water after filtration.

  In the above reaction (treatment), the raw material titanium dioxide hydrate is obtained by subjecting a titanium sulfate aqueous solution to thermal hydrolysis treatment according to a known technique.

The base-treated titanium compound was suspended in pure water so that the concentration when converted to TiO ₂ was 20 g / L. Therein, it was added with TiO ₂ amount to stirring 0.4 mole% citric acid. After that, when the temperature of the mixed sol solution reaches 95 ° C., concentrated hydrochloric acid is added so that the hydrochloric acid concentration becomes 30 g / L. The mixture is stirred for 3 hours while maintaining the liquid temperature at 95 ° C. A liquid was prepared.

  As described above, when the pH and zeta potential of the obtained titanium oxide sol solution were measured, the pH was 1.4 and the zeta potential was +40 mV. Moreover, when the particle size was measured with a Zetasizer Nano manufactured by Malvern, the monodispersity was 16%.

  Further, the titanium oxide sol solution was dried at 105 ° C. for 3 hours to obtain titanium oxide powder fine particles. The powder fine particles were measured by X-ray diffraction using JEOL Datum Co., Ltd. JDX-3530 type) and confirmed to be rutile titanium oxide fine particles. The volume average particle diameter of the fine particles was 10 nm.

  Then, 20.0% by mass of a titanium oxide sol aqueous dispersion containing rutile-type titanium oxide fine particles having a volume average particle diameter of 10 nm was added to 4 kg of pure water to obtain a sol solution serving as core particles.

Preparation of core-shell particles by shell coating To 2 kg of pure water, 0.5 kg of 10.0 mass% titanium oxide sol aqueous dispersion was added and heated to 90 ° C. Next, 1.3 kg of an aqueous silicic acid solution prepared so that the concentration when converted to SiO ₂ is 2.0% by mass is gradually added, subjected to heat treatment at 175 ° C. for 18 hours in an autoclave, and further concentrated. Thus, a sol solution (solid content concentration of 20% by mass) of core-shell particles (average particle size: 10 nm), which is made of titanium oxide having a rutile structure as the core particles and SiO ₂ as the coating layer, was obtained.

[Preparation of UV reflective film]
Using a slide hopper type coating apparatus, while keeping the coating solution for the low refractive index layer and the coating solution for the high refractive index layer at 40 ° C., the measurement was alternately performed on the substrate on which the intermediate layer and the barrier layer were formed. Two to thirty layers were simultaneously applied.

  The obtained coating liquid for the low refractive index layer was dried at 60 ° C. for 3 minutes so that the dried film thickness was 62 nm and the dried coating film for the high refractive index layer was 46 nm.

[Method of measuring water vapor transmission rate]
Metal that is a metal that corrodes by reacting with moisture at a size of 12 mm x 12 mm through a mask on the surface of a gas barrier film sample before applying a transparent conductive film using a vacuum evaporation system JEE-400 (manufactured by JEOL Ltd.) Calcium (granular) was deposited so that the deposited film thickness was 80 nm. Thereafter, the mask was removed in a vacuum state, and metal aluminum (φ3 to 5 mm, granular), which is a water vapor-impermeable metal, was vapor-deposited on the entire surface of one side of the sheet and temporarily sealed. Next, the vacuum state was released, and it was quickly transferred to a dry nitrogen gas atmosphere. A quartz glass having a thickness of 0.2 mm is bonded to the temporarily sealed metal aluminum vapor deposition surface via an ultraviolet curable resin (manufactured by Nagase ChemteX Corporation), and the ultraviolet curable resin is cured by irradiating ultraviolet rays. Sealed to prepare a water vapor barrier property evaluation sample.

  The obtained water vapor barrier property evaluation sample was stored under high temperature and high humidity of 60 ° C. and 90% RH using a constant temperature and humidity oven Yamato Humidic Chamber IG47M, and corrosion of metallic calcium was observed. Observations were made every 1 hour up to 6 hours after storage, every 3 hours up to 24 hours, every 6 hours up to 48 hours, and every 12 hours thereafter. The time required for the corrosion area of the calcium metal to reach 1% was determined, and the water vapor transmission rate was calculated according to the following formula.

Water vapor transmission rate (g / m ² /day)=0.029392/Time when corrosion area of metallic calcium became 1% [Measurement method of UV reflectance and visible light transmittance]
Using a spectrophotometer (U-4000 type, manufactured by Hitachi, Ltd.), the transmittance of the gas barrier film in the region of 280 to 380 nm was measured, the average value was obtained, and this was determined as the ultraviolet transmittance (%). The value subtracted from 100% was used as the ultraviolet reflectance. The higher this value is, the higher the ultraviolet blocking ability is.

  Moreover, the transmittance | permeability in 380 nm was measured and it was set as the visible light transmittance | permeability (%).

[Crack evaluation]
After cutting each gas barrier film to B5 size using a disk cutter DC-230 (CADL), each cut end was observed with a loupe, and the total number of cracks on the four sides was confirmed. Cracks were evaluated.
5: No cracks were observed 4: The number of cracks generated was 1 or more and 2 or less 3: The number of cracks generated was 3 or more and 5 or less 2: Number of cracks generated However, it is 6 or more and 10 or less. 1: The number of occurrence of cracks is 11 or more.

[Adhesion evaluation]
The adhesion was evaluated according to the following criteria by the cross-cut (cross-cut) method in JIS K5400.
5: Number of peeled mass 0-5 / 100
4: Peeling mass number 6 to 10/100
3: Peeling mass number 11-30 / 100
2: Number of peeled masses 31-50 / 100
1: Peeling mass number 51 or more / 100
Note that rank 3 or higher can withstand practical use.

(Examples 4-9, Comparative Examples 3-5)
Modification of the above-mentioned polysilazane coating film was carried out by using vacuum ultraviolet light instead of vacuum plasma (ex. Irradiator MODEL: MECL-M-1-200, wavelength 172 nm, stage temperature 100 ° C., integrated light amount 3 J / M, manufactured by M.D. A barrier layer was formed in the same manner as in Example 1 except that the irradiation was performed with irradiation of cm ² , oxygen concentration of 50 ppm, and water vapor concentration of 45 ppm (sample Nos. 2 to 10).

(Comparative Example 2)
[Formation of barrier layer on both sides of substrate]
As a base material, ultra-low heat yield PET Q83 (manufactured by Teijin DuPont Films Ltd.), which is a polyester film having a thickness of 125 μm and easily bonded to both surfaces, was used.

A UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 (manufactured by JSR Corporation), which is a photosensitive resin, is applied to both surfaces of the base material so that the film thickness after drying is 4.0 μm. did. The obtained coating film was irradiated with a high-pressure mercury lamp and cured to form a smooth layer. Irradiation was performed at 80 ° C. for 3 minutes in an air atmosphere at an irradiation energy amount of 1.0 J / cm ² .

  Next, a polysilazane coating film was formed on both surfaces of the substrate in the same manner as in Example 1, and modified with vacuum ultraviolet light in the same manner as in Example 4.

On this both surfaces, the barrier layer of Example 4 was formed in the same manner. Further, an ultraviolet reflecting film was prepared on one side of the substrate in the same manner as in Example 1 (Sample No. 1).
(Comparative Examples 6 and 7)
[Formation of UV cut layer]
(Comparative Example 6)
On one side of the barrier layer, after applying Toyo Ink Co., Ltd. UV curable hard coat agent Rio Durast TYT65-01 (TiO ₂ ) and applying with a wire bar so that the (average) film thickness after drying is 4 μm After drying at 80 ° C. for 1 minute, using a high-pressure mercury lamp, curing conditions: Curing was performed at 200 mJ / cm ² to form a UV cut layer (Sample 11).

(Comparative Example 7)
UV curing type hard coating agent using UV cut layer of Sample 11 Adeka Stub LA-32 (ultraviolet absorber) manufactured by ADEKA Co., Ltd. instead of Rio Duras TYT65-01 (TiO ₂ ) The sample was formed in the same manner as in Comparative Example 5 except that a solution dissolved in 349 (acrylic resin binder) to 20% by mass was used (Sample 12).

11 ... Gas barrier film,
12 ... base material,
13 ... Barrier layer,
14 ... UV reflective film,
15 ... high refractive index layer,
16 ... low refractive index layer,
31 ... Manufacturing equipment,
32 ... Delivery roller,
33, 34, 35, 36 ... transport rollers,
39, 40 ... film forming roller,
41... Gas supply pipe,
42... Power source for generating plasma,
43, 44 ... Magnetic field generator,
45 .. Winding roller,
101 ... Plasma CVD apparatus,
102 ... Vacuum tank,
103 ... cathode electrode,
105 ... susceptor,
106 ... heat medium circulation system,
107 ... vacuum exhaust system,
108 ... gas introduction system,
109 ... high frequency power supply,
110... Substrate
160: Heating and cooling device.

Claims (6)

A gas barrier film comprising: a base material; and a barrier layer formed by applying a solution containing a polysilazane compound on at least one surface of the base material,
A high refractive index layer comprising first metal oxide particles;
A low refractive index layer comprising a water-soluble binder resin and second metal oxide particles;
Further including an ultraviolet reflective film formed by alternately laminating,
The relationship between the average thickness dH of the high refractive index layer and the average thickness dL of the low refractive index layer satisfies the following expressions (1) and (2):
5 nm <| dH-dL | <40 nm Formula (1)
100 nm <| dH + dL | <150 nm Formula (2)
Gas barrier film characterized by satisfying the following conditions:
i) The reflectance of light having a wavelength of 280 nm to 380 nm is 20% or more;
ii) The transmittance of light having a wavelength of 380 nm is 80% or more.   The gas barrier film according to claim 1, wherein the barrier layer formed by applying a solution containing the polysilazane compound is formed by a modification treatment by irradiation with vacuum ultraviolet rays. The high refractive index layer further including a water-soluble binder resins, gas barrier film according to claim 1 or 2. The gas barrier film according to any one of claims 1 to 3 , wherein the first metal oxide particles include core-shell particles in which titanium oxide particles are coated with a silicon-containing hydrated oxide. The gas barrier film according to any one of claims 1 to 4, wherein a total number of the high refractive index layer and the low refractive index layer contained in the ultraviolet reflective film is 12 or more and 28 or less. The gas barrier film according to any one of claims 1 to 5, wherein a thickness per layer of the low refractive index layer is 30 nm or more and 80 nm or less.