JP2007021871A - Barrier film and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the barrier film of a gas-barrier thin film laminate which has improved gas-barrier performance, is excellent in smoothness and adhesion, and can correspond to a large-sized object and a method for producing the gas-barrier film high in productivity. <P>SOLUTION: The gas-barrier film comprises at least a barrier layer and a polymer layer on a substrate, wherein the polymer layer is formed by spraying a coating solution containing a polymerizable monomer on the surface of the substrate in the form of mist and curing the solution. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a transparent barrier film and a method for producing the same, and more particularly to a barrier film having excellent visible light transmittance and high barrier properties and a method for producing the same.

  Conventionally, a gas barrier film in which a thin film of metal oxide such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is a packaging of articles that require blocking of various gases such as water vapor and oxygen, Widely used in packaging applications to prevent the deterioration of food, industrial products and pharmaceuticals. Moreover, it is used with a liquid crystal display element, a solar cell, an electroluminescence (EL) substrate, etc. besides the packaging use. In particular, transparent substrates, which are being applied to liquid crystal display elements and EL elements, have recently been required to be lighter and larger, have long-term reliability and a high degree of freedom in shape, and can display curved surfaces. In addition to the high demands such as that, film substrates such as transparent plastics have begun to be used instead of glass substrates that are heavy and easily broken.

  In addition, the plastic film not only meets the above requirements, but also enables a roll-to-roll system, and thus is more advantageous than glass in terms of productivity and cost reduction.

  However, film substrates such as transparent plastics have a problem that gas barrier properties are inferior to glass. If a base material with inferior gas barrier properties is used, water vapor or air permeates, for example, causing deterioration of the liquid crystal in the liquid crystal cell, resulting in display defects and deterioration of display quality.

In order to solve such a problem, for example, it is known to form a metal oxide thin film on a film substrate to obtain a film substrate having gas barrier properties. Examples of the gas barrier film used for packaging materials and liquid crystal display elements include, for example, a film obtained by vapor-depositing silicon oxide on a plastic film (for example, see Patent Document 1), and a film obtained by vapor-depositing aluminum oxide (for example, Patent Document 2). Each of which has a water vapor barrier property of about 1 g / m ² / day.

In recent years, due to the development of organic EL displays that require further gas barrier properties, larger liquid crystal displays, high-definition displays, etc., the gas barrier performance for film substrates is also about 0.1 g / m ² / day for water vapor barriers. The demand is rising.

  In order to respond to this, as a means for expecting higher barrier performance, studies are being made on film formation by a sputtering method or a CVD method in which a thin film is formed using plasma generated by glow discharge under low pressure conditions. In addition, a technique has been proposed in which a barrier film having a structure in which organic films and inorganic films are alternately stacked is manufactured by a vacuum deposition method (see, for example, Patent Document 3).

  However, these thin film forming methods need to be processed under reduced pressure conditions, and in order to obtain a low pressure, the container needs an expensive vacuum chamber, and further, a vacuum exhaust device needs to be installed. In addition, since processing is performed in a vacuum, when processing a large-area substrate, a large vacuum container must be used, and a vacuum exhaust apparatus with a large output is required. As a result, the equipment becomes extremely expensive and, at the same time, when surface treatment is performed on a plastic substrate with a high water absorption rate, the absorbed water vaporizes, so it takes a long time to obtain a predetermined degree of vacuum, and the processing cost There was also a problem that became high. Furthermore, every time one treatment is performed, it is necessary to perform the next step such as forming the organic film by breaking the vacuum in the vacuum vessel, and in particular, in order to obtain a water vapor barrier property, The more organic and inorganic films were made, the greater the productivity was lost.

  In response to the above problems, a method of forming an inorganic film by using a discharge plasma treatment in the vicinity of atmospheric pressure in the formation of a barrier film having an alternately laminated structure of organic film / inorganic film is disclosed. Examples of film formation methods include coating and vacuum film formation (see, for example, Patent Document 4). However, in this method, although the inorganic film is formed by the atmospheric pressure plasma method, it is highly productive to form the organic film by a coating method that requires a drying process or a vacuum film forming method that requires a vacuum chamber. From the perspective of achieving In addition, since the disclosed method for forming an inorganic film uses expensive argon as a discharge gas, it causes a high raw material cost, and is described in JP 2001-49443 A as a discharge plasma treatment condition. Since the processing conditions using a known single frequency pulse electric field are used, the plasma density is low and a high-quality film cannot be obtained, and the film-forming speed is low and the productivity is very low.

  On the other hand, a method of forming an organic film (plasma polymerization film) using discharge plasma under a pressure near atmospheric pressure is disclosed (for example, see Patent Documents 5 and 6). However, these methods do not mention deterioration of gas barrier properties and bending barrier properties which are important in a gas barrier laminate having a laminated structure including an organic film and an inorganic film.

In addition, in plastic films that require such a high barrier property, it is known that foreign matter attached to the film surface and particles generated during film formation cause pinholes and inhibit high barrier properties. It has been found that completely removing a foreign substance having a minute size of 1 μm or less in a large area has a great impact on productivity, and has been a major obstacle in forming a large-area gas barrier film.
Japanese Patent Publication No.53-12953 JP 58-217344 A World Publication No. 00/026973 Pamphlet JP 2003-191370 A Japanese Examined Patent Publication No. 2-48626 Japanese Patent Laid-Open No. 10-340797

  The present invention has been made in view of the above problems, and the object thereof is a barrier film having high gas barrier performance, excellent in smoothness and adhesion, and capable of handling a large size, and a barrier film having high productivity. It is in providing the manufacturing method of.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
In a barrier film having at least a barrier layer and a polymer layer on a base material, the polymer layer was formed by spraying a coating liquid containing a polymerizable monomer on the surface of the base material in the form of a mist, followed by curing. A barrier film characterized by being a thing.

(Claim 2)
2. The barrier film according to claim 1, wherein an average light transmittance in a region of a wavelength of 400 or more and 700 nm or less is 80% or more.

(Claim 3)
The barrier film according to claim 1, wherein at least one polymer layer is provided between the substrate and the barrier layer.

(Claim 4)
The barrier film according to claim 1, wherein at least one of the polymer layers is in contact with the substrate.

(Claim 5)
The barrier film according to claim 1, wherein at least one of the polymer layers is in contact with at least one layer of the barrier layer.

(Claim 6)
The barrier film according to claim 4, wherein the polymer layer has a thickness of 0.5 μm or more and 10 μm or less.

(Claim 7)
The barrier film according to claim 1, wherein the polymer layer has a center line average surface roughness Ra of 10 nm or less.

(Claim 8)
8. The barrier according to claim 1, wherein the polymerizable monomer forming the polymer layer is at least one selected from a methacrylic compound, an acrylic compound, an epoxy compound, and an oxetane compound. the film.

(Claim 9)
In a method for producing a barrier film having at least a barrier layer and a polymer layer on a base material, the polymer layer is sprayed on the surface of the base material in the form of a mist with a coating liquid containing a polymerizable monomer, and then cured. A method for producing a barrier film, wherein

(Claim 10)
The method for producing a barrier film according to claim 9, wherein at least one polymer layer is formed between the base material and the barrier layer.

(Claim 11)
The method for producing a barrier film according to claim 9 or 10, wherein at least one of the polymer layers is in contact with the substrate.

(Claim 12)
The method for producing a barrier film according to any one of claims 9 to 11, wherein the curing treatment is an ultraviolet irradiation treatment.

(Claim 13)
The method for producing a barrier film according to any one of claims 9 to 11, wherein the curing treatment is an atmospheric pressure plasma treatment.

(Claim 14)
The method for producing a barrier film according to any one of claims 9 to 13, wherein an average particle diameter of the mist of the coating liquid is 5.0 µm or less.

(Claim 15)
The method for producing a barrier film according to any one of claims 9 to 13, wherein an average particle diameter of a mist of the coating solution is 1.0 µm or less.

  According to the present invention, it is a gas barrier thin film laminate having a high gas barrier property, has a property that the water vapor barrier property does not decrease by bending, is excellent in smoothness and adhesion between the formed thin film and the substrate, and large. It is possible to provide a barrier film that can be produced with a productivity several to several tens of times that of a conventional film in terms of area and a method for producing the same. Further, by applying the barrier film of the present invention as, for example, a display element, a lightweight and durable display can be provided at low cost.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventor, as a result, in a barrier film having at least a barrier layer and a polymer layer on a substrate, the polymer layer containing a polymerizable monomer in a mist form. A gas barrier thin film laminate having a high gas barrier property, which is formed by spraying the surface of the base material and then curing the film, or a method for producing the same. It has the characteristics that it does not deteriorate, has excellent smoothness and adhesion between the formed thin film and the substrate, has a large area, and can be produced with productivity several to several tens of times that of conventional films. Barrier film and manufacturing method thereof, and further, for example, by applying it as a display element, a lightweight and durable display can be produced at low cost. Found that it can be subjected, it is completed the invention.

  That is, in the production process of a barrier film that requires a high gas barrier property, for example, in the process of forming a thin film on a base material, foreign matter adhered to the surface of the base material, for example, fine dust or fine particles generated in the thin film formation process, etc. In some cases, the inventor may induce a pinhole. As a result of intensive studies on the means for reducing the pinhole, the present inventor has an adhesive roller, an air brush, etc. for a relatively large foreign substance of 1 μm or more. On the other hand, for extremely small foreign matters of 1 μm or less, a coating liquid containing a polymerizable monomer is sprayed onto the substrate in the form of a mist, and then the applied coating liquid is leveled ( After the coating was leveled, it was cured by energy irradiation after drying to form a polymer layer in which extremely small foreign matter was embedded in the film, and the surface was leveled. It has been found that by forming a barrier layer on a polymer layer, a barrier film having a large screen and having no defects can be continuously produced.

  Details of the present invention will be described below.

<Polymer layer>
The polymer layer according to the present invention is formed by forming a coating liquid containing a polymerizable monomer in the form of a mist, spraying it on the surface of the base material, and then curing it.

  The polymer layer according to the present invention is preferably provided at least one layer between the base material and the barrier layer, and more preferably at least one layer is in contact with the base material. As described above, by directly forming the polymer layer in contact with the base material, the foreign matter adhering to the surface of the base material is taken into the coating film, and as a result, the point-like failure with the pinhole is dramatically improved. Can be reduced. Accordingly, the film thickness of the polymer layer to be formed is preferably a film thickness that exceeds the particle size of the foreign matter attached to the surface of the substrate, but for coarse foreign matters, for example, large foreign matters of 1 μm or more, an adhesive roller The foreign matter can be forcibly removed with an airbrush or the like, and the size of the foreign matter to be shielded by the polymer layer according to the present invention is a very small size of 1 μm or less. The film thickness is preferably 0.5 μm or more and 10 μm or less.

  The polymer layer according to the present invention is preferably in contact with at least one barrier layer. Since the polymer layer according to the present invention is a coating film having extremely high smoothness due to the leveling effect after being coated on the base material, the planar uniformity of the barrier layer to be coated thereon can be improved. Therefore, the center line average surface roughness Ra of the polymer layer according to the present invention is preferably 10 nm or less, more preferably 0.1 nm or more and 10 nm or less, and particularly preferably 0.1 nm or more. 0 nm or less.

  The centerline average surface roughness Ra (nm) in the present invention is a value obtained according to JIS B601 and represents a minute uneven state in a minute area. In the present invention, an atomic force microscope (AFM) is used. ) Is used.

  An atomic force microscope (AFM) is a horizontal sample table on a piezo scanner using a Seiko Instruments SPI3800N probe station and a SPA400 multifunctional unit. When the cantilever is approached to the sample surface and reaches the region where the atomic force works, the cantilever is scanned in the XY direction, and the unevenness of the sample at that time is detected by the displacement of the piezo in the Z direction. A piezo scanner that can scan XY 20 μm and Z 2 μm is used. The cantilever is a silicon cantilever SI-DF20 manufactured by Seiko Instruments Inc., which has a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m, and is measured in a DFM mode (Dynamic Force Mode). A measurement area of 2 μm square is measured with 1 (or 2) field of view and scanning frequency of 1 Hz.

  The centerline average roughness (Ra) is obtained by extracting a portion of the measurement length L in the direction of the centerline from the obtained roughness curve, and setting the centerline direction of the extracted portion as the X axis and the direction of the vertical magnification ( When the Y axis is perpendicular to the X axis and the roughness curve is Y = F (X),

It is defined as the value given by.

  As the polymerizable monomer for forming the polymer layer according to the present invention, an organic compound having at least one unsaturated bond or cyclic structure in the molecule can be preferably used. Among them, in particular, a methacrylic compound, an epoxy compound, or Oxetane compound monomers or oligomers are preferred.

  Examples of the organic compound having an unsaturated bond according to the present invention include vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl enanthate. , Vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl sorbate, vinyl benzoate, etc., vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl Styrenes such as vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, styrene, 4-[(2-butoxyethoxy) methyl] styrene, 4-butoxymethoxy Styrene, 4-butylstyrene, 4-decylstyrene, 4- (2-ethoxymethyl) styrene, 4- (1-ethylhexyloxymethyl) styrene, 4-hydroxymethylstyrene, 4-hexylstyrene, 4-nonylstyrene, 4 -Octyloxymethyl styrene, 2-octyl styrene, 4-octyl styrene, 4-propoxymethyl styrene, maleic acids, dimethylmaleic acid, diethylmaleic acid, dipropylmaleic acid, dibutylmaleic acid, dicyclohexylmaleic acid, di-2 -Ethylhexylmaleic acid, dinonylmaleic acid, dibenzylmaleic acid and the like can be mentioned, but are not limited thereto.

  The methacrylic compound useful in the present invention is not particularly limited, and examples thereof include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryl. Monofunctional acrylic acid esters such as oxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, ε-caprolactone adduct of 1,3-dioxane alcohol, 1,3-dioxolane acrylate, or these acrylates as methacrylates Alternative methacrylic esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol Diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate, neopentyl glycol diacrylate, neopentyl glycol adipate diacrylate, hydroxypivalic acid Diacrylate of ε-caprolactone adduct of neopentyl glycol, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol Acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, diacrylate of diglycidyl ether of 1,6-hexanediol Bifunctional acrylic acid esters such as methacrylic acid, or methacrylic acid esters obtained by replacing these acrylates with methacrylates, such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipenta Erythritol tetraacrylate, hydroxypivalyl lua Polyfunctional acrylic acid ester acids such as dehydro-modified dimethylol propane triacrylate, or can be given methacrylate was replaced these acrylate with methacrylate.

  Epoxy compounds useful in the present invention are not particularly limited, but preferred aromatic epoxides are those prepared by reacting a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof with epichlorohydrin. Or polyglycidyl ethers such as di- or polyglycidyl ethers of bisphenol A or alkylene oxide adducts thereof, di- or polyglycidyl ethers of hydrogenated bisphenol A or alkylene oxide adducts thereof, and novolak type epoxy resins. . Here, examples of the alkylene oxide include ethylene oxide and propylene oxide. The alicyclic epoxide is obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide or peracid. Cyclohexene oxide or cyclopentene oxide-containing compounds are preferred. Preferred aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or Diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, polyethylene glycol or its alkylene oxide adduct Of polyalkylene glycols such as diglycidyl ether, polypropylene glycol or diglycidyl ether of its alkylene oxide adduct Glycidyl ether, and the like. Examples of the alkylene oxide include ethylene oxide and propylene oxide, which can be used in combination of two or more.

  The oxetane compound useful in the present invention is not particularly limited, and examples thereof include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3- Hydroxymethyl-3-normalbutyl oxetane, 3-hydroxymethyl-3-phenyloxetane, 3-hydroxymethyl-3-benzyloxetane, 3-hydroxyethyl-3-methyloxetane, 3-hydroxyethyl-3-ethyloxetane, 3 -Hydroxyethyl-3-propyloxetane, 3-hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-methyloxetane, 3-hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-propyloxetane 3-hydroxypropyl-3-phenyl oxetane, and 3-hydroxy-butyl-3-methyl oxetane and the like. Among these compounds, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are preferable as the oxetane monoalcohol compound from the viewpoint of availability.

  Each of these organic compounds is dissolved in an organic solvent and used as a coating solution. The organic solvent used here is not particularly limited as long as these organic compounds can be dissolved, but alcohols such as methanol, ethanol, propanol, n-butanol, 2-butanol, tert-butanol, and cyclohexanol, methyl ethyl ketone, methyl Ketones such as isobutyl ketone and acetone, esters such as ethyl acetate, methyl acetate, ethyl lactate, isopropyl acetate, amyl acetate, and ethyl butyrate, glycol ethers (propylene glycol mono (carbon atom number 1 to 4) alkyl ether (specific) Specifically, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene group Coal monobutyl ether), propylene glycol mono (C1-C4) alkyl ether esters (propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate)), hydrocarbons such as toluene, benzene, cyclohexane, n-hexane and other solvents Etc. Moreover, the solvent which mixed these suitably is used preferably.

  In the present invention, the liquid containing the thin film forming material is applied on the substrate or directly supplied to the space for energy treatment.

  In general, when applied onto a substrate, it is applied as a coating film by application such as dipping or as droplets by spraying or the like, but in the present invention, the application liquid containing a polymerizable monomer is based on a mist. It is characterized by being sprayed on the surface of the material.

  Moreover, when supplying the coating liquid containing a polymerizable monomer to the energy treatment space in the form of a mist, the average particle diameter of the droplets is 5 μm or less, preferably 1 μm or less from the viewpoint of plasma reactivity and productivity. . The average particle size of the droplets can be measured by simply irradiating the droplet group with laser light and calculating the particle size distribution from the intensity distribution pattern of the diffracted / scattered light emitted from it. The company's LDSA-1500A can be used.

  Next, a droplet forming method for applying a coating solution containing a polymerizable monomer according to the present invention in the form of a mist on a substrate will be described.

  FIG. 6 is a diagram showing a schematic configuration of a droplet generator system preferably used in the present invention.

  The droplet generator system 112 includes a raw material reservoir that stores a polymer layer forming coating liquid containing a polymerizable monomer (hereinafter referred to as a polymer layer forming coating liquid), that is, a pressure reservoir 114, a mass flow controller 115, And a droplet generator 116, an acceleration system 118, and a charge neutralization system 121.

The gas system 172 pumps pressurized gas, preferably dry nitrogen or other inert gas, through the line 134 to the pressurized reservoir 114 and the polymer layer forming coating solution from the pressurized reservoir 114 to the mass flow controller 115. Provide with enough pressure to do. The pressurized reservoir 114 is pressurized by opening the valve 141. Pressurized pressurized reservoir 114 is connected to mass flow controller 115 via line 135, and mass flow controller 115 is connected to droplet generator 116 via line 136. The mass flow controller 115 can control the flow of the coating liquid for forming a polymer layer to the droplet generator 116 to about 0.05 to 1 cm ³ / min. The coating liquid for forming the polymer layer moves to the droplet generator 116 through the inlet tube 136. Optionally, a return tube 137 returns the polymer layer-forming coating solution that has not become droplets or agglomerated from the droplet generator 116 to the pressurized reservoir 114.

In a preferred embodiment of the present invention, the amount of agglomerated polymer layer forming coating solution that has not become droplets is relatively small, ie, about 20% or less of the total polymer layer forming coating solution, thus The agglomerates are not reused, but are simply disposed of by purging the droplet generator 116 after deposition. This can eliminate potential problems such as an increase in the viscosity of the polymer layer forming coating solution. Valves 139 and 140 are then opened and pressurized gas flows through gas line 142 and is sent to droplet generator 116. The gas pressure in line 142 is automatically adjusted to a predetermined pressure. Preferably, this pressure is from 2.76 × 10 ^{5 to} 5.52 × 10 ⁵ Pa, more preferably 4.14 × 10 ⁵ Pa. Preferably, the gas is a mixture of an inert gas such as dry nitrogen and a gas that is easily ionized, preferably oxygen or carbon dioxide, most preferably oxygen. Add oxygen to increase droplet charge. Oxygen is easily ionized and helps to transfer charge to the liquid droplet droplets as the gas particles collide continuously in a room temperature gas. Preferably, the oxygen in the gas is 1-15% by volume, most preferably 5-10% by volume. The preferred embodiment process used 95% dry nitrogen and 5% oxygen.

  The valve 147 can then be opened and the droplets generated by the droplet generator 116 can be supplied via a conduit 149 onto the substrate in the chamber 120 of the atmospheric pressure plasma processing apparatus.

  This will be described in more detail below.

  The voltage can be applied to either apply an electrical filter to the droplet, or to either charge the droplet, or both. The voltage applied to the droplet generator system 112 is automatically controlled to a predetermined voltage by the power generator 159. Similarly, charged particles are accelerated in the chamber 120 of the atmospheric pressure plasma processing apparatus by a voltage applied from the power source 164 via the electric cable 166. The acceleration voltage is automatically controlled via the power source 164. Optionally, the charge neutralizer system 121 generates particles that are charged to a charge opposite to the droplet particles that adhere to the substrate. The charge neutralizer system includes an ionized particle source 169. After opening the supply valve 155A, the valve 155B of the gas system 155 is computer controlled to generate a gas flow through the ionized particle source 169 and the gas line 156, introducing ionized particles into the chamber, where the ionized particles are Point to the board. Alternatively, dry nitrogen may be directed to the lower side of the substrate using the gas system 155 so that the polymer layer forming coating solution does not adhere to the lower side of the substrate. The gas system 155 can be further controlled to allow additional dry nitrogen or other inert gas to enter the chamber 120 via the gas line 156. This is done when necessary to maintain the pressure at the desired level. Additional oxygen or carbon dioxide can be added if necessary to assist in the loading of the droplets.

  By generating droplets as described above, it is possible to generate droplets of very small particles as shown in FIG.

  The coating solution used here is preferably dissolved in a solvent having a low surface tension from the viewpoints of droplet atomization, aggregation prevention, and coating repellency prevention. It is preferable to perform in the vicinity.

(Curing treatment)
The polymer layer according to the present invention is applied with a polymer layer forming coating solution in a mist form on the substrate as described above, and then subjected to curing treatment by irradiating the coating surface with active energy rays.

As the active energy ray that can be used for the curing treatment applicable in the present invention, ultraviolet irradiation and electron beam irradiation are generally used. In the case of ultraviolet irradiation, the irradiation intensity is preferably ²⁰ to 300 mJ / cm ² , the irradiation time is preferably 0.5 seconds to 5 minutes, and more preferably 3 seconds to 2 minutes from the curing efficiency and work efficiency of the ultraviolet curable resin.

  In the present invention, atmospheric pressure plasma treatment is also effective as energy treatment other than ultraviolet rays and electron beams.

  The atmospheric pressure plasma treatment as used in the present invention means that gas is supplied between opposing electrodes under atmospheric pressure or a pressure near atmospheric pressure, and a high frequency electric field is generated between the electrodes to make the gas an excitation gas, It is the process which exposes the coating film formed by giving the coating liquid for polymer layer formation which concerns on this invention to excitation gas in mist form. Thereby, the said coating liquid for polymer layer formation is activated and hardened | cured, and forms a thin film on a base material.

  Regarding electrodes used for atmospheric pressure plasma treatment, gas supplied between the electrodes, generation of a high-frequency electric field, and the like, those described in WO02 / 48428 and JP-A-2004-68143 can be used.

  The pressure under atmospheric pressure or the pressure in the vicinity thereof is about 20 to 110 kPa, and preferably 93 to 104 kPa.

  The electrode is preferably a metal base material coated with a dielectric. It is preferable to coat a dielectric on at least one side of the opposed application electrode and the ground electrode, and more preferably coat both of the opposed application electrode and the ground electrode with a dielectric. The dielectric is preferably an inorganic substance having a relative dielectric constant of 6 to 45. Examples of such a dielectric include ceramics such as alumina and silicon nitride, silicate glass, borate glass, and the like. There are glass lining materials.

  In the present invention, the gas supplied between the electrodes contains at least a discharge gas. The discharge gas is a gas that can cause discharge by applying a voltage. Examples of the discharge gas include nitrogen, rare gas, hydrogen gas, and the like. These may be used alone as a discharge gas or may be used in combination. In the present invention, nitrogen is preferred as the discharge gas. It is preferable that 50-100 volume% of discharge gas is nitrogen gas. At this time, as the discharge gas other than nitrogen, it is preferable to contain a rare gas of less than 50% by volume. Moreover, it is preferable to contain 90-99.9 volume% of quantity of discharge gas with respect to the total gas quantity supplied to discharge space.

  In addition to the discharge gas, the gas supplied between the electrodes may contain an additive gas that promotes the reaction for forming a thin film. Examples of the additive gas include hydrogen and ammonia, but hydrogen is preferable, and it is preferable to mix a component selected from these. The content is preferably 0.01 to 5% by volume based on the total amount of gas, whereby the polymerization reaction of the polymerizable monomer is promoted, and a dense and high-quality thin film can be formed.

  The gas supplied between the electrodes is activated by itself as a excitation gas when a voltage is applied thereto. And when the coating liquid for polymer layer formation which concerns on this invention is exposed to the said excitation gas, it will be estimated that the said liquid changes to the state which can form a thin film on a base material.

  The high-frequency electric field generated between the electrodes may be an intermittent pulse wave or a continuous sine wave. However, in order to obtain a high effect of the present invention, it may be a continuous sine wave. preferable. The frequency of the high frequency electric field is preferably 100 to 150 MHz.

The power density supplied to the electrodes is preferably 1.0 W / cm ² or more, the upper limit is preferably 50 W / cm ² or less, more preferably 20W / cm ² or less.

  In addition, when the gas supplied between electrodes contains nitrogen as discharge gas, since a big electric field intensity | strength of a discharge start is required, it is preferable to superimpose two types of high frequency electric fields. By doing so, even when the discharge gas is nitrogen, high-density plasma generation can be achieved, a high-quality thin film can be obtained, high-speed film formation can be performed, and furthermore, low-cost and safe operation can be achieved. Reduction of environmental load can also be achieved. The two kinds of high-frequency electric fields can maintain a stable discharge state by satisfying the following relationship.

That is, the first than the frequency omega ₁ of the high frequency electric field of the second high-frequency electric field frequency omega ₂ is high and the first strength V ₁ of the high-frequency electric field, strength V ₂ and the second high-frequency electric field The relationship with the intensity IV of the discharge start electric field is that V ₁ ≧ IV> V ₂ or V ₁ > IV ≧ V ₂ is satisfied. Here, the frequency of the first high-frequency electric field is preferably 200 kHz or less. The lower limit is preferably about 1 kHz. On the other hand, the frequency of the second high frequency electric field is preferably 800 kHz or more. The higher the frequency of the second high-frequency electric field, the higher the plasma density and the higher the processing speed. The upper limit is preferably about 200 MHz.

  In this way, in the electric field generated between the electrodes, the coating solution containing the polymerizable monomer applied to the substrate or the coating solution containing the polymerizable monomer before being applied to the substrate is exposed and activated, Thin film on the material.

  Next, as a mist forming means for a coating liquid containing a polymerizable monomer, a coating liquid microdroplet method using an ultrasonic sprayer and an atmospheric pressure plasma processing apparatus equipped with the ultrasonic sprayer are shown in FIGS. 4 will be described. The embodiment of the present invention is not limited to these.

  FIG. 1 is a schematic view of an ultrasonic sprayer used when a coating liquid containing a polymerizable monomer is applied as droplets on a substrate or supplied between electrodes. Thereby, microdroplets (droplets) containing a polymerizable monomer can be formed.

  In FIG. 1, 1 is an ultrasonic atomizer, 11 is an introduction tube for introducing nitrogen gas, 12 is a raw material reservoir for storing a coating liquid L containing a polymerizable monomer as a droplet raw material, 13 is an ultrasonic generator, Reference numeral 14 denotes a power source connected to the ultrasonic wave generator 13, and reference numeral 15 denotes a discharge tube for discharging the generated droplets. When nitrogen gas is introduced from the introduction pipe 11 into the raw material storage unit 12 and the power source 14 is turned on to generate ultrasonic waves from the ultrasonic wave generation unit 13, droplets are generated. The droplets generated in this way are discharged out of the ultrasonic sprayer 1 through the discharge tube 15, and the droplets are sprayed in a mist form at an appropriate location of an atmospheric pressure plasma apparatus (not shown).

  FIG. 2 is a schematic view of a single-wafer atmospheric pressure plasma processing apparatus equipped with an ultrasonic atomizer. In FIG. 2, reference numeral 1 denotes an ultrasonic atomizer similar to that shown in FIG. The droplets M sprayed downward from the ultrasonic sprayer 1 are applied onto the substrate S in the spray space A. Reference numeral 21 denotes a fixed first electrode, and reference numeral 22 denotes a second electrode that supports the substrate S and can be repeatedly moved in the direction of the white arrow in the figure. The first electrode 21 and the second electrode 22 are provided to face each other with a predetermined gap, and this gap constitutes the discharge space D. The first electrode 21 and the second electrode 22 are connected to a filter 27A or 27B, which is a load, a matching box 26A or 26B, and a high-frequency power source 25A or 25B, respectively, and are grounded. The filter is inserted in order to superimpose two different types of high-frequency electric fields in the discharge space so that the high-frequency waves do not affect each other's power supply. The matching box is inserted to cancel the reactance component of the load and correct the impedance in order to effectively use the energy of the high-frequency power source.

  The first high-frequency electric field generated by the high-frequency power supply 25A and the second high-frequency electric field generated by the high-frequency power supply 25B satisfy the following relationship.

First than the frequency omega ₁ of the high frequency electric field of the second high-frequency electric field frequency omega ₂ is high and the strength V ₁ of the first high frequency electric field, strength V ₂ and the discharge start of the second high-frequency electric field The relationship with the electric field strength IV satisfies V ₁ ≧ IV> V ₂ or V ₁ > IV ≧ V ₂ . As described above, by superimposing two types of high-frequency electric fields satisfying this relationship, a stable and high-density discharge state can be achieved even when a gas such as nitrogen having a high discharge starting electric field strength is used. High-quality film formation can be performed.

  For example, a high frequency with a frequency of 100 kHz is used as the first high frequency electric field, and a high frequency with a frequency of 13.56 MHz is used as the second high frequency electric field facing the first high frequency electric field. Between the electrodes, a mixed gas of 0.1% by volume of oxygen gas and 1% by volume of hydrogen gas with respect to nitrogen gas is introduced to form a discharge space.

  The substrate S is placed on the second electrode 22 and repeatedly moves between the spray space A and the discharge space D. In the spray space A, droplets of a coating liquid containing a polymerizable monomer are applied on the substrate S. In the discharge space D, a discharge gas such as nitrogen is supplied, two kinds of high-frequency electric fields are superimposed, and high-density plasma is generated, and the substrate S to which droplets are applied is exposed. By repeating this, a polymer layer is formed.

  FIG. 3 is a schematic view of a roll-type atmospheric pressure plasma processing apparatus equipped with an ultrasonic atomizer. In FIG. 3, the same reference numerals as those in FIG. 2 are the same as the members described in FIG. In FIG. 3, S is a long base material such as a plastic film. The base material S is wound around the roll electrode 22R that is the second electrode, and is conveyed in the direction of the arrow in the drawing. The droplet M of the coating liquid containing the polymerizable monomer sprayed from the ultrasonic sprayer 1 is applied on the substrate S in the spray space A. Thereafter, when the base material S to which the droplet M is applied passes through the discharge space D formed between the first electrode 21 and the second electrode 22R, a polymer layer is formed.

  FIG. 4 is a schematic view of another type of atmospheric pressure plasma processing apparatus that can be used in the present invention. In FIG. 4, an atmospheric pressure plasma processing apparatus 30 is an apparatus having an electric field applying means 40 having two power sources, a gas / droplet supplying means 50, and an electrode temperature adjusting means 60.

  The polymerizable monomer supplied from the gas / droplet supply means 50 is contained between the opposing electrodes (discharge space) 32 of the roll electrode (first electrode) 35 and the plurality of rectangular tube electrodes (second electrodes) 36. A mixture MG of fine droplets (droplets) and nitrogen, which is a discharge gas, is supplied, activated here, and deposited on the substrate F to form a thin film.

A discharge space (between the counter electrodes) 32 between the roll rotating electrode (first electrode) 35 and the square tube electrode (second electrode) 36 is connected to the roll rotating electrode (first electrode) 35 from the first power source 41. frequency omega _1, electric field intensity V _1, the frequency omega ₂ of the second power source 42 to the first high-frequency electric field, also prismatic electrode (second electrode) 36 of the current I _1, the electric field intensity V _2, the current I ₂ The second high-frequency electric field is applied.

  A first filter 43 is installed between the roll rotation electrode (first electrode) 35 and the first power supply 41, and the first filter 43 easily passes a current from the first power supply 41 to the first electrode. The current from the second power supply 42 is grounded so that the current from the second power supply 42 to the first power supply is difficult to pass. Further, a second filter 44 is installed between the square tube electrode (second electrode) 36 and the second power source 42, and the second filter 44 has a current flowing from the second power source 42 to the second electrode. It is designed to make it difficult to pass the current from the first power supply 41 to the second power supply by grounding the current from the first power supply 41.

In the present invention, the roll rotation electrode 35 may be the second electrode, and the rectangular tube electrode 36 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power supply preferably applies a higher frequency electric field strength (V ₁ > V ₂ ) than the second power supply. Further, the frequency has the ability to satisfy ω ₁ <ω ₂ .

The current is preferably I ₁ <I ₂ . The current I ₁ of the first high-frequency electric field is preferably 0.3 to 20 mA / cm ² , more preferably 1.0 to 20 mA / cm ² . The current I ₂ of the second high-frequency electric field is preferably 10 to 100 mA / cm ² , more preferably 20 to 100 mA / cm ² .

  In the gas / droplet supply means 50, the gas / droplet MG generated by the gas / droplet generator 51 is introduced into the atmospheric pressure plasma processing container 31 from the air supply port 52 while controlling the flow rate.

  The base material F is unwound from the original winding (not shown) and conveyed, or is conveyed from the previous process, and the air entrained by the base material by the nip roll 65 via the guide roll 64 is blocked. While being in contact with the roll rotation electrode 35, it is transferred between the roll tube electrode 36 and the square tube electrode 36, and an electric field is generated from both the roll rotation electrode (first electrode) 35 and the square tube electrode (second electrode) 36. Then, discharge plasma is generated between the counter electrodes (discharge space) 32. The base material F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 35. The base material F passes through the nip roll 66 and the guide roll 67 and is wound up by a winder (not shown) or transferred to the next process.

  The discharged process waste liquid droplet G ′ is discharged from the exhaust port 53.

  In order to heat or cool the roll rotating electrode (first electrode) 35 and the rectangular tube electrode (second electrode) 36 during the formation of the thin film, the medium whose temperature is adjusted by the electrode temperature adjusting means 60 is fed by the liquid feed pump P. It sends to both electrodes through the piping 61, and temperature is adjusted from the inside of an electrode. Reference numerals 68 and 69 denote partition plates that partition the atmospheric pressure plasma processing vessel 31 from the outside.

  Each square tube electrode 36 shown in FIG. 4 has an effect of widening the discharge range (discharge area) as compared with the cylindrical electrode, and thus is preferably used in the present invention.

  The distance between the opposing first electrode and second electrode is the shortest distance between the surface of the dielectric and the surface of the conductive metallic base material of the other electrode when a dielectric is provided on one of the electrodes. Say that. When a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces. The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of performing 0.15 mm, 0.1 to 20 mm is preferable, and 0.5 to 2 mm is particularly preferable.

  As the atmospheric pressure plasma processing container 31, a processing container made of Pyrex (registered trademark) glass or the like is preferably used. However, it is also possible to use a metal made as long as insulation from the electrode can be obtained. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation.

  Hereinafter, a high frequency power source applicable to the atmospheric pressure plasma processing apparatus according to the present invention will be exemplified.

As the first power supply (high frequency power supply) installed in the atmospheric pressure plasma processing apparatus,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source (high frequency power source),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma processing apparatus.

In the present invention, the electric power applied between the electrodes facing each other supplies power (power density) of 1 W / cm ² or more to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. Then, energy is applied to the thin film forming droplet to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. be able to. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

"Base material"
The base material used for the barrier film of the present invention will be described.

  The substrate used in the present invention is particularly limited as long as a thin film such as a plate-like, sheet-like or film-like planar shape or a three-dimensional shape such as a lens or other molded product can be formed on the surface thereof. There is no. There is no limitation on the form or material of the substrate as long as the substrate is exposed to a mixed gas in a plasma state regardless of whether it is in a stationary state or in a transferred state, and a uniform thin film is formed. The shape may be a planar shape or a three-dimensional shape, and examples of the planar shape include a glass plate and a resin film. Resin etc. can be used for material. Specifically, examples of the resin include a resin lens, a resin film, a resin sheet, and a resin plate.

  Since the resin film can be continuously transferred between or in the vicinity of the electrodes of the atmospheric pressure plasma processing apparatus according to the present invention to form a polymer layer or a barrier layer, a batch such as a vacuum system such as sputtering is used. Suitable for mass production, which is not a formula, and is suitable as a production method with high continuous productivity.

  The material of the molded product such as resin film, resin sheet, resin lens, resin molded product is cellulose ester such as cellulose triacetate, cellulose diacetate, cellulose acetate propionate or cellulose acetate butyrate, polyethylene terephthalate or polyethylene naphthalate. Polyester, Polyolefin such as polyethylene and polypropylene, Polyvinylidene chloride, Polyvinyl chloride, Polyvinyl alcohol, Ethylene vinyl alcohol copolymer, Syndiotactic polystyrene, Polycarbonate, Norbornene resin, Polymethylpentene, Polyetherketone, Polyimide, Polyether Sulfone, polysulfone, polyetherimide, polyamide, fluororesin, polymethylacrylate , Mention may be made of acrylate copolymers and the like.

  These materials can be used alone or in combination as appropriate. Among them, ZEONEX and ZEONOR (manufactured by ZEON CORPORATION), amorphous cyclopolyolefin resin film ARTON (manufactured by JSR Corporation), polycarbonate film Pure Ace (manufactured by Teijin Limited), cellulose triacetate film Konica Minolta Commercially available products such as Tuck KC4UX and KC8UX (manufactured by Konica Minolta Opto Co., Ltd.) can be preferably used. Furthermore, even for materials with a large intrinsic birefringence such as polycarbonate, polyarylate, polysulfone and polyethersulfone, conditions such as solution casting film formation, melt extrusion film formation, and further stretching conditions in the vertical and horizontal directions What can be used can be obtained by setting etc. suitably.

  Among these, a cellulose ester film that is optically close to isotropic is preferably used for the optical element. As the cellulose ester film, a cellulose triacetate film and cellulose acetate propionate are preferably used as described above. As the cellulose triacetate film, a commercially available Konica Minoltack KC4UX or the like is useful.

  Those obtained by coating gelatin, polyvinyl alcohol, acrylic resin, polyester resin, cellulose ester resin or the like on the surface of these resins can also be used. Moreover, you may provide an anti-glare layer, a clear hard coat layer, an antifouling layer, etc. in the barrier layer coating surface side of these resin films. Moreover, you may provide an adhesive layer, an alkali barrier coat layer, a solvent resistant layer, etc. as needed.

《Barrier layer》
In the barrier film of the present invention, it has at least one barrier layer on the base material, and preferably, after the polymer layer according to the present invention is subjected to the mist method and the curing treatment on the base material, A barrier layer is provided.

  The barrier layer according to the present invention can be formed by various methods. In the present invention, it is preferable to form the barrier layer using the above-mentioned atmospheric pressure plasma method.

  In the formation of the barrier layer using the atmospheric pressure plasma method, it is desirable to form a dense inorganic film, particularly as a raw material (thin film forming component) of the inorganic film used for forming the barrier layer according to the present invention. , Organometallic compounds, halogen metal compounds, metal hydride compounds, and the like.

  The organometallic compound useful in the present invention is preferably a compound represented by the following general formula (I), but is not limited thereto.

Formula (I)
R ¹ _x MR ² _y R ³ _z
In the above general formula (I), M is a metal (for example, Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, Pb, Bi, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc.), R ¹ is an alkyl group, R ² is an alkoxy group, R ³ is a β-diketone coordination group, β- It is a group selected from a ketocarboxylic acid ester coordinating group, a β-ketocarboxylic acid coordinating group and a ketooxy group (ketooxy coordinating group). When the valence of the metal M is m, x + y + z = m, and x = 0 ~ M, or x = 0 to m-1, y = 0 to m, z = 0 to m, both Or is a positive integer.

Examples of the alkyl group represented by R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group represented by R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 3,3,3-trifluoropropoxy group. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. The group selected from the β-diketone coordination group, β-ketocarboxylic acid ester coordination group, β-ketocarboxylic acid coordination group and ketooxy group (ketooxy coordination group) represented by R ³ includes β-diketone coordination group Examples of the group include 2,4-pentanedione (also referred to as acetylacetone or acetoacetone), 1,1,1,5,5,5-hexamethyl-2,4-pentanedione, 2,2,6,6-tetra Methyl-3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione, and the like. Examples of β-ketocarboxylic acid ester coordination groups include, for example, acetoacetic acid methyl ester, acetoacetic acid And ethyl ester, propyl acetoacetate, ethyl trimethylacetoacetate, methyl trifluoroacetoacetate and the like, β-ketocarboxylic acid Examples of the coordination group include acetoacetic acid, trimethylacetoacetic acid, and the like, and examples of the ketooxy coordination group include acetooxy group (or acetoxy group), propionyloxy group, butyryloxy group, acryloyloxy group, methacryloyloxy group. Etc. The number of carbon atoms in these groups is preferably 18 or less including the above-mentioned organometallic compounds. Further, as illustrated, it may be linear or branched, or a hydrogen atom substituted with a fluorine atom.

In the present invention, from the viewpoint of handling, an organometallic compound with a low risk of explosion is preferable, and an organometallic compound having at least one oxygen in the molecule is preferable. As such, an organometallic compound containing at least one alkoxy group of R ² , a β-diketone coordination group, a β-ketocarboxylic acid ester coordination group, a β-ketocarboxylic acid coordination group and a ketooxy group of R ³ A metal compound having at least one group selected from a group (ketooxy coordination group) is preferred.

  Specific organometallic compounds are shown below.

  Examples of the organosilicon compound include tetraethylsilane, tetramethylsilane, tetraisopropylsilane, tetrabutylsilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethylsilanedi (2 , 4-pentanedionate), methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, etc., as silicon hydrogen compounds, tetrahydrogen silane, hexahydrogen disilane, etc., as halogenated silicon compounds, tetrachlorosilane , Methyltrichlorosilane, diethyldichlorosilane and the like, and any of them can be preferably used in the present invention. Two or more of these may be mixed and used at the same time.

  Examples of titanium compounds include organic titanium compounds, titanium hydrogen compounds, and titanium halides. Examples of organic titanium compounds include triethoxy titanium, trimethoxy titanium, triisopropoxy titanium, tributoxy titanium, and tetraethoxy titanium. , Tetraisopropoxy titanium, methyl dimethoxy titanium, ethyl triethoxy titanium, methyl triisopropoxy titanium, triethyl titanium, triisopropyl titanium, tributyl titanium, tetraethyl titanium, tetraisopropyl titanium, tetrabutyl titanium, tetradimethylamino titanium, dimethyl titanium di (2,4-pentanedionate), ethyltitanium tri (2,4-pentanedionate), titanium tris (2,4-pentanedionate), titanium tris (acetomethylacetate) ), Triacetoxy titanium, dipropoxypropionyloxy titanium, etc., dibutylyloxy titanium, titanium hydrogen compound as monotitanium hydrogen compound, dititanium hydrogen compound, etc., and titanium halide as trichlorotitanium, tetrachlorotitanium, etc. Any of them can be preferably used in the present invention. Two or more of these may be mixed and used at the same time.

Examples of the tin compound include organic tin compounds, tin hydrogen compounds, and tin halides. Examples of the organic tin compounds include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetra Octyl tin, tetraethoxy tin, methyl triethoxy tin, diethyl diethoxy tin, triisopropyl ethoxy tin, diethyl tin, dimethyl tin, diisopropyl tin, dibutyl tin, diethoxy tin, dimethoxy tin, diisopropoxy tin, dibutoxy tin, tin dibutyrate Tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate, etc., tin hydride compounds, etc. Examples of tin halides include tin dichloride and tin tetrachloride. Any of them can be preferably used in the present invention. Two or more of these may be mixed and used at the same time. In addition, since the tin oxide film formed using these can reduce the surface specific resistance value to 1 × 10 ¹² Ω / □ or less, it is also useful as an antistatic layer.

  Other organometallic compounds include, for example, antimony ethoxide, arsenic triethoxide, barium 2,2,6,6-tetramethylheptanedionate, beryllium acetylacetonate, bismuth hexafluoropentanedionate, dimethylcadmium, calcium 2,2,6,6-tetramethylheptanedionate, chromium trifluoropentanedionate, cobalt acetylacetonate, copper hexafluoropentanedionate, magnesium hexafluoropentanedionate-dimethyl ether complex, gallium ethoxide, tetraethoxygermane , Tetramethoxygermane, hafnium t-butoxide, hafnium ethoxide, indium acetylacetonate, indium 2,6-dimethylaminoheptanedionate Ferrocene, lanthanum isopropoxide, lead acetate, tetraethyl lead, neodymium acetylacetonate, platinum hexafluoropentanedionate, trimethylcyclopentadienylplatinum, rhodium dicarbonylacetylacetonate, strontium 2,2,6,6-tetramethyl Examples include heptanedionate, tantalum methoxide, tantalum trifluoroethoxide, tellurium ethoxide, tungsten ethoxide, vanadium triisopropoxide oxide, magnesium hexafluoroacetylacetonate, zinc acetylacetonate, and diethylzinc.

  The barrier layer according to the present invention is an atmospheric pressure plasma method in which two or more electric fields having different frequencies are applied to nitrogen gas containing a thin film forming gas of the above-mentioned compound forming the barrier layer. It is preferable to form using the atmospheric pressure plasma processing apparatus described. By forming the barrier layer using the atmospheric pressure plasma method, a barrier film with higher quality and higher productivity can be manufactured.

  In the atmospheric pressure plasma method, using an atmospheric pressure plasma processing apparatus as shown in FIG. 4, a raw material gas and a raw material containing the organometallic compound between opposed electrodes under atmospheric pressure or pressure near atmospheric pressure. Supplying a mixed gas of a reactive gas composed of a decomposition gas for decomposing gas to obtain an inorganic compound and a discharge gas excited to a plasma state, and generating a high-frequency electric field between the electrodes, the mixing By using a gas as an excitation gas and exposing the substrate having a polymer layer to the excitation gas, a barrier layer with high film surface uniformity is formed.

  Decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound includes hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide gas, Examples thereof include nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). The ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, but the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

  In the barrier layer according to the present invention, the inorganic compound contained in the barrier layer is preferably at least one selected from silicon oxide, silicon oxynitride, silicon nitride, alumina oxide, and mixtures thereof, and in particular, transmits moisture. From the viewpoint of the properties, light transmittance and suitability for atmospheric pressure plasma CVD described later, silicon oxide is preferable.

  The inorganic compound according to the present invention can obtain, for example, a film containing at least one of O atoms and N atoms and Si atoms by further combining oxygen gas and nitrogen gas at a predetermined ratio with the organic silicon compound. .

  The barrier film including the barrier layer according to the present invention preferably has high transparency such that the average light transmittance in the region where the wavelength is 400 or more and 700 nm or less is 80% or more, and more preferably 90% or more. Is more preferable. The upper limit average light transmittance is not particularly limited because it is naturally limited by the barrier layer and polymer layer to be formed.

  According to JIS R 1635, the average light transmittance referred to in the present invention is, for example, a transmittance (at each wavelength of 400 nm to 700 nm using a spectrophotometer 1U-4000 type manufactured by Hitachi, Ltd.) at each wavelength ( %) Was measured at 60 points. Subsequently, the average value of the transmittance of each wavelength is obtained, and this is used as the average light transmittance.

  The barrier film having such optical characteristics can be used for applications such as a transparent substrate of an organic EL device (OLED), for example.

The water vapor permeability of the barrier film of the present invention is 0.1 g when measured in accordance with the JIS K7129 B method when used in applications requiring high gas barrier properties such as organic EL displays and high-definition color liquid crystal displays. / m less than ² / day, and is preferably an oxygen permeability of less than ^{0.1ml / m 2 / day / atm} .

  The barrier film of the present invention can also be sealed by bonding an OLED on the barrier film via an epoxy adhesive or the like. As the epoxy adhesive, those commercially available from Nagase ChemteX Corporation can be used as the OLED sealing material.

  Next, an OLED having an improved gas barrier property using the barrier film of the present invention will be described.

  The organic EL device has a base material on which at least an electrode and an organic compound layer are formed, and the barrier film of the present invention is sealed so as to cover the organic EL device.

  As another form, the organic EL device has a substrate on which at least an electrode and an organic compound layer are formed, and the barrier film of the present invention covers at least the electrode and the organic compound layer of the organic EL device. The form bonded together is mentioned.

  In another form, the organic EL device has at least an electrode and an organic compound layer formed on the barrier film of the present invention, and the barrier film of the present invention is sealed so as to cover the organic EL device. A form is mentioned.

  As another form, the organic EL device has at least an electrode and an organic compound layer formed on the barrier film of the present invention, and the barrier film of the present invention is bonded so as to cover at least the electrode and the organic compound layer of the organic EL device. The form which is is mentioned.

  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.

Example << Preparation of Barrier Film >>
[Preparation of barrier film 1]
(Formation of polymer layer)
<Preparation of coating solution for polymer layer formation>
The following additives were mixed and dissolved to prepare a coating solution for forming a polymer layer.

Dipentaerythritol hexaacrylate monomer 60 mass parts Dipentaerythritol hexaacrylate dimer 20 mass parts Dipentaerythritol hexaacrylate trimer or higher component 20 mass parts Diethoxybenzophenone photopolymerization initiator 2 mass parts Isopropyl alcohol 50 mass parts Part 50 parts by weight of ethyl acetate 50 parts by weight of methyl ethyl ketone <Mist droplet formation>
By using the above-prepared coating liquid for forming a polymer layer (droplet raw material L) at 25 ° C., droplets M for forming a polymer layer were generated by the ultrasonic sprayer 1 shown in FIG. The frequency of the ultrasonic atomizer was 2 MHz, the nitrogen gas flow rate was 10 L / min, and the temperature was 80 ° C.

(Droplet spraying to substrate and UV irradiation)
Using the processing apparatus shown in FIG. 3, a DC electric field of +1 kV was applied to the supply port, and the droplet M was sprayed onto the substrate S (polyether sulfone film). The processing apparatus of FIG. 3 includes a backup roll 22R that holds a substrate S having a cooling function, a mist sprayer, and an ultraviolet irradiation unit, and the ultraviolet irradiation unit is sprayed immediately after spraying because it is located downstream of the spray space. The droplets are exposed to ultraviolet light.

Here, the energy density of ultraviolet irradiation was set to 120 mJ / cm ^2, and the treatment was performed while adjusting the conveyance speed so that the irradiation time was 1 sec, thereby forming a polymer layer having a film thickness of 3.0 μm. In addition, the backup roll 22R holding the substrate S during film formation was maintained at 30 ° C. and kept warm.

<Measurement of droplet size distribution>
In the above-described droplet spraying step, the particle size distribution of the droplet droplets was measured 30 mm above the base material using an OPTICS / RTS5113 of the spray tech series manufactured by Sysmex Corporation. The obtained particle size distribution is shown in Table 5 (A).

(Formation of barrier layer)
A barrier layer was formed on the base material provided with the barrier layer by atmospheric pressure plasma CVD.

  As the atmospheric pressure plasma processing apparatus, a roll electrode type discharge processing apparatus shown in FIG. 4 was used.

  A plurality of rod-shaped electrodes facing the roll electrode are installed in parallel to the film transport direction, and the following raw materials and power are input to each electrode portion, and an adhesion layer, a ceramic layer, a protection layer are formed on the polymer layer. A barrier layer composed of

  The dielectric was coated with 1 mm of single-sided ceramic sprayed material with both opposing electrodes. The electrode gap after coating was set to 1 mm. The metal base material coated with the dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. The power source used here was a high frequency power source (80 kHz) manufactured by Applied Electric, and a high frequency power source (13.56 MHz) manufactured by Pearl Industry.

<Adhesion layer>
Discharge gas: Nitrogen gas Reactive gas 1: 1% by volume of hydrogen gas with respect to the total gas
Reactive gas 2: 0.5% by volume of tetraethoxysilane with respect to the total gas
Low frequency power supply power: power supply frequency = 80 kHz, power density = 10 W / cm ²
High frequency side power supply power: power supply frequency = 13.56 MHz, output density = 5 W / cm ²
<Ceramic layer>
Discharge gas: nitrogen gas Reactive gas 1: 5% by volume of oxygen gas with respect to the total gas
Reactive gas 2: 0.1% by volume of tetraethoxysilane with respect to the total gas
Low frequency power supply power: power supply frequency = 80 kHz, power density = 10 W / cm ²
High frequency side power supply power: power supply frequency = 13.56 MHz, output density = 8 W / cm ²
<Protect layer>
Discharge gas: Nitrogen gas Reactive gas 1: 1% by volume of hydrogen gas with respect to the total gas
Reactive gas 2: 0.5% by volume of tetraethoxysilane with respect to the total gas
Low frequency power supply power: power supply frequency = 80 kHz, power density = 10 W / cm ²
High frequency side power supply power: power supply frequency = 13.56 MHz, output density = 5 W / cm ²
Each layer is formed in the order of an adhesion layer, a ceramic layer, and a protection layer on the polymer layer, and each film thickness is 50 nm for the adhesion layer, 20 nm for the ceramic layer, and 400 nm for the protection layer. The substrate holding temperature when forming the barrier layer was 120 ° C.

[Preparation of barrier film 2]
In the production of the barrier film 1, the curing treatment of the polymer layer is changed to the atmospheric pressure plasma treatment using the atmospheric pressure plasma treatment apparatus shown in FIG. A barrier film 2 was produced in the same manner except that a polymer layer having a thickness of 3.0 μm was formed.

(Droplet spray on substrate, formation of plasma)
Using the atmospheric pressure plasma processing apparatus shown in FIG. 3, a DC electric field of +1 kV was applied to the supply port, and droplets of the coating liquid for forming the polymer layer were sprayed onto the substrate S (polyether sulfone film). In the atmospheric pressure plasma processing apparatus of FIG. 3, a high frequency power source with a frequency of 100 kHz is connected to the electrode 22R holding the base material S, a high frequency power source with a frequency of 13.56 MHz is connected to the rod-shaped electrode 21 facing the electrode 22R, and between the power source body and the electrode. Is connected to a matching box for impedance matching. In addition, a filter is installed between the matching box and the electrode so that no mutual current flows. A discharge gas was formed in the discharge space D by introducing a mixed gas of 1% by volume of hydrogen gas with respect to nitrogen gas. Since the portion exposed to the plasma gas is located downstream of the spray space A, the sprayed droplets are exposed to the plasma gas immediately after spraying.

The output density of the high-frequency power source with a frequency of 100 kHz was 3 W / cm ² and the output density of the high-frequency power source with 13.56 MHz was 5 W / cm ² .

  The electrode 22R that holds the substrate S during film formation was maintained at 120 ° C. and kept warm.

[Preparation of barrier film 3]
In the production of the barrier film 1, the formation of the polymer layer is replaced by a mist spraying method using an ultrasonic sprayer, and a polymer layer forming coating solution is formed by a wet coating method using a die coater. A barrier film 3 was produced in the same manner except that the energy treatment of ultraviolet irradiation was performed in the same manner as in the production. The film thickness of the polymer layer was 3.0 μm. However, the electrode 22R that holds the substrate S during film formation was set to 50 ° C.

[Preparation of barrier film 4]
In the production of the barrier film 1, a barrier film 4 was produced in the same manner except that the polymer layer was not applied.

<< Evaluation of barrier film >>
The following evaluation was performed about each barrier film produced as mentioned above.

[Evaluation of barrier properties: measurement of water vapor permeability]
The water vapor transmission rate was measured using a WOPET-003 type manufactured by CRIETECH.

Here, up to 10 ^-2 order, after comparing and evaluating the reference samples with the Mocon oxygen permeability measuring device OX-TRAN2 / 21 · L type and the water vapor permeability measuring device PERMATRAN-W3 / 33G type, the Mocon device Was calibrated with reference to the above, and extrapolated to the order of 10 ⁻⁷ by simulation.

[Measurement of surface roughness]
The center line average surface roughness (nm) was measured in accordance with the method defined in JIS B 0601.

[Evaluation of adhesion]
A cross-cut test based on JIS K 5400 was performed. On the surface of the formed thin film, using a single-edged razor, eleven cuts were made vertically and horizontally at intervals of 1 mm at 90 degrees with respect to the surface to make 100 1 mm square grids. A commercially available cellophane tape is affixed on top of this, and one end of the tape is peeled off vertically by hand, and the ratio (%) of the area where the thin film has not been peeled off to the tape area affixed from the score line is measured and adhered. A measure of gender.

  The results obtained as described above are shown in Table 1.

  As is clear from the results shown in Table 1, the barrier film produced by the constitution or manufacturing method defined in the present invention has a high gas barrier property (low water vapor transmission rate) with suppressed generation of pinholes and the like. And it turns out that it is excellent in flatness and adhesiveness.

  Furthermore, as a result of evaluating the occurrence of dark spots by laminating the barrier films prepared above as sealing films on OLEDs and storing them at 60 ° C. and 90% RH for 500 hours, taking 50 times magnified photographs. In the sample using the barrier film of the invention, generation of dark spots was not observed, but in the sample using the barrier film 4 as a comparative example, generation of many dark spots was observed. As described above, it can be seen that the barrier film of the present invention maintains the performance excellent in the water vapor blocking effect as compared with the comparative example.

It is the schematic of the ultrasonic atomizer used when apply | coating the coating liquid containing a polymerizable monomer as a droplet on a base material, or supplying between electrodes. 1 is a schematic view of a single-wafer atmospheric pressure plasma processing apparatus equipped with an ultrasonic atomizer. It is the schematic of a roll-type atmospheric pressure plasma processing apparatus provided with the ultrasonic atomizer. It is the schematic which shows another example of the atmospheric pressure plasma processing apparatus which can be applied to this invention. It is a figure which shows the particle size distribution of a droplet. It is a figure which shows schematic structure of the droplet generator system preferably used for this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ultrasonic sprayer 11 Introducing pipe 12 Raw material storage part 13 Ultrasonic wave generation part 14 Power supply 15 Release pipe 21 1st electrode 22, 32 2nd electrode 22R, 35 Roll rotation electrode 25A, 25B High frequency power supply 26A, 26B Matching box 27A, 27B Filter 30 Atmospheric pressure plasma processing apparatus 31 Atmospheric pressure plasma processing vessel 32, D Discharge space 36 Rectangular tube electrode 40 Electric field applying means 41 First power supply 42 Second power supply 43 First filter 44 Second filter 50 Gas / droplet supply means 51 Gas / Droplet Generator 52 Air Supply Port 53 Exhaust Port 60 Electrode Temperature Control Means 64 Guide Roll 65 Nip Roll 68, 69 Partition A A Spray Space M Gas / Droplet F, S Substrate G ′ Discharge Drop

Claims (15)

In a barrier film having at least a barrier layer and a polymer layer on a base material, the polymer layer was formed by spraying a coating liquid containing a polymerizable monomer on the surface of the base material in the form of a mist, followed by curing. A barrier film characterized by being a thing. 2. The barrier film according to claim 1, wherein an average light transmittance in a region of a wavelength of 400 or more and 700 nm or less is 80% or more. The barrier film according to claim 1, wherein at least one polymer layer is provided between the substrate and the barrier layer. The barrier film according to claim 1, wherein at least one of the polymer layers is in contact with the substrate. The barrier film according to claim 1, wherein at least one of the polymer layers is in contact with at least one layer of the barrier layer. The barrier film according to claim 4, wherein the polymer layer has a thickness of 0.5 μm or more and 10 μm or less. The barrier film according to claim 1, wherein the polymer layer has a center line average surface roughness Ra of 10 nm or less. 8. The barrier according to claim 1, wherein the polymerizable monomer forming the polymer layer is at least one selected from a methacrylic compound, an acrylic compound, an epoxy compound, and an oxetane compound. the film. In a method for producing a barrier film having at least a barrier layer and a polymer layer on a base material, the polymer layer is sprayed on the surface of the base material in the form of a mist with a coating liquid containing a polymerizable monomer, and then cured. A method for producing a barrier film, wherein The method for producing a barrier film according to claim 9, wherein at least one polymer layer is formed between the base material and the barrier layer. The method for producing a barrier film according to claim 9 or 10, wherein at least one of the polymer layers is in contact with the substrate. The method for producing a barrier film according to any one of claims 9 to 11, wherein the curing treatment is an ultraviolet irradiation treatment. The method for producing a barrier film according to any one of claims 9 to 11, wherein the curing treatment is an atmospheric pressure plasma treatment. The method for producing a barrier film according to any one of claims 9 to 13, wherein an average particle diameter of the mist of the coating liquid is 5.0 µm or less. The method for producing a barrier film according to any one of claims 9 to 13, wherein an average particle diameter of a mist of the coating solution is 1.0 µm or less.

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