JP2007230115A - Manufacturing method of transparent gas-barrier film, transparent gas-barrier film obtained thereby and apparatus for manufacture of transparent gass-barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a transparent gas-barrier film which enables efficient manufacture of a transparent gas-barrier film having excellent gas-barrier performance. <P>SOLUTION: The manufacturing method of a transparent gas-barrier film is based on forming a gas-barrier organic thin-film layer and a gas-barrier inorganic thin-film layer on one or both sides of a transparent substrate film 18 in the same vacuum vessel 12. The gas-barrier organic thin-film layer is formed by evaporating the material for the gas-barrier organic thin-film layer to generate vapor of the material, bringing the vapor into contact with the transparent substrate film 18 to form a coating film and hardening the coating film to form a gas-barrier organic thin-film layer, and the formation of the coating film is carried out in the vacuum vessel 12. In the formation of the coating film, the vapor is brought into contact with the transparent substrate film 18 under a pressure of the coating atmosphere lower than that of the inside of the vacuum vessel 12. The pressure of the coating atmosphere lower than that of the inside of the vacuum vessel 12 is produced e.g. with a vacuum pump 19 other than the evacuating mechanism for the vacuum vessel 12. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a transparent gas barrier film, a transparent gas barrier film, and an apparatus for producing a transparent gas barrier film.

Conventionally, a glass substrate has been used as a supporting substrate in various electric / electronic elements such as an organic EL (Electroluminescence) element, a liquid crystal display element, and a solar cell. However, recently, plastic substrates have come to be used instead of glass substrates because of their excellent characteristics such as lightness, impact resistance, and flexibility.

  However, the plastic substrate has a property that the gas permeability of oxygen, water vapor or the like is remarkably large as compared with a substrate formed of an inorganic material such as glass. For this reason, when a plastic substrate is used as the support substrate for the various electric / electronic elements described above, there is a risk that problems such as deterioration of the elements may occur. For example, in the organic EL element, when water vapor or oxygen penetrates into the organic thin film layer serving as a light emitting region, problems such as deterioration of light emission efficiency due to deterioration of the element and generation / growth of dark spots are caused.

Various techniques for improving the gas barrier property of the plastic substrate without impairing the transparency have been developed for such problems. For example, a method of depositing silicon oxide on a plastic substrate (see Patent Document 1) and a method of depositing aluminum oxide (see Patent Document 2) have been proposed. According to these methods, 1 g / m ² / The water vapor transmission rate can be reduced to about day. However, in recent electronic devices typified by the organic EL element, a very high gas barrier property is required for the supporting substrate. Particularly, the water vapor transmission rate is 0.1 g / m ² / day or less. Gas barrier properties are required.

In response to such demands, a method has been proposed in which a gas barrier layer having a multilayer structure in which organic thin film layers and inorganic thin film layers are alternately stacked is formed on a plastic substrate by vacuum deposition (Patent Document 3, (See Patent Document 4). In this method, when the organic thin film layer is formed by a vacuum deposition method, a very thin film can be formed, the film thickness can be controlled well, and contamination (contamination) can be prevented. In addition, this method has an advantage that when the organic thin film layer and the inorganic thin film layer are alternately laminated, the method can be performed under a constant atmospheric condition without changing the atmospheric condition from vacuum to normal pressure or from normal pressure to vacuum.
Japanese Patent Publication No.53-12953 JP 58-217344 A Pamphlet of International Patent No. WO00 / 26973 JP-A-7-263144

  However, the method of forming the gas barrier layer by alternately laminating the organic thin film layer and the inorganic thin film layer by the vacuum deposition method has a problem that the gas barrier property is insufficient. In order to solve this problem, if the number of layers is increased or each layer is thickened, there is a problem that the production efficiency is lowered.

  Then, the objective of this invention is providing the manufacturing method of the transparent gas barrier film which can manufacture efficiently the transparent gas barrier film excellent in gas barrier property, the transparent gas barrier film, and the manufacturing apparatus of a transparent gas barrier film. It is.

  In order to achieve the above object, the production method of the present invention includes a step of forming a gas barrier organic thin film layer on a transparent substrate film and a step of forming a gas barrier inorganic thin film layer on the transparent substrate film. The method for producing a transparent gas barrier film, wherein both the steps are carried out using the same vacuum chamber, wherein the step of forming the gas barrier organic thin film layer vaporizes the gas barrier organic thin film layer forming material. A coating film forming step of forming a coating film by contacting the generated vapor with the transparent substrate film; and a coating film curing step of curing the coating film to form the transparent gas barrier organic thin film layer, The coating film forming step is performed in the vacuum chamber, and in the coating film forming step, the vapor is brought into contact with the transparent substrate film under an atmospheric pressure condition lower than the pressure in the vacuum chamber. And features.

  The transparent gas barrier film of the present invention is obtained by the method for producing a transparent gas barrier film of the present invention.

  And the manufacturing apparatus of this invention has a vacuum chamber, a means to form a gas barrier organic thin film layer on a transparent base film, and a means to form a gas barrier inorganic thin film layer on the transparent base film An apparatus for producing a gas barrier film, wherein the means for forming the gas barrier organic thin film layer comprises: material vapor generating means for generating a material vapor by vaporizing the gas barrier organic thin film layer forming material; and A coating film forming means for forming a coating film by introducing it into the vacuum chamber and contacting the transparent substrate film; and a coating film curing means for curing the coating film to form the gas barrier organic thin film layer. Furthermore, it has a pressure reducing means for bringing the material vapor into contact with the transparent substrate film under an atmospheric pressure condition lower than the pressure in the vacuum chamber.

  In order to achieve the above object, the present inventors have made a series of studies and found that the reason why the gas barrier property is poor in the conventional method of forming a gas barrier layer by vacuum deposition is as follows. It was. That is, in the vacuum chamber, the vapor generated by vaporizing the organic thin film layer forming material is brought into contact with the plastic substrate to form a coating film, and this is cured to form the organic thin film layer. Since it diffuses without forming the coating film, the inside of the vacuum chamber is contaminated by drifting in the vacuum chamber or adhering to the inner wall of the vacuum chamber. In this state, when the inorganic thin film layer is formed, the vapor of the organic thin film layer forming material floating or adhering to the inner wall is taken into the inorganic thin film layer, and as a result, the characteristics of the obtained inorganic thin film layer are large. Deteriorated, especially gas barrier properties. Based on this finding, the present invention has been reached. That is, according to the manufacturing method of the present invention, in the coating film forming step, the vapor barrier organic thin film is used to bring the vapor into contact with the transparent substrate film under an atmospheric pressure condition lower than the pressure in the vacuum chamber. It is possible to prevent the vapor of the layer forming material from diffusing into the vacuum chamber, and as a result, it is possible to efficiently produce a transparent gas barrier film having excellent gas barrier properties. Moreover, since the transparent gas barrier film of this invention is manufactured by the manufacturing method of the said this invention, it is excellent in gas barrier property. And the manufacturing apparatus of this invention is an apparatus which can implement the manufacturing method of the said this invention efficiently.

In the present invention, the atmospheric pressure condition lower than the pressure in the vacuum chamber is not particularly limited, but for reasons such as prevention of contamination and oxygen inhibition, the atmospheric pressure is the gas barrier organic thin film layer forming material. It is preferable that the vapor pressure of the forming material is lower than the vapor pressure of the forming material at a temperature at which the vapor is introduced into the coating film forming site, and higher than the vapor pressure of the forming material at the temperature of the transparent substrate film. For example, the atmospheric pressure is in the range of 10 ⁻² to 10 ⁴ Pa, preferably in the range of 10 ⁻² to 10 ³ Pa, and more preferably in the range of 5 × 10 ⁻² to 10 ² Pa. is there.

In the manufacturing method of the present invention, it is preferable that the atmospheric pressure condition lower than the pressure in the vacuum chamber is realized by evacuating separately from the evacuation of the vacuum chamber. In the manufacturing apparatus of the present invention, it is preferable that the decompression means is a vacuum suction means provided separately from the vacuum suction means of the vacuum chamber.

In the manufacturing method of this invention, it is preferable that the vapor pressure of the said gas barrier organic thin film layer forming material in the temperature of the said transparent base film is lower than the pressure in the said vacuum chamber. More preferably, the pressure in the vacuum chamber during the formation of the gas barrier organic thin film layer is higher than the vapor pressure of the gas barrier organic thin film layer forming material at the temperature of the transparent substrate film, and the coating film formation It is higher than the pressure at the point. In the production apparatus of the present invention, it is preferable that the vapor pressure of the gas barrier organic thin film layer forming material at the temperature of the transparent substrate film can be set lower than the pressure in the vacuum chamber. More preferably, in the production apparatus of the present invention, the pressure of the vacuum chamber in forming the gas barrier organic thin film layer is higher than the vapor pressure of the gas barrier organic thin film layer forming material at the temperature of the transparent substrate film. It can be set higher than the pressure at the coating film forming portion. For example, the pressure of the vacuum chamber when forming the gas barrier organic thin film layer is in the range of 2 × 10 ⁻² to 10 ⁵ Pa, preferably in the range of 5 × 10 ⁻² to 2 × 10 ⁴ Pa. More preferably, it is the range of 10 < ^-1 > -5 * 10 < ³ > Pa.

In the manufacturing method of this invention, it is preferable to implement the said coating-film hardening process in the said vacuum chamber. Moreover, the manufacturing apparatus of this invention WHEREIN: It is preferable that the said coating-film hardening means is arrange | positioned in the said vacuum chamber.

  In the present invention, the temperature of the transparent base film during the formation of the gas barrier organic thin film layer is not particularly limited. For example, the vapor pressure of the gas barrier organic thin film layer forming material and the gas barrier organic film to be formed It can be determined appropriately from the relationship with the thickness of the thin film layer. For example, the temperature of the transparent substrate film in the formation of the gas barrier organic thin film layer is in the range of −100 ° C. to 200 ° C., preferably in the range of −50 ° C. to 150 ° C., more preferably − It is in the range of 50 ° C to 100 ° C.

  In the present invention, the gas barrier organic thin film layer forming material is not particularly limited and may be a single material, at least one main material selected from the group consisting of monomers and oligomers, a polymerization initiator, It may be a mixed material with at least one additive selected from the group consisting of a crosslinking agent, an acid generator, a filler (filler), an adhesion enhancing agent, and a sensitizer. In addition, the said additive is not limited to the above-mentioned thing, Other additives can also be used. The gas barrier organic thin film layer forming material is preferably liquid at room temperature and normal pressure. However, in the case of a mixed material, it may be liquid in a mixed state. And may be solid.

  Examples of the monomer and oligomer include aliphatic acrylate, alicyclic acrylate, aromatic acrylate, functional group-containing acrylate, phosphorus acrylate, metal acrylate, aliphatic methacrylate, alicyclic methacrylate, aromatic methacrylate, and functional group. Examples thereof include resin monomers or resin oligomers such as containing methacrylate, phosphorus methacrylate, and metal methacrylate. Examples of the functional group of the functional group-containing acrylate and functional group-containing methacrylate include OH group, allyl group, glycidyl group, carboxyl group, chloro group, and bromo group. In addition, examples of the monomer and oligomer include resin monomers or oligomers such as alicyclic epoxy resins, functional group-containing epoxy resins, functional group-containing silicone resins, pyrrolidone, and acetic acid resins. Examples of the functional group of the functional group-containing epoxy resin include an acrylate functional group and a glycidyl group. Examples of the functional group of the functional group-containing silicone resin include acrylate functional groups.

  An epoxide compound can also be used as the monomer. The epoxide compound preferably has two or more epoxy groups. By having two or more epoxy groups, polymerization can be facilitated in forming the gas barrier organic thin film layer, and a gas barrier organic thin film layer having excellent characteristics can be obtained. Examples of the epoxide compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and bisphenol APO adduct di. Examples thereof include glycidyl ether and 2,2-dibromoneopentyl glycol diglycidyl ether.

  Examples of the polymerization initiator include benzoin derivatives, thioxanthone, hydroxyacetophenone, aminoacetophenone, Michler ketone, acylphosphine oxide, acyloxime type initiator, sulfonium salt initiator, iodonium initiator, diazonium salt initiator, ferrocenium initiator, Examples include diamine compounds, triamine compounds, diol compounds, triol compounds, dialkoxide compounds, and the like. The crosslinking agent, the acid generator and the filler (filler) are not particularly limited, and conventionally known ones can be used.

  The thickness of the gas barrier organic thin film layer is not particularly limited, and is, for example, in the range of 0.001 to 50 μm, and preferably in the range of 0.002 to 15 μm.

In the production method of the present invention, the gas barrier organic thin film layer forming material is an active energy ray curable material, and the coating film curing step is performed by irradiating the active energy ray to the coating film. preferable. The active energy ray is preferably ultraviolet light, and the active energy ray curable material is preferably an ultraviolet curable material. In the production apparatus of the present invention, the gas barrier organic thin film layer forming material is an active energy ray curable material, and the coating film curing means includes the active energy ray irradiating means for the coating film. preferable. The active energy ray is preferably ultraviolet light, and the active energy ray irradiating means is preferably ultraviolet irradiating means. The irradiation intensity of the ultraviolet irradiation means is not particularly limited, and is preferably higher than the polymerization initiation intensity of the ultraviolet curable material to be used and lower than the decomposition intensity of the ultraviolet curable material. For example, the ultraviolet irradiation intensity is in the range of 20 to 250 W / cm, preferably in the range of 30 to 200 W / cm, and more preferably in the range of 40 to 150 W / cm. Moreover, the amount of ultraviolet irradiation is not particularly limited. For example, when the gas barrier organic thin film layer is formed while a transparent substrate film is conveyed using a roll, the ultraviolet irradiation intensity and the conveyance speed of the transparent substrate film are used. (Or the rotation speed of the roll) or the like. For example, the ultraviolet irradiation amount ^is in the range of ^{20mJ / cm 2 ~20J / cm 2} , preferably in the range from ^{30mJ / cm 2 ~15J / cm 2} , more preferably 50mJ ^/ cm ² ~10J ^/ cm 2 Range.

In the production method of the present invention, when two rolls are arranged in the vacuum chamber and the transparent substrate film is conveyed from one roll of the two rolls to the other roll, the coating film forming step and It is preferable to carry out the coating film curing step. Moreover, in the manufacturing apparatus of this invention, when the two rolls are arrange | positioned in the said vacuum chamber and the said transparent base film is conveyed from one roll of the said two rolls to the other roll, the said coating-film formation Preferably, the coating film is formed by the means, and then the coating film is cured by the coating film curing means to form the gas barrier organic thin film layer.

In the production method and production apparatus of the present invention, the gas barrier organic thin film layer is formed on one side or both sides of the transparent substrate film. Similarly, in the production method and production apparatus of the present invention, the gas barrier inorganic thin film layer is formed on one side or both sides of the transparent substrate film. For example, a gas barrier organic thin film layer and a gas barrier inorganic thin film layer may be laminated on one side of the transparent base film, or such a laminated gas barrier layer may be formed on both sides of the transparent base film. . Further, for example, a single layer or a plurality of gas barrier organic thin film layers are formed on one surface of the transparent substrate film, and a single layer or a plurality of gas barrier inorganic thin film layers are formed on the other surface. Also good.

In the present invention, the gas barrier inorganic thin film layer is preferably formed under vacuum. The pressure condition under vacuum in the formation of the gas barrier inorganic thin film layer is, for example, in the range of 1 × 10 ⁻⁴ to 1 × 10 ² Pa, preferably in the range of 1 × 10 ^{−3 to} 1 Pa. More preferably, it is the range of 1 * 10 ^<-2 > -0.1Pa.

In the manufacturing method of the present invention, the gas barrier inorganic thin film layer forming step physically vaporizes the gas barrier inorganic thin film layer forming material with an evaporation source, and generates plasma generated by a plasma generation source different from the evaporation source. It is preferable to use the step of forming the gas barrier inorganic thin film layer by activating the vaporized forming material. In the manufacturing apparatus of the present invention, the gas barrier inorganic thin film layer forming means includes an evaporation source for physically vaporizing the gas barrier inorganic thin film layer forming material, and a plasma generation source different from the evaporation source. Preferably, the gas barrier inorganic thin film layer is formed by activating the vaporized forming material using plasma generated by the another plasma generation source.

The plasma generation source is not particularly limited, and examples thereof include a pressure gradient plasma gun, a direct current discharge plasma generator, and a high frequency discharge plasma generator, and among these, a pressure gradient plasma gun is preferable. The evaporation source is not particularly limited, and examples thereof include an electron beam generator, a resistance heating evaporation apparatus, an induction heating type evaporation apparatus, and the like. Among these, an electron beam generator is preferable.

  In the present invention, the material for forming the gas barrier inorganic thin film layer is not particularly limited, and for example, at least one oxide such as Si, Al, Ti, Zn, In-Sn, Ta, Ni, and Zr, or oxynitride A nitride or the like can be used.

  In the present invention, the thickness of the gas barrier inorganic thin film layer is not particularly limited, and is, for example, in the range of 0.005 to 1 μm, preferably in the range of 0.01 to 0.5 μm, more preferably, It is in the range of 0.04 to 0.4 μm.

  In the present invention, the transparent substrate film is not particularly limited, but has high transparency and a high glass transition temperature in order to prevent cracking during heating of the gas barrier organic thin film layer and the gas barrier inorganic thin film layer, A polymer film having low hygroscopicity is preferred. Regarding the transparency, the light transmittance at a wavelength of 550 nm is preferably 80% or more. The glass transition temperature is preferably 50 ° C. or higher, and more preferably the glass transition temperature is 70 ° C. or higher. The hygroscopicity of the film is preferably 5% by weight or less, more preferably 1% by weight or less as measured by a gravimetric method, and it is particularly preferable that the dimensional change due to moisture absorption is small.

  Examples of the transparent base film include polycarbonate resins, norbornene resins, cycloolefin resins, epoxy resins, acrylic resins, polyethersulfone resins, polyethylene terephthalate resins (PET), and polyethylene naphthalate resins. And films formed from resins such as polyarylate resins and cyclic olefin resins. The thickness of the transparent substrate film is not particularly limited, and is, for example, in the range of 25 to 500 μm, and preferably in the range of 100 to 300 μm from the viewpoint of achieving both strength and thinning.

  In the production method of the present invention, one of the gas barrier organic thin film layer and the gas barrier inorganic thin film layer is formed on the transparent substrate film, and the other layer is formed on the formed layer. Is preferably formed. By alternately laminating the gas barrier organic thin film layer and the gas barrier inorganic thin film layer, the gas barrier property of the obtained transparent gas barrier film can be further improved. The number of stacked layers is not particularly limited. Further, as described above, the gas barrier organic thin film layer and the gas barrier inorganic thin film layer may be formed only on one side of the transparent base film or on both sides. .

In the production method of the present invention, it is preferable that the gas barrier organic thin film layer forming step and the gas barrier inorganic thin film layer forming step are performed in the same vacuum chamber. Similarly, in the production apparatus of the present invention, it is preferable that the gas barrier organic thin film layer forming means and the gas barrier inorganic thin film layer forming means are provided in the same vacuum chamber. In these cases, when the two rolls are arranged in the vacuum chamber and the transparent base film is transported from one roll of the two rolls to the other roll, the gas barrier organic thin film layer and the roll When one of the gas barrier inorganic thin film layers is formed, then the transport direction is reversed, and when the transparent substrate film is transported from the other roll to the one roll, the other is formed on the formed layer. It is preferable to form the layer.

In the production method of the present invention, as the transparent substrate film, a transparent substrate film having a smoothing layer on one side or both sides thereof can be used. The smoothing layer is preferably a smoothing layer formed by a wet film formation method. Moreover, in the manufacturing apparatus of this invention, it is preferable to have a smoothing layer formation means which forms a smoothing layer in the single side | surface or both surfaces of the said transparent base film further. The smoothing layer forming means is preferably a wet film forming method.

  As the material for forming the smoothing layer, for example, a material mainly composed of a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, etc. is used. It is preferable to use a material having low permeability and excellent adhesion to the transparent base film, the gas barrier organic thin film layer, and the gas barrier inorganic thin film layer. In order to improve the adhesion of the smoothing layer, the transparent substrate film may be subjected to a primer treatment with a silane coupling agent or the like.

  The material for forming the smoothing layer is, for example, epoxy resin, phenoxy resin, phenoxy ether resin, phenoxy ester resin, acrylic resin, melamine resin, phenol resin, urethane resin, alkyd resin, silicone resin, and a mixed resin of these resins, Polyester, polyvinyl alcohol, polyvinyl pyrrolidone, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyvinylidene fluoride, polychlorotrifluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkoxyethylene copolymer, etc. I can give you. These may be used alone or in combination of two or more. The smoothing layer can be formed, for example, by applying a solution or emulsion of the forming material on the transparent substrate film by a known method, and drying or curing the formed coating film. .

  The thickness of the smoothing layer is not particularly limited, but is, for example, in the range of 0.02 to 50 μm, and preferably in the range of 0.1 to 10 μm. Further, the transparency of the smoothing layer is preferably such that the light transmittance at 550 nm is 80% or more, like the transparent substrate film.

The production method of the present invention preferably further includes an overcoat layer forming step of forming an overcoat layer on one side or both sides of the transparent gas barrier film. The overcoat layer forming step is preferably a wet film forming method. Similarly, the production apparatus of the present invention preferably further includes an overcoat layer forming means for forming an overcoat layer on one side or both sides of the transparent gas barrier film. The overcoat layer forming means is preferably a wet film forming method.

  As the material for forming the overcoat layer, for example, the same material as that for forming the smoothing layer can be used. Moreover, the formation method of the said overcoat layer can use the method similar to the formation method of the said smoothing layer, for example. The thickness of the overcoat layer is not particularly limited, but is, for example, in the range of 50 nm to 50 μm.

In the transparent gas barrier film of the present invention, the water vapor permeability is preferably as low as possible, for example, 0.1 g / m ² / day or less, preferably 1 × 10 ⁻² g / m ² / day or less, More preferably, it is 1 × 10 ⁻³ g / m ² / day or less, further preferably 1 × 10 ⁻⁸ g / m ² / day or less, and most preferably 0 g / m ² / day. . The water vapor transmission rate can be measured by, for example, the method used in Examples described later.

  Next, an example of the manufacturing apparatus of the transparent gas barrier film of the present invention is shown in FIG. As shown in the figure, the manufacturing apparatus includes a vacuum chamber 12, a plasma generation source 1, an inorganic material evaporation source 2, a hearth 3, a reflective electrode 4, a main roll 5, two winding rolls 7a and 7b, and two auxiliary rolls 11. The vaporizer 13, the vaporized organic material application unit 14, the vacuum pump 19, and the ultraviolet lamp unit 16 are included as main components. The plasma generation source 1 is disposed on one outer wall (the left outer wall in the figure) of the vacuum chamber 12, and the reflective electrode 4 faces the other outer wall (the right side in the figure) in a state of facing the plasma generation source 1. It is arranged on the outer wall. An annular electromagnet coil (plasma focusing coil) 8 for guiding the plasma into the vacuum chamber 12 is disposed around the plasma generation source 1. In addition, an annular plate magnet 10 and an electromagnet coil (plasma focusing coil) 9 for converging plasma are arranged at positions corresponding to the arrangement position of the plasma generation source 1 and around the reflective electrode 4. Further, a reaction gas introduction pipe 6 is disposed on the outer wall of the vacuum chamber 12 above the position where the reflective electrode 4 is disposed, whereby, for example, a reaction gas such as nitrogen gas or oxygen gas is evacuated. It can be introduced into the tank 12. Inside the vacuum chamber 12, one main roll 5, two take-up rolls 7a, 7b and two auxiliary rolls 11 are arranged, and from one take-up roll 7a to the other take-up roll 7b, A transparent substrate film 18 is stretched over the main roll 5 and the two auxiliary rolls 11. A vaporized organic material application unit 14 is disposed at a predetermined position around the main roll 5, and this is connected to a vaporizer 13 disposed outside the vacuum chamber 12 via a vaporized organic material introduction pipe 17. It is connected. In this example, the vaporizer 13 is the material vapor generating means, and the vaporized organic material introduction pipe 17 and the vaporized organic material application unit 14 are the coating film forming means. For example, the vaporizer 13 instantaneously vaporizes the liquid material on its wall surface (flash evaporation) and supplies it to the vacuum chamber 12. The temperature of the vaporizer 13 is preferably higher than the boiling point of the liquid material inside and lower than the decomposition temperature of the liquid material. For example, the temperature of the vaporizer is in the range of 10 to 500 ° C, preferably in the range of 20 to 450 ° C, and more preferably in the range of 50 to 400 ° C. The vaporized organic material introduction tube 17 can be heated by a heating means (not shown). Further, the vaporized organic material application unit 14 is connected to a vacuum pump 19 disposed outside the vacuum chamber 12 through a vacuum drawing pipe 15. In this example, the vacuum drawing pipe 15 and the vacuum pump 19 The decompression means of the present invention is configured. An ultraviolet lamp unit 16 is disposed at a position corresponding to between the main roll 5 and the auxiliary roll 11 on the take-up roll 7b side. In this example, the ultraviolet lamp unit 16 is the coating film curing means of the present invention. Although not shown, the ultraviolet lamp unit 16 is arranged in a box under an atmospheric pressure environment and is always cooled by cooling air introduced from the outside. An inorganic material evaporation source 2 is disposed at the bottom of the vacuum chamber 12, and a hearth 3 is disposed thereon. In this example, a pressure gradient plasma gun is used for the plasma generation source 1, and an electron beam generator is used for the evaporation source 2.

  The electron beam generator 2 is composed of, for example, an anode and a tungsten filament-like cathode, and generates heat electrons by energizing and heating the tungsten filament, and a magnetic field generated by applying an acceleration voltage to the anode, The path of the thermal electrons is changed and the gas barrier inorganic thin film layer forming material is irradiated with an electron beam. If such an electron beam generator 2 is used, a gas barrier inorganic thin film layer having high smoothness, adhesion, and gas barrier properties is formed by setting a thermoelectron generation amount and an acceleration voltage suitable for the forming material. It is possible.

  The production of the transparent gas barrier film using this production apparatus is performed, for example, as follows. That is, first, the vapor barrier 13 vaporizes the gas barrier organic thin film layer forming material to generate vapor, which is sent to the vaporized organic material application unit 14 through the vaporized organic material introduction pipe 17. On the other hand, the transparent base film 18 is conveyed from the one winding roll 7 a to the main roll 5 via the auxiliary roll 11. Then, on the main roll 5, the vapor of the gas barrier organic thin film layer forming material is brought into contact with the transparent base film 18 from the vaporized organic material application unit 14 to form a coating film. During the formation of this coating film, the vaporized organic material application part 14 is evacuated by the vacuum pump 19 through the vacuum drawing pipe 15, so that the atmospheric pressure (hereinafter, Is also lower than the pressure in the vacuum chamber 12. Therefore, the coating film can be formed without the vapor diffusing into the vacuum chamber 12. The atmospheric pressure is as described above. Next, the transparent base film 18 on which the coating film is formed is irradiated with ultraviolet rays by the ultraviolet lamp unit 16 while being conveyed to the other winding roll 7b side, whereby the coating film is cured and the gas barrier organic material is cured. A thin film layer is formed. During the conveyance or curing, the pressure in the vacuum chamber 12 is set higher than the vapor pressure of the forming material at the temperature of the transparent substrate film 18 to prevent the formation material from diffusing into the vacuum chamber 12. can do. The pressure in the vacuum chamber 12 is as described above. Thus, the said gas barrier organic thin film layer can be continuously formed on the transparent base film 18, and a transparent gas barrier film can be manufactured continuously. The conveyance speed of the transparent substrate film 18 is not particularly limited, and may be appropriately adjusted so that the gas barrier organic thin film layer has the above-described thickness according to the vapor amount of the forming material.

On the other hand, the gas barrier inorganic thin film layer can be formed, for example, as follows. That is, first, the inside of the vacuum chamber 12 is brought into a high vacuum state at the pressure as described above. Then, the gas barrier inorganic thin film layer forming material in the hearth 3 is irradiated with the electron beam generated by the electron beam generator 2 to physically vaporize the forming material, and the gas barrier inorganic film is formed on the transparent base film 18. A thin film layer is formed. During this formation, the vaporized forming material is activated using plasma generated by a pressure gradient plasma gun 1 arranged separately from the electron beam generator 2, and the transparent substrate film 18 is activated. A gas barrier inorganic thin film layer is formed thereon. In the case of using a reactive gas such as nitrogen gas or oxygen gas, the plasma also acts on the reaction between the vaporized forming material and the reactive gas. The conveying speed of the transparent substrate film 18 is not particularly limited, and may be appropriately adjusted so that the gas barrier inorganic thin film layer has the above-described thickness according to the vapor amount of the forming material. The gas barrier inorganic thin film layer may be formed directly on the transparent base film 18 or may be formed on a previously formed gas barrier organic thin film layer. Further, when the gas barrier organic thin film layer and the gas barrier inorganic thin film layer are alternately formed, for example, when the transparent base film 18 is transported from one winding roll 7a to the other roll 7b, the gas barrier property An organic thin film layer is formed, then the transport direction is reversed, and when the transparent base film 18 is transported from the other roll 7b to the one roll 7a, on the formed gas barrier organic thin film layer. The step of forming the gas barrier inorganic thin film layer may be repeated once or more. Further, in the above process, the order of forming the gas barrier organic thin film layer and the gas barrier inorganic thin film layer may be reversed. First, after forming the gas barrier inorganic thin film layer, the gas barrier organic thin film layer is formed thereon. The order of forming may be used.

  In the formation of the gas barrier inorganic thin film layer, the acceleration voltage of the electron beam generator 2 is preferably in the range of 1 to 20 kV, and the current supplied to the filament is preferably in the range of 10 to 200 mA. . By setting the accelerating voltage and the energization current in the above ranges, the forming material can be suitably vaporized, and the transparent base film 18 is not thermally or mechanically damaged without being transparent. The gas barrier inorganic thin film layer having no defect can be formed on the film 18. More preferably, the acceleration voltage is in the range of 2 to 10 kV, and the energization current is in the range of 30 to 70 mA.

  In the formation of the gas barrier inorganic thin film layer, the discharge current of the pressure gradient plasma gun 1 can be appropriately adjusted according to the type of the forming material, the presence or absence of the use of the reaction gas, etc. It is the range of 110A, Preferably it is the range of 50-110A, More preferably, it is the range of 80-110A. Since the acceleration voltage of the pressure gradient plasma gun 1 varies depending on the pressure in the vacuum chamber 12, it may be adjusted by the discharge current.

  Next, examples of the present invention will be described. However, the present invention is not limited to the following examples. Moreover, each characteristic in the following Example was measured by the following method.

(1) Thickness of gas barrier thin film layer The thickness of the gas barrier organic thin film layer and the gas barrier inorganic thin film layer is determined by embedding the formed gas barrier thin film layer with an epoxy resin, and observing the cross section of the sample with an ultrathin slice method. (The product name: H-800, acceleration voltage 200 kV, manufactured by HITACHI, Inc.)

(2) Water vapor transmission rate The water vapor transmission rate was measured in a 40 ° C, 90% RH environment using a water vapor transmission rate measuring device (trade name PERMATRAN-W, manufactured by MOCON). In addition, since the measuring range of the water vapor transmission rate measuring device is 0.1 g / m ² / day or more, the water vapor transmission rate of the transparent gas barrier film having a lower water vapor transmission rate is as follows. Measured. That is, first, metallic calcium was vapor-deposited with a thickness of 100 nm on the surface of the transparent gas barrier film on the side of the transparent base film using a vacuum vapor deposition apparatus (manufactured by ULVAC). Next, in a vacuum state, aluminum is vapor-deposited with a thickness of 300 μm so as to cover the metal calcium vapor deposition surface from a separate aluminum vapor deposition source, taken out from the vacuum vapor deposition apparatus, and the vapor deposition cup does not immediately expose the vapor deposition surface to the atmosphere. Sealing was performed to obtain a sample for measuring water vapor transmission rate. The obtained water vapor transmission rate measurement sample was exposed in a constant temperature and humidity oven under conditions of 40 ° C. and 90% RH for 24 hours, and the corrosion state of the metallic calcium was observed. The corrosion state of the metallic calcium was observed by taking a picture using a digital camera, an optical microscope, and a laser microscope (manufactured by KEYENCE). The corroded portion was observed as a discoloration or white portion in the image, as the calcium metal reacted with moisture to form calcium hydroxide. The water content that reacted with metallic calcium was calculated from the total area of the corroded portion, and the water vapor permeability was determined.

(3) Visible light transmittance Visible light transmittance was measured using an ultraviolet-visible spectrophotometer (trade name: V-560-DS) manufactured by JASCO Corporation and represented by a transmittance of 550 nm.

A transparent gas barrier film was produced using the production apparatus of FIG. That is, first, a gas barrier organic thin film layer forming material (a mixture of polyethylene diacrylate, stearyl acrylate and a photopolymerization initiator (trade name: Irgacure 907)) was vaporized by the vaporizer 13 at a temperature of 150 ° C. to generate steam. . On the other hand, a transparent substrate film (PET film having a thickness of 100 μm, manufactured by Mitsubishi Polyester Co., Ltd., trade name: Diafoil O400K) 18 is conveyed from the take-up roll 7a to the main roll 5 via the auxiliary roll 11, and an ultimate pressure of 3 Under the conditions of × 10 ⁻⁴ Pa, argon flow rate 40 sccm, coating part pressure 10 Pa, vacuum chamber 12 pressure 300 Pa, transparent substrate film 18 transport speed 0.25 m / min, the generated vapor passes through the vaporized organic material introduction pipe 17. It is introduced into the vaporized organic material application part 14 and is brought into contact with the transparent substrate film 18 to form a coating film. Then, the ultraviolet lamp unit 16 irradiates ultraviolet rays under the condition of an output of 100 W / cm to cure the coating film. A gas barrier organic thin film layer (thickness: 200 nm) is formed on the transparent substrate film 18 and wound on the winding roll 7b. It was. Next, the conveyance direction was reversed, and the transparent base film 18 was conveyed from the winding roll 7 b to the main roll 5 via the auxiliary roll 11. In this state, Hearth 3 under the conditions of ultimate pressure 3 × 10 ⁻⁴ Pa, nitrogen flow rate 20 sccm, argon flow rate 23 sccm, film forming pressure 3 × 10 ⁻² Pa, transparent substrate film 18 transport speed 0.25 / min. The SiO pellet was vaporized by irradiating an electron beam from the electron beam generator 2 at an acceleration voltage of 6 kV and a filament current of 43 mA. Then, plasma is generated from the pressure gradient type plasma gun 1 under the conditions of the acceleration voltage 15A and the discharge current 100A, the vaporized SiO is activated by the plasma, and the reaction between the vaporized SiO and the nitrogen is caused. A transparent gas barrier film was obtained by forming a gas barrier inorganic thin film layer (silicon oxynitride film) on the gas barrier organic thin film layer. The obtained transparent gas barrier film was wound up on a winding roll 7 a via an auxiliary roll 11. The gas barrier inorganic thin film layer had a thickness of 60 nm. Moreover, when the composition of the gas barrier inorganic thin film layer was analyzed by electron spectroscopy for chemical analysis (ESCA), the elemental composition was Si: N: O = 1: 0.53: 1.03. Further, in the obtained transparent gas barrier film, the water vapor transmission rate was 0.03 g / m ² / day, and the visible light transmission rate was 86%.

  According to the method for producing a transparent gas barrier film and the apparatus for producing a transparent gas barrier film of the present invention, it is possible to efficiently produce a transparent gas barrier film having excellent gas barrier properties. The transparent gas barrier film of the present invention includes various display devices (displays) such as organic EL display devices, field emission display devices and liquid crystal display devices, and various electric and electronic devices such as solar cells and electric double layer capacitors. The substrate can be used as a substrate or a sealing material, and its use is not limited, and can be used in all fields in addition to the above-described use.

FIG. 1 is a configuration diagram showing an example of the transparent gas barrier film production apparatus of the present invention.

Explanation of symbols

1 Plasma source (pressure gradient plasma gun)
2 Evaporation source (electron beam generator)
3 Hearth 4 Reflective electrode 5 Main roll 6 Reaction gas introduction pipes 7a and 7b Winding rolls 8 and 9 Plasma focusing coil 10 Plate magnet 11 Auxiliary roll 12 Vacuum tank 13 Vaporizer 14 Vaporized organic material application part 15 Vacuum drawing pipe 16 Ultraviolet irradiation Lamp unit 17 Vaporized organic material introduction pipe 18 Transparent substrate film 19 Vacuum pump

Claims (14)

A step of forming a gas barrier organic thin film layer on the transparent substrate film and a step of forming a gas barrier inorganic thin film layer on the transparent substrate film, wherein both steps are carried out using the same vacuum chamber; A method for producing a transparent gas barrier film, wherein the step of forming the gas barrier organic thin film layer comprises contacting the transparent base film with vapor generated by vaporizing the gas barrier organic thin film layer forming material A coating film forming step for forming the transparent gas barrier organic thin film layer by curing the coating film, and the coating film forming step is performed in the vacuum chamber, In the coating film forming step, the vapor is brought into contact with the transparent substrate film under an atmospheric pressure condition lower than the pressure in the vacuum chamber. The method for producing a transparent gas barrier film according to claim 1, wherein the atmospheric pressure condition lower than the pressure in the vacuum chamber is realized by vacuuming separately from the vacuuming of the vacuum chamber. The method for producing a transparent gas barrier film according to claim 1 or 2, wherein a vapor pressure of the gas barrier organic thin film layer forming material at a temperature of the transparent base film is lower than a pressure in the vacuum chamber. The gas barrier organic thin film layer forming material is an active energy ray curable material, and the coating film curing step is performed by irradiating the coating film with the active energy rays. The manufacturing method of the transparent gas barrier film of description. The method for producing a transparent gas barrier film according to claim 4, wherein the active energy ray is ultraviolet light, and the active energy ray curable material is an ultraviolet curable material.   The method for producing a transparent gas barrier film according to claim 1, wherein the coating film curing step is performed in the vacuum chamber. Two rolls are arranged in the vacuum chamber, and the coating film forming process and the coating film curing process are performed when the transparent substrate film is conveyed from one roll of the two rolls to the other roll. The method for producing a transparent gas barrier film according to claim 6. In the step of forming the gas barrier inorganic thin film layer, the gas barrier inorganic thin film layer forming material is physically vaporized by an evaporation source, and the vaporization is performed using plasma generated by a plasma generation source different from the evaporation source. The method for producing a transparent gas barrier film according to claim 1, wherein the gas barrier inorganic thin film layer is formed by activating the formed material. The method for producing a transparent gas barrier film according to claim 8, wherein the plasma generation source is a pressure gradient plasma gun. The method for producing a transparent gas barrier film according to claim 8 or 9, wherein the evaporation source is an electron beam generator.   One of the gas barrier organic thin film layer and the gas barrier inorganic thin film layer is formed on the transparent base film, and the other layer is formed on the formed layer. The manufacturing method of the transparent gas barrier film in any one of 10. When two rolls are arranged in the vacuum chamber and the transparent base film is transported from one of the two rolls to the other roll, the gas barrier organic thin film layer and the gas barrier inorganic thin film One of the layers is formed, then the transport direction is reversed, and when the transparent substrate film is transported from the other roll to the one roll, the other layer is formed on the formed layer. The method for producing a transparent gas barrier film according to claim 11. A transparent gas barrier film produced by the production method according to claim 1. An apparatus for producing a transparent gas barrier film, comprising: a vacuum chamber; means for forming a gas barrier organic thin film layer on a transparent base film; and means for forming a gas barrier inorganic thin film layer on the transparent base film. The means for forming the gas barrier organic thin film layer includes: material vapor generating means for vaporizing the gas barrier organic thin film layer forming material to generate material vapor; and introducing the material vapor into the vacuum chamber to form the transparent A coating film forming means for contacting the base film to form a coating film; and a coating film curing means for curing the coating film to form the gas barrier organic thin film layer. An apparatus for producing a transparent gas barrier film, comprising a decompression means for bringing the material vapor into contact with the transparent base film under an atmospheric pressure condition lower than a pressure.

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