JP2006321052A - Method for producing gas barrier laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a gas barrier laminate excellent in gas barrier properties and steam barrier properties. <P>SOLUTION: In the manufacturing method of the gas barrier laminate obtained by laminating a metal layer or a metal oxide layer and an overcoat layer on a base material, the metal layer or the metal oxide layer is formed on the base material and its surface is subjected to activation treatment before the overcoat layer is provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  Gas barrier properties, particularly oxygen barrier properties, are often required for packaging materials used for packaging foods and various other articles. Conventionally, various barrier materials have been used for food packaging materials. Specific examples thereof include a packaging material having a barrier layer made of a halogen-containing polymer such as polyvinylidene chloride, a metal foil such as aluminum foil, a packaging material having a barrier layer made of a metal or a metal compound typified by an aluminum deposition layer, A packaging material having a barrier layer made of a vinyl alcohol polymer or an ethylene-vinyl alcohol copolymer is known.

  Moreover, as a use of barrier materials other than food packaging materials, use as a base material of a display element is known, for example. As a base material for a display element, a base material using glass is known, but the glass base material has an excellent water vapor barrier property, but has a drawback of being heavy and easily broken. For this reason, the resin base material which has the outstanding barrier property which can be used as a base material of a display element was calculated | required. However, although the conventional resin base material is light and difficult to break, the barrier property against water vapor and oxygen is not sufficient, and there remains a problem that the performance of the display element deteriorates with time.

As a means for obtaining a barrier material having excellent gas barrier properties, a gas barrier film in which an inorganic oxide layer is provided on the surface of a plastic film by a vapor deposition method has been recently proposed (see Patent Document 1). For the purpose of further improving the gas barrier property and protecting the inorganic oxide layer, a gas barrier film has been proposed in which a layer containing a resin and an inorganic layered compound is overcoated on a plastic film provided with an inorganic oxide layer by vapor deposition. (See Patent Document 2). Also disclosed is a gas barrier laminated film obtained by applying a solution containing a water-soluble polymer and one or more metal alkoxides on a vapor deposition layer made of an inorganic compound provided on a substrate, followed by heating and drying. (See Patent Document 3).
Japanese Patent Laid-Open No. 5-320873 JP-A-11-165369 Japanese Patent Laid-Open No. 7-164591

  In recent years, the required performance of packaging materials in the market has further increased, and a barrier material that is excellent not only in gas barrier properties but also in water vapor barrier properties is being demanded. Specifically, a barrier material having an excellent water vapor barrier property is required not only for the above uses but also for application fields used for the purpose of coating articles. However, conventional barrier materials still have room for improvement in terms of their water vapor barrier properties, and there is a demand for barrier materials that are excellent not only in gas barrier properties but also in water vapor barrier properties. is there.

An object of the present invention is to provide a method for producing a gas barrier laminate excellent in gas barrier properties and water vapor barrier properties.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have completed the present invention. That is, the present invention is a method for producing a gas barrier laminate in which a metal layer or a metal oxide layer and an overcoat layer are laminated on a substrate, wherein the metal layer or the metal oxide layer is formed on the substrate, Provided is a method for producing a gas barrier laminate, wherein an overcoat layer is provided after the surface of the metal layer or metal oxide layer is activated.

  According to the production method of the present invention, a gas barrier laminate having excellent gas barrier properties and water vapor barrier properties can be obtained at a low cost by a simple method. The gas barrier laminate obtained by the production method of the present invention can be used as a packaging material for foods, medicines, medical devices, machine parts, clothing, etc., or as a covering material for various articles that require water vapor barrier properties.

  Hereinafter, embodiments of the present invention will be described. In the following description, specific examples are shown as compounds that express a specific function, but the present invention is not limited thereto. Further, the exemplified materials may be used alone or in combination unless otherwise specified. Unless otherwise specified, “composition” means a solid composition.

  In the present invention, the laminate includes a substrate, a metal layer or metal oxide layer, and an overcoat layer. There is no restriction | limiting in particular as a polymer used for comprising the said base material, For example, Polyolefins, such as polyethylene and a polypropylene; Polycycloolefin; Polyesters, such as a polyethylene terephthalate, a polybutylene terephthalate, a polyethylene naphthalate; Nylon 6, nylon Examples thereof include polyamides such as 66; polyvinyl chloride; polyurethane; and polymers such as polyethersulfone and polycarbonate. Examples of other materials used for constituting the base material include paper. In a preferred embodiment, the substrate is a layer containing a thermoplastic resin. In a more preferred embodiment, the layer containing the thermoplastic resin is a thermoplastic resin film having a thickness of 10 to 1000 μm, more preferably 10 to 100 μm.

  In the present invention, from the viewpoint of the mechanical properties of the laminate, the substrate is preferably at least one layer selected from the group consisting of a polyester layer, a polyamide layer and a polyolefin layer. In the present invention, when the water vapor barrier property of the laminate is particularly important, the substrate is preferably at least one layer selected from the group consisting of a polycycloolefin layer and a polyether sulfone layer.

Examples of the metal layer used in the present invention include an aluminum layer, a titanium layer, a silicon layer, and a silicon nitride layer. Examples of the metal oxide layer include a silicon oxynitride layer, a silicon oxide layer, an aluminum oxide layer, and a silicon oxide layer. -Aluminum oxide composite layers and titanium oxide layers can be mentioned. Among these, a preferable metal layer or metal oxide layer is selected from the group consisting of an aluminum layer, a silicon nitride layer, a silicon oxynitride layer, a silicon oxide layer, an aluminum oxide layer, a silicon oxide-aluminum oxide composite layer, and a titanium oxide layer. At least one layer.
The method for forming the metal layer or metal oxide layer on the substrate is not particularly limited, but physical vapor deposition (PVD) such as vapor deposition, sputtering, ion plating, etc .; various chemical vapor deposition A wet coating method such as a sol-gel method or a polysilazane method. From the viewpoint of the barrier properties of the obtained laminate, physical vapor deposition (PVD) and chemical vapor deposition (CVD) are more preferable. Although the thickness of the metal layer or metal oxide layer to be formed is not particularly limited, from the viewpoint of preventing the occurrence of cracks, the thickness is preferably 0.001 to 1 μm, and 0.01 to 0.5 μm. Is more preferable.

  In the present invention, the surface of the metal layer or metal oxide layer formed on the substrate is subjected to an activation treatment, whereby the surface of the metal layer or metal oxide layer is activated. Bonding at the interface is strengthened, and the resulting laminate is provided with a high gas barrier property and flexibility capable of withstanding deformation.

  Examples of the method for activating the surface of the metal layer or metal oxide layer formed on the substrate include a method of irradiating energy rays and a method of performing an acid treatment. From the viewpoint of preventing productivity and corrosion of the apparatus, a method of irradiating energy rays is more preferable. Examples of energy rays used include ultraviolet rays, electron beams, inert atom ions, oxygen ions, and excited oxygen (molecules or atoms). Among these, ultraviolet rays and electron beams are more preferable from the viewpoint of productivity, and ultraviolet rays are particularly preferable. When irradiating energy rays, it may be in the air, in an inert gas atmosphere such as nitrogen or argon, or in a vacuum atmosphere.

  The time to irradiate the surface of the metal layer or metal oxide layer formed on the substrate with energy rays cannot be defined unconditionally because it depends on the intensity of the energy rays and the atmosphere to irradiate, but the resulting laminate is high. From the viewpoint of gas barrier properties and productivity, 0.1 second to 10 minutes is preferable, and 1 second to 60 seconds is more preferable. When the time is shorter than 0.1 seconds, the surface of the metal layer or metal oxide layer formed on the substrate is not sufficiently activated, and a highly gas barrier laminate may not be obtained. When it is longer than 10 minutes, not only the productivity is deteriorated, but also the substrate may be deteriorated.

As a method for performing the acid treatment, after forming a metal layer or a metal oxide layer on the substrate, it may be exposed to an acid atmosphere, or an aqueous acid solution may be applied to the surface of the metal layer or the metal oxide layer. It may be applied. Examples of the acid used include sulfuric acid, nitric acid, phosphoric acid, acetic acid and the like in addition to hydrogen halides such as hydrogen fluoride and hydrogen chloride. Among these, from the viewpoint of the barrier properties of the obtained laminate, hydrogen halide is more preferable, and hydrogen fluoride is more preferable.
The irradiation with energy rays and the acid treatment may be carried out independently or in combination.

  After activating the surface of the metal layer or metal oxide layer formed on the above-described substrate, an overcoat layer is provided. The overcoat layer can be provided by applying a coating agent containing a polymer having a high film forming property to a metal layer or metal oxide layer that has been activated according to a conventional method, and then drying. The thickness of the overcoat layer is preferably 0.1 μm to 100 μm. If the thickness is less than 0.1 μm, the effects of gas barrier properties and flexibility due to the provision of the overcoat layer may not be sufficiently exhibited, and the upper limit of the thickness is 100 μm in consideration of economy. Is preferred.

In the present invention, the coating agent used for coating the surface of the metal layer or metal oxide layer is not particularly limited, but from the viewpoint of obtaining a laminate having excellent flexibility, a polymer is preferably included. Examples of such polymers include polyvinyl alcohol copolymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers, modified polyvinyl alcohol such as polyvinyl butyral, starch, methyl starch, ethyl starch, chitosan, and amylose. Examples thereof include hydroxyl group-containing polymers including cellulose derivatives such as polysaccharides, hydroxyethyl cellulose, and ethyl cellulose. Polymers that do not contain hydroxyl groups include polyacrylic acid, polymethacrylic acid, polyacrylamide, and polyvinylamine. , Polyethylene glycol, poly (p-styrenesulfonic acid), and the like. These polymers can be used alone or in admixture of two or more.
The degree of polymerization of the polymer used in the present invention is not particularly limited, but the degree of polymerization is preferably 100 to 10,000 from the viewpoint of obtaining a laminate excellent in flexibility, water vapor barrier property and gas barrier property, and 200 -5000 is more preferable, and 300-3000 is particularly preferable.

  When a hydroxyl group-containing polymer is used as a component of the coating agent, a laminate excellent in water vapor barrier properties can be obtained. Among the hydroxyl group-containing polymers, the degree of modification with polyvinyl alcohol and ethylene is preferably 1 to 20 mol%. More preferably, 2-18 mol%, still more preferably 3-15 mol% ethylene-vinyl alcohol copolymer is preferable, and polyvinyl alcohol is particularly preferable.

  In addition, when the above-mentioned polymer containing no hydroxyl group is used as a component of the coating agent, a laminate having excellent gas barrier properties can be obtained. Among them, polyacrylic acid and polymethacrylic acid are more preferable, and polyacrylic acid is preferable. Acid is particularly preferred.

  The coating agent used in the present invention preferably contains a metal alkoxide-derived inorganic compound in addition to the polymer. The metal alkoxide includes silicon alkoxide, one or more metal alkoxides other than silicon alkoxide, an oligomer derived from silicon alkoxide, an oligomer derived from one or more metal alkoxides other than silicon alkoxide, and other than silicon alkoxide and silicon alkoxide. Selected from oligomers derived from one or more metal alkoxides.

  The silicon alkoxide preferably has a chemical structure having one silicon atom and having 2, 3 or 4 alkoxy groups bonded to the silicon atom. Here, the number of alkoxy groups bonded to the silicon atom is more preferably 3 or 4, and particularly preferably 4. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. When the number of alkoxy groups bonded to the silicon atom is 2 or 3, the silicon atom further includes an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group; a phenyl group, a naphthyl group, or the like An aryl group in which a halogen atom such as a chlorine atom or a fluorine atom is bonded. Specific examples of the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, chlorotrimethoxysilane, and preferably tetramethoxysilane. , Tetraethoxysilane.

  As the metal alkoxide other than silicon alkoxide, it has one or more divalent or more, preferably trivalent or tetravalent metal atoms such as titanium, boron, aluminum, zirconium, etc., and this has one or more, preferably two or more, More preferably, a compound having a chemical structure in which three or more alkoxy groups are bonded is preferable. Specific examples of the alkoxy group bonded to the metal atom and the substituents other than the alkoxy group include the same as those exemplified for the silicon alkoxide. Specific examples of the metal alkoxide include alkoxy titanium compounds such as tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, and methyltriisopropoxy titanium; trimethoxyborane, triethoxyborane, triisopropoxyborane, tributoxyborane, and the like Alkoxyboron compounds; alkoxymethoxy compounds such as trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, tributoxyaluminum, diethoxyaluminum chloride; tetraethoxyzirconium, tetraisopropoxyzirconium, methyltriiso Examples include alkoxyzirconium compounds such as propoxyzirconium.

  Moreover, when the coating agent contains a metal alkoxide, a silane coupling agent may be added. Specific examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-chloropropyl. Examples include trimethoxysilane, γ-chloropropyltriethoxysilane, γ-bromopropyltrimethoxysilane, γ-bromopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. Preferred silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-aminopropyltrimethoxy. Examples include silane and γ-aminopropyltriethoxysilane.

  As addition amount of a silane coupling agent, 0.1 mol%-40 mol% are preferable with respect to metal alkoxides other than a silane coupling agent, 0.5 mol%-30 mol% are more preferable, 1 mol%- 20 mol% is most preferred.

  Oligomer derived from silicon alkoxide, oligomer derived from one or more metal alkoxides other than silicon alkoxide, and oligomer derived from one or more metal alkoxides other than silicon alkoxide and silicon alkoxide are silicon alkoxide and silicon It is an oligomer that can be produced by hydrolyzing and condensing one kind of metal alkoxide selected from one or more kinds of metal alkoxides other than alkoxide alone or in combination of two or more kinds.

  Specific examples of oligomers derived from the above silicon alkoxide include tetramethoxysilane dimer or oligomers of trimers or higher, tetraethoxysilane dimer or oligomers of trimers or higher, oligodimethylsiloxane, and the like. Examples thereof include tetramethoxysilane dimers or oligomers of trimers or higher, tetraethoxysilane dimers or oligomers of trimers or higher. The degree of polymerization is not necessarily limited, but is preferably in the range of 2 to 25, and more preferably in the range of 2 to 10.

  Examples of oligomers derived from one or more metal alkoxides other than silicon alkoxide, and oligomers derived from one or more metal alkoxides other than silicon alkoxide and silicon alkoxide include silicon and / or titanium, aluminum, zirconium and the like. 1 or more, preferably a trivalent or tetravalent metal atom (excluding a silicon atom), to which 1 or more, preferably 2 or more, more preferably 3 or more alkoxy groups are bonded. It is preferable that it is an oligomer that can be produced by hydrolyzing and condensing one kind of compound having a chemical structure alone or in combination of two or more kinds according to a known method. Preferable specific examples include tetraisopropoxy titanium dimer or oligomers of the trimer or higher. The degree of polymerization is not necessarily limited, but is preferably in the range of 2 to 25, and more preferably in the range of 2 to 10.

  When the coating agent contains both a polymer and a metal alkoxide-derived inorganic compound, the polymer solution is mixed with the metal alkoxide solution to prepare the coating agent, and the activated metal layer or metal oxide It is preferable to dry after applying the coating agent on the layer. Examples of the solvent used for dissolving the polymer and the metal alkoxide include water, alcohols such as methanol and ethanol, ether compounds such as tetrahydrofuran and diethyl ether, and the like. Among these, water and alcohol are more preferable in consideration of safety and environmental impact.

  When preparing the above-mentioned coating agent, a metal salt, a metal complex, an inorganic layered compound, a crosslinking agent, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, etc., if necessary, within a range not impairing the effects of the present invention. Can be added. Examples of metal salts or metal complexes include metal oxide fine powder produced by wet hydrolysis and polycondensation of the above metal alkoxide compounds; dry hydrolysis, polycondensation or combustion of metal alkoxide compounds. Fine powder of prepared metal oxide; fine silica powder prepared from water glass; inorganic acid metal salt such as carbonate, hydrochloride and nitrate; organic acid metal salt such as oxalate; acetylacetate such as aluminum acetylacetonate Examples thereof include metal complexes such as a nate metal complex, a cyclopentadienyl metal complex, and a cyano metal complex.

  Examples of the inorganic layered compound include montmorillonite, saponite, hectorite, beidellite, stevensite, nontrite, and mica. These may be either natural products or synthetic products.

  In order to strengthen the bond between the metal layer or metal oxide layer and the overcoat layer and improve the barrier property of the laminate, the laminate may be subjected to heat treatment after the overcoat layer is provided. The temperature of the heat treatment is preferably 40 ° C to 300 ° C, more preferably 80 ° C to 250 ° C, and most preferably 120 ° C to 240 ° C. The heat treatment can be performed in air, under a nitrogen atmosphere, under an argon atmosphere, or the like.

  The laminated body manufactured by the method of the present invention can be given additional functions such as impact resistance by laminating other layers on the laminated body. The layer structure at that time includes substrate / metal oxide layer / overcoat layer / adhesive layer / other layer, and other layers / adhesive layer / substrate / metal oxide layer / overcoat layer. Conceivable. For example, when a polyamide film is selected as the other layer to be laminated, it can be laminated on the laminate using a known method such as a dry lamination method.

  Although the thickness of a laminated body is not specifically limited in this invention, It is preferable that it is 10-1000 micrometers, and it is more preferable that it is 10-200 micrometers. If the thickness of the laminate is less than 10 μm, sufficient barrier properties and strength may not be exhibited, and the upper limit of the thickness is preferably 1000 μm from an economical viewpoint.

The laminate produced by the method of the present invention has excellent water vapor barrier properties. Specifically, the degree of water vapor barrier property is preferably 0.5 g / m ² · day or less, more preferably 0.1 g / m ² · day, at a water vapor transmission rate in an atmosphere of 40 ° C.-90% RH. It is as follows. In a more preferred embodiment, the laminate produced by the method of the present invention has an excellent oxygen barrier property, and the degree of the oxygen barrier property is oxygen in a 20 ° C.-85% RH atmosphere. The transmission rate is preferably 0.1 cc / m ² · day · atm or less, and more preferably 0.01 cc / m ² · day · atm or less.

The shape and application of the laminate produced by the method of the present invention are not particularly limited. In a preferred embodiment, this laminate is used as a film, and in a more preferred embodiment, it is used as a barrier film having gas barrier properties and water vapor barrier properties.
Since the laminate produced by the method of the present invention can maintain excellent barrier properties even after being exposed to high humidity conditions and bending conditions, it is possible to take advantage of its properties to package electronic materials and foods. It is particularly useful as a material.

  Since the laminate produced by the method of the present invention has excellent gas barrier properties and water vapor barrier properties, it can be used as a protective film for members that are easily deteriorated by oxygen or water. Can extend the service life. In another preferred embodiment, the laminate produced by the method of the present invention can be used as a protective film for various display media such as EL elements and liquid crystal display elements. For example, the structure of the organic EL element is basically that a transparent electrode, a light emitting layer, a metal electrode, and a back sealant are formed on a translucent substrate, but the laminate manufactured by the present invention is transparent. It can be used as an optical substrate or a back sealant. In addition, the configuration of the liquid crystal display element is basically a configuration having a TFT side base material and a color filter side base material with the liquid crystal sandwiched therebetween, but the laminate manufactured by the present invention can be used as the base material. it can.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. In the following examples, “%” and “part” mean “% by weight” and “part by weight” unless otherwise specified.
The laminates obtained in the examples and comparative examples were evaluated for appearance according to the following method, and the water vapor transmission rate and the oxygen transmission rate were measured.

(1) Evaluation of appearance of laminate The appearance of the laminate was visually evaluated. Evaluation was according to the following criteria.
A: Colorless, transparent, free of bumps and excellent in appearance.
○: Slightly opaque and / or irregularities are observed, but there is no major problem in appearance.
X: Opaque and / or bumpy and poor in appearance.

(2) Water vapor transmission rate Two samples (12 cm × 12 cm square) were prepared from the laminate obtained by the above method. Using the water vapor transmission rate measuring device ("MOCON PERMATRAN-3 / 33" manufactured by Modern Control Co., Ltd.), the water vapor transmission rate was measured for each of the two samples under the conditions of a temperature of 40 ° C and a humidity of 90% RH. From the average value, the water vapor transmission rate (unit: g / m ² · day) of the laminate was determined.

(3) Oxygen transmission rate Two samples (12 cm × 12 cm squares) were produced from the laminate obtained by the above method. Using the oxygen permeation rate measuring device (“MOCON OX-TRAN 2/20” manufactured by Modern Control Co., Ltd.), the 10 samples were subjected to conditions of a temperature of 20 ° C., a humidity of 85% RH, and an oxygen pressure of 2.5 kgf / cm ² . Then, the oxygen permeation rate was measured, and the oxygen permeation rate (unit: cc / m ² · day · atm) of the laminate was determined from the average value thereof.

<Reference Example 1>
Using a biaxially stretched polyester film “OPET” (trade name “Lumirror”, thickness 12 μm, manufactured by Toray Industries, Inc.) as a base material, this is mounted in a vacuum chamber of a sputtering apparatus, and the inside of the chamber is on the order of 10 ⁻⁴ Pa. Then, vacuum was applied, 0.04 Pa was introduced as a discharge gas at a partial pressure, and oxygen was introduced as a reaction gas at a partial pressure of 0.04 Pa. When the pressure was stabilized, discharge was started, plasma was generated on the Si target, and a sputtering process was started. When the process was stabilized, the shutter was opened and a silicon oxide film was formed on the OPET. When the film thickness reached 50 nm, the shutter was closed to finish the film formation, and a laminate (OPET / silicon oxide) having a silicon oxide film with a thickness of 50 nm was produced.

<Reference Example 2>
A biaxially stretched polyester film “OPET” (trade name “Lumirror”, thickness 12 μm, manufactured by Toray Industries, Inc.) is used as a base material, and this is mounted in a vacuum tank of a vacuum deposition apparatus, and the inside of the tank is 10 ⁻⁵ Torr level. Vacuum was applied until Al2O3 was evaporated by electron beam heating of 15 KW, and an aluminum oxide film was formed on OPET to a thickness of 50 nm. A laminate (OPET / aluminum oxide) having an aluminum oxide film having a thickness of 50 nm was produced.

<Example 1>
With the silicon oxide side of the laminate (OPET / silicon oxide) produced in Reference Example 1 being the ultraviolet irradiation side, an ultraviolet irradiation device (VUV irradiation device: manufactured by Ushio Electric Co., Ltd., lamp house: H0017, lamp unit: UEM- 20-172, lighting power source: B0005, 5-inch chamber: P0032, center wavelength: 172 nm, half-value width: 14 nm, radiation intensity: 10 mW / cm ² ). Ultraviolet irradiation was performed under reduced pressure (about 2 Torr) for 10 seconds, and an overcoat was applied immediately after release to the atmosphere.

  Polyvinyl alcohol (trade name “Poval PVA-105” manufactured by Kuraray Co., Ltd.) having a viscosity average polymerization degree of 500 and a saponification degree of 98.5 mol% as a hydroxyl group-containing polymer, and tetramethoxysilane (Shin-Etsu Chemical Co., Ltd.) as a metal alkoxide. Used). 360.0 parts by weight of distilled water was added to 40.0 parts by weight of polyvinyl alcohol and dissolved by heating at 90 ° C. for 1 hour to prepare a solution (S1) containing polyvinyl alcohol having a solid content concentration of 10% by weight (first step). .

  Next, after dissolving 146.7 parts by weight of tetramethoxysilane in 146.7 parts by weight of methanol, 5.8 parts by weight of distilled water and 24.0 parts by weight of 0.1N (normal) -hydrochloric acid were added to prepare a sol. did. The obtained sol was reacted at 10 ° C. for 60 minutes with stirring to prepare a solution (S2) (second step).

After diluting the solution (S2) obtained by the above method with 175.5 parts by weight of distilled water, the diluted solution is quickly added to the solution (S1) prepared in the first step with stirring to obtain a solution. (S3) was prepared (third step). The pH of the solution (S3) was 2.9. The solution (S3) was allowed to stand for 30 minutes in an atmosphere at 25 ° C. after the preparation.
A part of the solution (S3) was used, and it was confirmed separately that this formed a solid overcoat layer by removing the solvent (fourth step). The content of polyvinyl alcohol in the formed overcoat layer was 40% by weight, and the content of silicon oxide was 60% by weight.

On the silicon oxide surface of the activated laminate (OPET / silicon oxide), the solution (S3) after standing was applied by a bar coater so that the thickness after drying was 1 μm. The laminated body after coating was dried at 120 ° C. for 5 minutes, and then heat treated at 200 ° C. for 30 seconds. In this way, a laminate (OPET (12 μm) / silicon oxide (50 nm) / overcoat layer (1 μm)) having a colorless and transparent coating film was obtained.
The appearance of the laminate is good (evaluation: ◎ judgment), the water vapor transmission rate is 0.1 g / m ² · day or less of the measurement limit, and the oxygen transmission rate is also 0.01 cc / m ² · day · which is the measurement limit. It was below atm.

<Example 2>
With the aluminum oxide side of the laminate (OPET / aluminum oxide) produced in Reference Example 2 being the ultraviolet irradiation side, an ultraviolet irradiation device (VUV irradiation device: manufactured by Ushio Electric Co., Ltd., lamp house: H0017, lamp unit: UEM- 20-172, lighting power source: B0005, 5-inch chamber: P0032, center wavelength: 172 nm, half-value width: 14 nm, radiation intensity: 10 mW / cm ² ). Ultraviolet irradiation was performed under reduced pressure (about 2 Torr) for 10 seconds, and an overcoat was applied immediately after release to the atmosphere.

On the aluminum oxide surface of the activated laminate (OPET / aluminum oxide), the solution (S3) of Example 1 was applied with a bar coater so that the thickness after drying was 1 μm. The laminated body after coating was dried at 120 ° C. for 5 minutes, and then heat treated at 200 ° C. for 30 seconds. In this way, a laminate (OPET (12 μm) / aluminum oxide (50 nm) / overcoat layer (1 μm)) having a colorless and transparent coating film was obtained.
The appearance of the laminate is good (evaluation: ◎ judgment), the water vapor transmission rate is 0.1 g / m ² · day or less of the measurement limit, and the oxygen transmission rate is also 0.01 cc / m ² · day · which is the measurement limit. It was below atm.

<Comparative Example 1>
A laminate having a colorless and transparent coating film (OPET (12 μm) / silicon oxide (50 nm) / overcoat layer (1 μm)) in the same manner as in Example 1, except that the activation treatment was not performed in Example 1. Got. Using the laminate obtained in this comparative example, the water vapor transmission rate and the oxygen transmission rate were measured. The appearance of the laminate in this comparative example was good (evaluation: 判定 judgment), the water vapor transmission rate was 0.3 g / m ² · day, and the oxygen transmission rate was 0.02 cc / m ² · day · atm. It was.

Claims (9)

A method for producing a gas barrier laminate in which a metal layer or a metal oxide layer and an overcoat layer are laminated on a substrate, wherein the metal layer or the metal oxide layer is formed on the substrate, and the metal layer or the metal oxide A method for producing a gas barrier laminate comprising providing an overcoat layer after activating the surface of a physical layer. The manufacturing method of the gas-barrier laminated body of Claim 1 which activates the surface of a metal layer or a metal oxide layer by irradiating an energy ray. The manufacturing method of the gas-barrier laminated body of Claim 1 which activates the surface of a metal layer or a metal oxide layer by giving an acid treatment. The method for producing a gas barrier laminate according to any one of claims 1 to 3, wherein the substrate is at least one layer selected from the group consisting of a polyester layer, a polyamide layer, and a polyolefin layer. The method for producing a gas barrier laminate according to any one of claims 1 to 3, wherein the substrate is at least one layer selected from the group consisting of a polycycloolefin layer and a polyether sulfone layer. The metal layer or the metal oxide layer is at least one layer selected from the group consisting of an aluminum layer, a silicon nitride layer, a silicon oxynitride layer, a silicon oxide layer, an aluminum oxide layer, a silicon oxide-aluminum oxide composite layer, and a titanium oxide layer. The method for producing a gas barrier laminate according to any one of claims 1 to 5. The method for producing a gas barrier laminate according to any one of claims 1 to 6, wherein the overcoat layer is a composition containing a hydroxyl group-containing polymer. The method for producing a gas barrier laminate according to any one of claims 1 to 7, wherein the overcoat layer is a composition containing an inorganic compound derived from a metal alkoxide. A gas barrier laminate produced by the production method according to claim 1 and having a water vapor transmission rate of 0.1 g / m ² · day or less in a 40 ° C.-90% RH atmosphere.