Gas barrier composition and laminate

Abstract

The present invention provides a gas barrier composition that can form a coating film with excellent gas barrier properties and interlayer adhesion (peel strength), and that exhibits excellent storage stability at low, room, and high temperatures. [Solution] A gas barrier composition comprising a polyalcohol polymer, a polycarboxylic acid polymer, an inorganic layered compound, and water, wherein the polyalcohol polymer comprises at least one selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, and ethylene vinyl alcohol copolymer, the polycarboxylic acid polymer has a weight-average molecular weight of 4500 or more and 11000 or less, and the content of the polycarboxylic acid polymer is 0.5 parts by mass or more and 6 parts by mass or less per 100 parts by mass of the inorganic layered compound.

Description

[Technical Field] 【0001】 The present invention relates to a gas barrier composition and a laminate. [Background technology] 【0002】 Conventionally, in packaging bags used for food, medical, and other applications, various gas barrier layers have been considered to block gases such as oxygen and water vapor. 【0003】 For example, Patent Document 1 discloses an aqueous layered silicate dispersion obtained from a layered silicate, a protective colloid, and an aqueous dispersant, which is suitable for homogeneously mixing the layered silicate into a coating composition that can be diluted with water, characterized in that the protective colloid is poly(propylene oxide) which does not have hydrophobic end groups, has an average of one or more hydroxyl groups per molecule, and may contain up to 40% by weight of -CH2-CH2-O- units. [Prior art documents] [Patent Documents] 【0004】 [Patent Document 1] Special Publication No. 01-503628 [Overview of the Initiative] [Problems that the invention aims to solve] 【0005】 Patent Document 1 uses an ionic protective colloid (for example, tetrasodium pyrophosphate) to disperse the layered silicate. 【0006】 Conventional gas barrier compositions were capable of forming coatings with excellent gas barrier properties and interlayer adhesion (peel strength). 【0007】 On the other hand, when transporting gas barrier compositions during the summer or winter, the surrounding environment is expected to be either very hot or very cold, so storage stability at low, normal, and high temperatures is required. Conventional gas barrier compositions have not adequately considered storage stability unaffected by ambient temperature, leaving room for further improvement. 【0008】 Therefore, in view of the above-mentioned problems, the present invention provides a gas barrier composition that can form a coating film with excellent gas barrier properties and interlayer adhesion (peel strength), and that exhibits excellent storage stability at all temperatures, including low temperatures (5°C), room temperatures (23°C), and high temperatures (60°C). [Means for solving the problem] 【0009】 The present inventors have found that all of the above problems can be solved by comprising a polyalcohol-based polymer, a polycarboxylic acid-based polymer, an inorganic layered compound, and water, wherein the polyalcohol-based polymer comprises at least one selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, and ethylene vinyl alcohol copolymer, and the weight-average molecular weight and content of the polycarboxylic acid-based polymer are within a specific range. 【0010】 In other words, the present invention is a gas barrier composition comprising a polyalcohol-based polymer, a polycarboxylic acid-based polymer, an inorganic layered compound, and water, wherein the polyalcohol-based polymer comprises at least one selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, and ethylene vinyl alcohol copolymer, the polycarboxylic acid-based polymer has a weight-average molecular weight of 4500 to 11000, and the content of the polycarboxylic acid-based polymer is 0.5 to 6 parts by mass per 100 parts by mass of the inorganic layered compound. Furthermore, in the gas barrier composition of the present invention, the content of the inorganic layered compound is preferably 10 parts by mass or more per 100 parts by mass of the polyalcohol-based polymer. Furthermore, in the gas barrier composition of the present invention, the content of the polycarboxylic acid polymer is preferably 1 part by mass or more and 5 parts by mass or less per 100 parts by mass of the inorganic layered compound. Furthermore, in the gas barrier composition of the present invention, it is preferable that the polycarboxylic acid polymer has a weight-average molecular weight of 5,000 or more and 10,000 or less. Furthermore, in the gas barrier composition of the present invention, the content of the inorganic layered compound is preferably 17.5 parts by mass or more per 100 parts by mass of the polyalcohol-based polymer. Furthermore, in the gas barrier composition of the present invention, the inorganic layered compound is preferably a layered silicate compound. Furthermore, the present invention also includes a laminate comprising a coating layer formed from the gas barrier composition of the present invention. [Effects of the Invention] 【0011】 The present invention provides a gas barrier composition that can form a coating film with excellent gas barrier properties and interlayer adhesion (peel strength), and that exhibits excellent storage stability at low, room, and high temperatures. [Modes for carrying out the invention] 【0012】 <Gas barrier composition> The gas barrier composition of the present invention comprises a polyalcohol-based polymer, a polycarboxylic acid-based polymer, an inorganic layered compound, and water. The polyalcohol-based polymer comprises at least one selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, and ethylene vinyl alcohol copolymer. The polycarboxylic acid-based polymer has a weight-average molecular weight of 4500 to 11000. The content of the polycarboxylic acid-based polymer is 0.5 to 6 parts by mass per 100 parts by mass of the inorganic layered compound. 【0013】 (Polyalcohol-based polymer) The gas barrier composition of the present invention comprises a polyalcohol-based polymer. 【0014】 The above polyalcohol-based polymer contains at least one selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, and ethylene vinyl alcohol copolymer. 【0015】 As the above polyvinyl alcohol, the degree of polymerization is preferably 100 to 5000, more preferably 500 to 3000. In addition, the saponification degree of the above polyvinyl alcohol is preferably 60 mol% or more, more preferably 75 mol% or more. In this specification, the saponification degree can be determined by the following formula. (Formula) Saponification degree = (number of hydroxyl groups) / {(number of hydroxyl groups) + (number of acetyl groups)} × 100 [mol%] In the case of commercially available products, numerical values in catalogs etc. may be referred to. 【0016】 Examples of the above modified polyvinyl alcohol include butenediol-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, carboxylic acid-modified polyvinyl alcohol, amino group-modified polyvinyl alcohol, etc. 【0017】 As the above ethylene vinyl alcohol copolymer, those obtained by saponifying an ethylene-vinyl acetate copolymer are preferred. 【0018】 The above ethylene vinyl alcohol copolymer preferably has an ethylene content of 1 to 60 mol%. When the above ethylene content is less than 1 mol%, the water resistance, moisture resistance decrease, and the gas barrier property under high humidity may be impaired, and the stress cracking resistance may decrease. In addition, when the above ethylene content is greater than 60 mol%, although the water resistance and moisture resistance are improved, the gas barrier property may decrease. 【0019】 The above-mentioned ethylene vinyl alcohol copolymer preferably has a degree of saponification of 95 mol% or more. If the degree of saponification is less than 95 mol%, gas barrier properties and oil resistance may also decrease. 【0020】 The content of the polyalcohol-based polymer is preferably 50% to 95% by mass, and more preferably 60% to 90% by mass, relative to the total solid content of the gas barrier composition of the present invention. 【0021】 (Polycarboxylic acid polymers) The gas barrier composition of the present invention comprises a polycarboxylic acid polymer. 【0022】 Examples of the polycarboxylic acid polymers mentioned above include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyitaconic acid, acrylic acid-methacrylic acid copolymers, acrylic acid-maleic acid copolymers, and their salts. Examples of the salts mentioned above include sodium salts and ammonium salts. Among these, polyacrylic acid and / or its sodium salts and ammonium salts are preferred. 【0023】 The above polycarboxylic acid polymers have a weight-average molecular weight of 4500 to 11000. From the viewpoint of suitably dispersing the inorganic layered compound and suitably imparting storage stability, it is preferable that the weight-average molecular weight is 5,000 or more and 10,000 or less. In this specification, "weight-average molecular weight" can be measured using GPC (gel permeation chromatography). For commercially available products, values ​​from catalogs or other sources may be referenced. 【0024】 The content of the above polycarboxylic acid polymer is 0.5 parts by mass or more and 6 parts by mass or less per 100 parts by mass of the inorganic layered compound. From the viewpoint of suitably dispersing the inorganic layered compound and suitably imparting storage stability, it is preferable that the amount of the inorganic layered compound is 1 part by mass or more and 5 parts by mass or less per 100 parts by mass of the inorganic layered compound. 【0025】 The content of the polycarboxylic acid polymer relative to the polyalcohol polymer should be within a range that satisfies both the numerical range for the content of the polycarboxylic acid polymer relative to the inorganic layered compound and the numerical range for the content of the inorganic layered compound relative to the polyalcohol polymer, which will be described later. 【0026】 (Inorganic layered compounds) The gas barrier composition of the present invention comprises an inorganic layered compound. 【0027】 As the inorganic layered compounds mentioned above, inorganic layered compounds that swell and cleave in a dispersion medium can be used. For example, kaolinites with a 1:1 phyllosilicate structure, antigorites belonging to the Jamonite group, smectites with a 2:1 structure depending on the number of interlayer cations, vermiculites with a 2:1 structure of hydrated silicate minerals, and micas can be used. 【0028】 Specific examples of the above inorganic layered compounds include kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beiderite, hectorite, saponite, souconite, stevensite, tetrasilyl mica, sodium teniolite, muscovite, margalite, talc, vermiculite, phlogopite, xanthophyllite, chlorite, etc., which may be natural or synthetic. Additionally, flake-like silica can also be used. These can be used individually, or two or more can be used in combination. Among these, layered silicate compounds are preferred from the viewpoint of gas barrier properties and coating properties, and montmorillonite is more preferred. 【0029】 The content of the inorganic layered compound is preferably 5% by mass or more and 50% by mass or less, relative to the total solid content of the gas barrier composition of the present invention, and more preferably 10% by mass or more and 40% by mass or less. 【0030】 The content of the inorganic layered compound is preferably 10% by mass or more per 100 parts by mass of the polyalcohol-based polymer, more preferably 17.5 parts by mass or more, even more preferably 20 parts by mass or more, particularly preferably 25 parts by mass or more, and most preferably 30 parts by mass or more, from the viewpoint of suitably imparting gas barrier properties (especially under the conditions of 25°C / 70%RH). 【0031】 (water) The gas barrier composition of the present invention contains water. For the water used, for example, purified water, distilled water, ion-exchanged water, RO water, etc., can be used. 【0032】 The water content is preferably 30% by mass or more and 97% by mass or less, relative to the total mass of the gas barrier composition of the present invention. 【0033】 (alcohol) The gas barrier composition of the present invention preferably contains an alcohol. 【0034】 Examples of the alcohols mentioned above include methanol, ethanol, propanol, butanol, ethylene glycol, and propylene glycol. These can be used individually, or two or more can be used in combination. In particular, from the viewpoint of drying properties and safety, it is preferable to include at least one selected from the group consisting of ethanol, n-propyl alcohol, and isopropyl alcohol. 【0035】 The alcohol content is preferably 0% by mass or more and 50% by mass or less based on the total mass of the gas barrier composition of the present invention. Furthermore, from the viewpoint of the drying properties of the gas barrier composition, the alcohol content is more preferably 10% by mass or more based on the total mass of the gas barrier composition of the present invention. 【0036】 (others) The gas barrier composition of the present invention may optionally contain additives such as leveling agents, defoaming agents, antiblocking agents such as wax and silica, release agents such as metal soaps and amides, ultraviolet absorbers, and antistatic agents. 【0037】 The amount of each additive can be determined appropriately depending on the type of additive. 【0038】 (Method for producing a gas barrier composition) The method for producing the gas barrier composition of the present invention is not particularly limited, and the above materials may be mixed and dispersed using known stirring or dispersion devices. 【0039】 <Laminate> The laminate of the present invention includes a coating layer formed from the gas barrier composition of the present invention. 【0040】 The above-mentioned coating layer can be formed by applying the gas barrier composition using conventional methods such as a roll coating method using a gravure cylinder, a doctor knife method, an air knife / nozzle coating method, a bar coating method, a spray coating method, a dip coating method, or a coating method combining these methods, and then drying it. Any known drying method may be used. 【0041】 From the viewpoint of thinning the laminate, the amount of the above gas barrier composition to be applied is 2 g / m² after drying. 2 Preferably, it is 1 g / m 2 The following is more preferable: Furthermore, from the viewpoint of adequately imparting gas barrier properties to the laminate, the amount of the gas barrier composition applied after drying should be 0.1 g / m². 2 Preferably, it is 0.2 g / m 2 It is more preferable that the above conditions are met. 【0042】 The laminate of the present invention may optionally have a sealant layer, an adhesive layer, and a substrate layer. In this case, the layers are laminated in the following order: sealant layer, coating layer formed from the gas barrier composition, adhesive layer, and substrate layer. 【0043】 (Sealant layer) The sealant layer described above is composed of a resin that can be melted and fused by heat. Examples of such resins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, and ethylene-propylene copolymer. These may be used individually or in combination of two or more types. 【0044】 The thickness of the sealant layer may be, for example, 10 to 100 μm, or 15 to 50 μm. 【0045】 (adhesive layer) The adhesive layer described above can be formed by applying and drying a solvent-free, solvent-based, aqueous, or heat-melt type adhesive, which mainly contains polyurethane, polyester urethane, polyester, polycarbonate polyurethane, polyamide, epoxy resin, polyacrylic acid, polymethacrylic acid, polyethyleneimine, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, polyvinyl acetate, polyolefin, modified polyolefin, polybutadiene, wax, casein, or a mixture thereof. 【0046】 The amount of adhesive applied after drying to form the above adhesive layer is 0.1 to 5 g / m². 2 It is preferable to apply it in such a manner. The adhesive used to form the above adhesive layer should have a dry application rate of 0.5 to 3 g / m². 2 It is preferable that it be so. 【0047】 (base material layer) Examples of the above-mentioned base material layers include various plastic films made of polyolefins, modified polyolefins, polyesters, nylons, polystyrenes, etc., which have been conventionally used in flexible packaging, and composite films made of two or more of these materials. The above-mentioned substrate layer is preferably subjected to metal deposition treatment, corona discharge treatment, or surface coating treatment. 【0048】 The thickness of the above-mentioned substrate layer is not particularly limited, but is preferably 0.5 to 1000 μm, more preferably 1 to 500 μm, even more preferably 1 to 100 μm, and particularly preferably 1 to 50 μm. 【0049】 The above metal deposition process can be carried out using vacuum processes such as vacuum deposition, sputtering, and plasma vapor deposition (PVD / CVD) to deposit inorganic oxides. Examples of the inorganic oxides mentioned above include oxides of metals such as silicon, aluminum, zinc, tin, iron, and manganese, and oxides of inorganic compounds containing one or more of these metals. 【0050】 The thickness of the deposited layer formed by the above metal deposition treatment is not particularly limited, but is preferably 0.1 to 500 nm, and more preferably 0.5 to 40 nm. 【0051】 (others) The laminate of the present invention may optionally have a printed layer. The above-mentioned printed layer is a layer composed of ink containing pigments, binder resins, solvents, etc., on which characters, images, etc., are formed. The printed layer may be formed, for example, on the sealant layer or the substrate layer. 【0052】 The above inks should be selected from publicly available options, taking into consideration factors such as color tone and other design aspects, adhesion, and safety for use in food containers. 【0053】 The above-mentioned printed layer can be formed by printing the above-mentioned ink using gravure printing, offset printing, gravure offset printing, flexographic printing, inkjet printing, or the like. The thickness of the printed layer is preferably, for example, 0.1 to 2.0 μm. 【0054】 The laminate of the present invention may optionally have an anchor coat layer. The above-mentioned anchor coating layer can be obtained, for example, by applying and drying an anchor coating agent containing a resin and a solvent. 【0055】 Examples of resins included in anchor coating agents include polyester resins, polyether resins, polyurethane resins, polyethyleneimine resins, isocyanate resins, butadiene resins, acrylic resins, ethylene vinyl alcohol resins, vinyl-modified resins, epoxy resins, modified styrene resins, modified silicone resins, alkyl titanates, water-soluble polymers, and water-suspendable polymers. These may be used individually or in combination of two or more types. 【0056】 Furthermore, the resin included in the above-mentioned anchor coating agent may be a two-component curing resin consisting of a main component and a hardener, and it is more preferable to use a polyester resin, polyurethane resin, or acrylic resin as the main component. The curing agent is not particularly limited, and general curing agents such as isocyanate-based and epoxy-based curing agents can be used. 【0057】 From the viewpoint of adhesion, the resin contained in the above anchor coating agent preferably includes at least one selected from the group consisting of polyester resins, polyether resins, polyurethane resins, polyethyleneimine resins, water-soluble polymers, and water-suspended polymers. 【0058】 The solvent contained in the above anchor coating agent is not limited as long as it can dissolve the resin contained in the above anchor coating agent. For example, methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxolane, tetrahydrofuran, cyclohexanone, acetone, normal propanol, isopropanol, ethanol, water, etc. may be mentioned. These may be used alone or in combination of two or more. 【0059】 The solvent contained in the above anchor coating agent preferably contains 80 to 99% by mass based on the total amount of the anchor coating agent. 【0060】 As the coating method of the above anchor coating agent, roll coating method using a gravure cylinder or the like, doctor knife method, air knife / nozzle coating method, bar coating method, spray coating method, dip coating method, and coating methods combining these methods, etc., ordinary methods can be used. 【0061】 Regarding the coating amount of the above anchor coating agent, from the viewpoint of improving the adhesion between the above sealant layer and the coating layer of the gas barrier composition described later, the coating amount after drying is 2 g / m 2 The following is preferable, 1 g / m 2 The following is more preferable, 0.5 g / m 2 The following is even more preferable. In addition, as the drying method, a known method may be appropriately used. 【0062】 In this specification, the following matters are disclosed. 【0063】 The present disclosure (1) is a gas barrier composition comprising a polyalcohol polymer, a polycarboxylic acid polymer, an inorganic layered compound, and water, wherein the polyalcohol polymer comprises at least one selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, and ethylene vinyl alcohol copolymer, the polycarboxylic acid polymer has a weight-average molecular weight of 4500 or more and 11000 or less, and the content of the polycarboxylic acid polymer is 0.5 parts by mass or more and 6 parts by mass or less per 100 parts by mass of the inorganic layered compound. Disclosure (2) is the gas barrier composition according to Disclosure (1), wherein the inorganic layered compound is contained in an amount of 10 parts by mass or more per 100 parts by mass of the polyalcohol-based polymer. Disclosure (3) is a gas barrier composition according to Disclosure (1) or (2), wherein the content of the polycarboxylic acid polymer is 1 part by mass or more and 5 parts by mass or less per 100 parts by mass of the inorganic layered compound. Disclosure (4) is a gas barrier composition according to any one of Disclosures (1) to (3), wherein the polycarboxylic acid polymer has a weight-average molecular weight of 5,000 or more and 10,000 or less. Disclosure (5) is a gas barrier composition according to any one of Disclosures (1) to (4), wherein the inorganic layered compound is a layered silicate compound. Disclosure (6) is a gas barrier composition according to any one of Disclosures (1) to (5), wherein the content of the inorganic layered compound is 17.5 parts by mass or more per 100 parts by mass of the polyalcohol-based polymer. Disclosure (7) is a laminate comprising a coating layer formed from any of the gas barrier compositions described in Disclosure (1) to (6). [Examples] 【0064】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "mass%" and "parts" means "parts by mass". 【0065】 The materials used in the examples and comparative examples are as follows: 【0066】 (Polyalcohol-based polymer) Kuraray Poval 5-98 (polyvinyl alcohol, saponification degree 98.0-99.0 mol%, manufactured by Kuraray Co., Ltd.) Nichigo G Polymer AZF8035Q (butenediol-modified polyvinyl alcohol, saponification degree ≥ 98.0 mol%, manufactured by Mitsubishi Chemical Corporation) Exceval AQ-4104 (ethylene vinyl alcohol copolymer, saponification degree 98.0-99.0 mol%, manufactured by Kuraray Co., Ltd.) The degree of saponification was determined by referring to the values ​​listed in the catalog. (Polycarboxylic acid polymers) Aron A-30SL (ammonium polyacrylate, weight-average molecular weight 6000, solids content 40% by mass, manufactured by Toagosei Co., Ltd.) Sharol AH-103PC (ammonium polyacrylate, weight-average molecular weight 10,000, solids content 44% by mass, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Aron A-10SL (polyacrylic acid, weight-average molecular weight 5000, solids content 40% by mass, manufactured by Toagosei Co., Ltd.) Aron T-50 (sodium polyacrylate, weight-average molecular weight 6000, solids content 43% by mass, manufactured by Toagosei Co., Ltd.) Aron A-30 (ammonium polyacrylate, weight-average molecular weight 100,000, solids content 30% by mass, manufactured by Toagosei Co., Ltd.) Sodium pyrophosphate (industrial grade, 100% solids by mass, manufactured by Yoneyama Chemical Industries Co., Ltd.) Sodium tripolyphosphate (industrial grade, 100% solids by mass, manufactured by Yoneyama Chemical Industries Co., Ltd.) The weight-average molecular weight was determined by referring to the values ​​listed in the catalog. (Inorganic layered compounds) Kunipia F (montmorillonite, manufactured by Kunimine Industries Co., Ltd.) 【0067】 <Preparation of aqueous solutions of polyalcohol-based polymers> (Polyalcohol-based polymer aqueous solution 1) 15 parts by mass of Kurarepoval 5-98 was added to 85 parts by mass of purified water while stirring, and dissolved by stirring at 90°C to obtain an aqueous solution of polyalcohol-based polymer 1 with a solid content of 15% by mass. 【0068】 (Polyalcohol-based polymer aqueous solution 2) 15 parts by mass of Nichigo G Polymer AZF8035Q was added to 85 parts by mass of purified water while stirring, and dissolved by stirring at 90°C to obtain an aqueous solution of polyalcohol-based polymer 2 with a solid content of 15% by mass. 【0069】 (Polyalcohol-based polymer aqueous solution 3) 15 parts by mass of Exceval AQ-4104 was added to 55 parts by mass of purified water while stirring, dissolved by stirring at 95°C, and then diluted with a mixed solution of purified water / NPA (n-propyl alcohol) = 1 / 2 to obtain an aqueous solution of polyalcohol-based polymer 3 with a solid content of 15% by mass. 【0070】 <Preparation of inorganic layered compound dispersion> (Inorganic layered compound dispersion 1) 0.3 parts by mass of Aron A-30SL and 4.0 parts by mass of Kunipia F were added to 95.7 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion liquid 1. 【0071】 (Inorganic layered compound dispersion 2) 0.1 parts by mass of Aron A-30SL and 4.0 parts by mass of Kunipia F were added to 95.9 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion liquid 2. 【0072】 (Inorganic layered compound dispersion 3) 0.5 parts by mass of Aron A-30SL and 4.0 parts by mass of Kunipia F were added to 95.5 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion liquid 3. 【0073】 (Inorganic layered compound dispersion 4) 0.27 parts by mass of Sharol AH-103PC and 4.0 parts by mass of Kunipia F were added to 95.73 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion liquid 4. 【0074】 (Inorganic layered compound dispersion 5) 0.3 parts by mass of Aron A-10SL and 4.0 parts by mass of Kunipia F were added to 95.7 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion liquid 5. 【0075】 (Inorganic layered compound dispersion 6) 0.28 parts by mass of Aron T-50 and 4.0 parts by mass of Kunipia F were added to 95.72 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion liquid 6. 【0076】 (Inorganic layered compound dispersion 7) 4.0 parts by mass of Kunipia F was added to 96.0 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion liquid 7. 【0077】 (Inorganic layered compound dispersion 8) 0.01 parts by mass of Aron A-30SL and 4.0 parts by mass of Kunipia F were added to 95.99 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion 8. 【0078】 (Inorganic layered compound dispersion 9) 1.0 part by mass of Aron A-30SL and 4.0 parts by mass of Kunipia F were added to 95.0 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion liquid 9. 【0079】 (Inorganic layered compound dispersion 10) 0.4 parts by mass of Aron A-30 and 4.0 parts by mass of Kunipia F were added to 95.6 parts by mass of purified water while stirring, and then thoroughly dispersed in a high-pressure dispersion device at a pressure of 50 MPa to obtain inorganic layered compound dispersion liquid 10. 【0080】 (Inorganic layered compound dispersion 11) 0.12 parts by mass of sodium pyrophosphate and 4.0 parts by mass of Kunipia F were added to 95.88 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain an inorganic layered compound dispersion 11. 【0081】 (Inorganic layered compound dispersion 12) 0.12 parts by mass of sodium tripolyphosphate and 4.0 parts by mass of Kunipia F were added to 95.6 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion 12. 【0082】 (Inorganic layered compound dispersion 13) 0.05 parts by mass of Aron A-30SL and 4.0 parts by mass of Kunipia F were added to 95.95 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain an inorganic layered compound dispersion 13. 【0083】 (Inorganic layered compound dispersion 14) 0.6 parts by mass of Aron A-30SL and 4.0 parts by mass of Kunipia F were added to 95.4 parts by mass of purified water while stirring, and then thoroughly dispersed at a pressure of 50 MPa using a high-pressure dispersion device to obtain inorganic layered compound dispersion liquid 14. 【0084】 (Example 1) <Preparation of gas barrier compositions> 45.0 parts by mass of an inorganic layered compound dispersion 1 was mixed with 2.6 parts by mass of purified water, 24.4 parts by mass of NPA (n-propanol), and 28.0 parts by mass of an aqueous solution of a polyalcohol-based polymer 1 while stirring. Subsequently, the gas barrier composition was prepared by thoroughly dispersing the material at a pressure of 50 MPa using a high-pressure dispersion device. 【0085】 <Fabrication of laminates> A 25μm OPP film (P2161, manufactured by Toyobo Co., Ltd.) was coated with an anchor coating agent (Takelac A-3210 / Takenate A-3072, manufactured by Mitsui Chemicals) at a dry (coating amount after drying) of 0.1g / m². 2 The material was coated using a wire bar, dried with a hand dryer, and then an anchor coat layer was created. Next, the gas barrier composition is applied to the anchor coat layer at a dry (amount applied after drying) of 0.6 g / m². 2 The coating was applied using a wire bar and then dried with a hand dryer. After standing at room temperature for one day, the resulting gas barrier composition is coated with an adhesive (Takelac A-969v / Takenate A-5, manufactured by Mitsui Chemicals) at a dry (coating amount after drying) of 3 g / m². 2 It was applied in this manner and dried with a hand dryer. A 25 μm CPP film (P1128, manufactured by Toyobo Co., Ltd.) was laminated onto the above adhesive layer, and the laminate was aged at 40°C for 3 days to produce a laminate. 【0086】 (Examples 2-15, Comparative Examples 1-6) <Preparation of gas barrier compositions> A gas barrier composition was prepared in the same manner as in Example 1, except that the materials listed in Tables 1 and 2 were used. 【0087】 <Fabrication of laminates> A laminate was prepared in the same manner as in Example 1, except that a coating layer was formed using the gas barrier composition described above. 【0088】 [Table 1] 【0089】 [Table 2] 【0090】 <Storage stability> Each gas barrier composition was placed in a 70 mL glass bottle and stored for one month at temperatures of 5°C, 23°C, and 60°C. After storage, the samples were left to stand overnight at 23°C, then shaken, and the viscosity was measured using a Type B viscometer (manufactured by Toki Sangyo Co., Ltd.). The change in viscosity due to storage was evaluated according to the following criteria. The initial viscosity was measured using a Type B viscometer (manufactured by Toki Sangyo Co., Ltd.) after the prepared gas barrier composition was left to stand overnight at 23°C, then shaken. ○: The viscosity after one month was less than twice the initial viscosity. ×: The viscosity after one month was more than double the initial viscosity. 【0091】 <Oxygen permeability> For each laminate, oxygen permeability was measured using an oxygen permeability analyzer (OX-TRAN1 / 50, manufactured by MOCON) under conditions of 25°C / 0%RH and 25°C / 70%RH. The oxygen permeability is 1 cc / m³ under conditions of 25°C / 0%RH. 2 • 5 cc / m² under conditions of day·atm or less and 25℃ / 70%RH 2 Items below the following thresholds were deemed acceptable. 【0092】 <Peel strength> Each laminate was cut into 15 mm wide strips, and the T-type peel strength (N / 15 mm) was measured using a peel tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) as the peel strength. Furthermore, materials with a T-type peel strength of 1.3 N / 15 mm or higher were deemed acceptable. 【0093】 [Table 3] 【0094】 [Table 4] 【0095】 From the examples, it was confirmed that laminates prepared with the gas barrier composition of the present invention can form coatings with excellent gas barrier properties and interlayer adhesion (peel strength), and that they exhibit excellent storage stability at low, room, and high temperatures. Furthermore, in Comparative Example 4, the thickening was so severe that mixing was impossible, and therefore, each evaluation could not be performed. Furthermore, since the gas barrier composition was used immediately after manufacturing, the gas barrier properties and interlayer adhesion were sufficient even in the comparative example. However, if a gas barrier composition that has been stored (especially one with a storage stability rating of "×") is used, it is expected that it will not be possible to form a coating film of the gas barrier composition, or that the gas barrier properties and interlayer adhesion will be insufficient. [Industrial applicability] 【0096】 This invention provides a gas barrier composition that can form a coating film with excellent gas barrier properties and interlayer adhesion (peel strength), and that exhibits excellent storage stability at low, room, and high temperatures.

Claims

[Claim 1] It contains a polyalcohol-based polymer, a polycarboxylic acid-based polymer, an inorganic layered compound, and water. The polyalcohol-based polymer comprises at least one selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, and ethylene vinyl alcohol copolymer. The polycarboxylic acid polymer has a weight-average molecular weight of 4500 or more and 11000 or less. The content of the polycarboxylic acid polymer is 0.5 parts by mass or more and 6 parts by mass or less per 100 parts by mass of the inorganic layered compound. The content of the inorganic layered compound is 17.5 parts by mass or more per 100 parts by mass of the polyalcohol-based polymer. Gas barrier composition. [Claim 2] The gas barrier composition according to claim 1, wherein the content of the inorganic layered compound is 10 parts by mass or more per 100 parts by mass of the polyalcohol-based polymer. [Claim 3] The gas barrier composition according to claim 1 or 2, wherein the content of the polycarboxylic acid polymer is 1 part by mass or more and 5 parts by mass or less per 100 parts by mass of the inorganic layered compound. [Claim 4] The gas barrier composition according to claim 1 or 2, wherein the polycarboxylic acid polymer has a weight-average molecular weight of 5,000 or more and 10,000 or less. [Claim 5] The gas barrier composition according to claim 1 or 2, wherein the inorganic layered compound is a layered silicate compound. [Claim 6] A laminate comprising a coating layer formed from the gas barrier composition according to claim 1 or 2.