WO2016093225A1 - Procédé de fabrication d'un liquide de revêtement formant barrière contre les gaz et matériau d'emballage formant barrière contre les gaz - Google Patents

Procédé de fabrication d'un liquide de revêtement formant barrière contre les gaz et matériau d'emballage formant barrière contre les gaz Download PDF

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WO2016093225A1
WO2016093225A1 PCT/JP2015/084391 JP2015084391W WO2016093225A1 WO 2016093225 A1 WO2016093225 A1 WO 2016093225A1 JP 2015084391 W JP2015084391 W JP 2015084391W WO 2016093225 A1 WO2016093225 A1 WO 2016093225A1
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gas barrier
component
coating liquid
layer
packaging material
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PCT/JP2015/084391
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English (en)
Japanese (ja)
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大森　望
晴香 大森
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凸版印刷株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09D201/08—Carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/80—Processes for incorporating ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention relates to a method for producing a gas barrier coating liquid, a gas barrier coating liquid, and a gas barrier packaging material.
  • packaging materials used for packaging foods, pharmaceuticals, etc. it is required to prevent the contents from being altered.
  • food packaging materials are required to be able to suppress oxidation and alteration of proteins, fats and oils, and to maintain flavor and freshness.
  • pharmaceutical packaging materials that require handling in aseptic conditions, it is required to suppress the alteration of the active ingredients in the contents and maintain the efficacy of the pharmaceuticals.
  • Such alteration of the contents is mainly caused by oxygen or water vapor that permeates the packaging material or other gases that react with the contents.
  • packaging materials used for packaging foods and pharmaceuticals are required to have properties (gas barrier properties) that do not allow gas such as oxygen and water vapor to permeate.
  • a gas barrier film composed of a polymer (gas barrier polymer) that has a relatively high gas barrier property, or a laminate (lamination) using the gas barrier film as a film substrate.
  • a gas barrier polymer a polymer containing a highly hydrophilic high hydrogen bonding group in the molecule, represented by poly (meth) acrylic acid or polyvinyl alcohol, has been used.
  • Packaging materials made of these polymers exhibit very excellent gas barrier properties such as oxygen under dry conditions.
  • the packaging materials made of these polymers have a problem that the gas barrier property such as oxygen is greatly lowered due to the hydrophilicity of the polymer under high humidity conditions, and a problem that the resistance to humidity and hot water is poor. It was.
  • a polycarboxylic acid polymer layer and a polyvalent metal compound-containing layer are laminated adjacent to each other on the substrate, and the polycarboxylic acid polymer layer and the polyvalent metal compound are contained.
  • a gas barrier packaging material is prepared by producing a polyvalent metal salt of a polycarboxylic acid polymer by reacting between two layers with a layer (see, for example, Patent Documents 1 to 3). ).
  • the gas barrier packaging material thus obtained is known to have a high oxygen gas barrier property even under high humidity.
  • such a gas barrier packaging material requires a plurality of types of coating liquids in production, and needs to be applied a plurality of times, requiring labor.
  • Patent Document 4 a solution or dispersion of a mixture containing a polycarboxylic acid polymer, a polyvalent metal compound, either a volatile base or an acid, and a solvent is placed on two inorganic layers.
  • a method has been proposed in which two organic thin films each coated and having an inorganic layer laminated on one surface are obtained, and the two organic thin films are laminated to obtain a laminated film for a moisture-proof film.
  • a method using a solution or dispersion of a mixture containing a polycarboxylic acid polymer, a polyvalent metal compound, a volatile base, and a solvent is also proposed.
  • the liquid stability of the solution or dispersion is insufficient, and precipitation is likely to occur during storage. If precipitation occurs in the liquid, a uniform film cannot be formed.
  • the volatile base or acid remains, the reaction between the polycarboxylic acid polymer and the polyvalent metal compound is hindered, and the gas barrier property becomes insufficient. It is necessary to remove the acid sufficiently.
  • a large amount of volatile base or acid is blended, a large amount of heat is required for drying.
  • ammonia is used as the volatile base, there is also a problem that the working environment is deteriorated due to a large amount of ammonia volatilizing.
  • the present invention has been made in view of the above circumstances, and even when the content of a volatile base or acid is small, the coating property is good, and the polyvalent metal salt of a polycarboxylic acid polymer in one liquid
  • An object of the present invention is to provide a gas barrier coating solution that can form a layer containing the gas barrier, has excellent liquid stability, a method for producing the gas barrier coating solution, and a gas barrier packaging material using the gas barrier coating solution.
  • the method for producing a gas barrier coating liquid according to the first aspect of the present invention includes a polycarboxylic acid polymer, a first polyvalent metal ion, and a first solvent, and the content of the first polyvalent metal ion.
  • the content of the first polyvalent metal ion in the first solution may be an amount that neutralizes 40 mol% or less of the carboxyl group of the polycarboxylic acid polymer.
  • the gas barrier coating liquid according to the second aspect of the present invention is obtained by the method for producing a gas barrier coating liquid according to the above aspect.
  • the gas barrier packaging material according to the third aspect of the present invention is formed by drying a coating film formed from the gas barrier coating liquid according to the above aspect, and 1490 cm ⁇ 1 to 1659 cm ⁇ when the infrared absorption spectrum is measured.
  • maximum peak height in absorbance within the first range and (alpha) is the ratio of the 1660 cm -1 ⁇ absorbance maximum peak height in the range of 1750 cm -1 and ( ⁇ ) ( ⁇ / ⁇ ) of 1 or more layers Is provided.
  • the coating property is good even when the content of the volatile base or acid is small, and a layer containing a polyvalent metal salt of a polycarboxylic acid polymer can be formed in one liquid,
  • a gas barrier coating solution having excellent liquid stability, a method for producing the gas barrier coating solution, and a gas barrier packaging material using the gas barrier coating solution.
  • a method for producing a gas barrier coating liquid according to an embodiment of the present invention includes: The following (A) component (polycarboxylic acid polymer), the following (B) component (first polyvalent metal ion) and a solvent (first solvent), The step of preparing the solution (1) (first solution) such that the content of the polyvalent metal ion is an amount that neutralizes a part of the carboxyl group of the component (A) (hereinafter referred to as “step (i) ) "), (B) component (second polyvalent metal ion), the following (C) component (volatile base or acid excluding carbonic acid), the following (D) component (carbonate ion) and solvent (second solvent)
  • the first polyvalent metal ion refers to the polyvalent metal ion used in the step (i)
  • the second polyvalent metal ion refers to the step (ii).
  • the first polyvalent metal ion and the second polyvalent metal ion may be the same ion or different ions.
  • the “polycarboxylic acid polymer” is a polymer having two or more carboxyl groups in the molecule.
  • the component (A) include (co) polymers of ethylenically unsaturated carboxylic acids; copolymers of ethylenically unsaturated carboxylic acids and other ethylenically unsaturated monomers; alginic acid, carboxymethylcellulose, pectin And acidic polysaccharides having a carboxyl group in the molecule. These polycarboxylic acid polymers may be used alone or in combination of two or more.
  • Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • Examples of other ethylenically unsaturated monomers copolymerizable with the ethylenically unsaturated carboxylic acid include saturated carboxylic acid vinyl esters such as ethylene, propylene, and vinyl acetate, alkyl acrylates, alkyl methacrylates, and alkyl itacos. Nates, vinyl chloride, vinylidene chloride, styrene, acrylamide, acrylonitrile and the like.
  • the component (A) from the viewpoint of gas barrier properties of the obtained gas barrier packaging material, at least one polymerizable property selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid and crotonic acid.
  • Polymers containing structural units derived from monomers are preferred.
  • the polymer may be a homopolymer or a copolymer.
  • the other structural units include, for example, an ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated carboxylic acid. Examples include a polymer.
  • a polymer containing a structural unit derived from at least one polymerizable monomer selected from the group consisting of acrylic acid, maleic acid, methacrylic acid and itaconic acid is preferable.
  • the proportion of structural units derived from at least one polymerizable monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and maleic acid is 80 mol% or more.
  • it is 90 mol% or more (however, all the structural units are 100 mol%).
  • the number average molecular weight of the component (A) is preferably 2,000 to 10,000,000. If the number average molecular weight of the component (A) is 2,000 or more, the resulting gas barrier packaging material is more excellent in water resistance, and there is no case where gas barrier properties and transparency are deteriorated by moisture, or whitening does not occur. If the number average molecular weight of the component (A) is 10,000,000 or less, the viscosity of the gas barrier coating liquid according to this embodiment does not become too high, and the coating property is not easily impaired.
  • the number average molecular weight of the component (A) is more preferably 5,000 to 1,000,000 from the viewpoint of water resistance of the obtained gas barrier packaging material.
  • the number average molecular weight of (A) component is the number average molecular weight of polystyrene conversion calculated
  • GPC gel permeation chromatography
  • the component (B) is a polyvalent metal ion.
  • “Polyvalent metal ion” is a metal ion having a valence of 2 or more.
  • Specific examples of polyvalent metal ions include alkaline earth metal ions such as beryllium ions, magnesium ions, calcium ions, titanium ions, zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, Examples include transition metal ions such as zinc ions, aluminum ions, and the like.
  • These (B) components may be used individually by 1 type, or may use 2 or more types together.
  • divalent metal ions are preferable from the viewpoint of gas barrier properties and manufacturability of the gas barrier packaging material.
  • at least one selected from the group consisting of alkaline earth metal ions, cobalt ions, nickel ions, copper ions and zinc ions is preferable, and selected from the group consisting of magnesium ions, calcium ions, copper ions and zinc ions. At least one is particularly preferred.
  • the component (C) is a volatile base or acid (excluding carbonic acid).
  • Examples of the volatile base include ammonia, methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, morpholine, ethanolamine and the like. Among these, ammonia is preferable from the viewpoints of coating solution stability and gas barrier properties.
  • volatile acid various inorganic acids and organic acids can be used, and examples thereof include hydrochloric acid, acetic acid, sulfuric acid, oxalic acid, citric acid, malic acid, and tartaric acid.
  • a component is a carbonate ion.
  • carbonate ion is a general term for CO 3 2 ⁇ and HCO 3 ⁇ . Included in the gas barrier coating solution (D) component, CO 3 2-But well, HCO 3 - but well, CO 3 2-and HCO 3 - or in both even.
  • the solvent (first solvent, second solvent) is not particularly limited, and examples thereof include water, an organic solvent, a mixed solvent of water and an organic solvent, and the like.
  • a 1st solvent shows the solvent used for the said process (i)
  • a 2nd solvent shows the solvent used for the said process (ii).
  • the first solvent and the second solvent may be the same solvent or different solvents.
  • the water is preferably purified water, and examples thereof include distilled water and ion exchange water.
  • the organic solvent it is preferable to use at least one organic solvent selected from the group consisting of lower alcohols having 1 to 5 carbon atoms and lower ketones having 3 to 5 carbon atoms. Specific examples of the organic solvent include methanol, ethanol, propanol, 2-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, acetone, and methyl ethyl ketone.
  • a mixed solvent of water and an organic solvent the above-described mixed solvent using water or an organic solvent is preferable, and a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms is more preferable.
  • a solvent having a water ratio of 20% by mass to 95% by mass and an organic solvent ratio of 80% by mass to 5% by mass is typically used. The total is 100% by mass).
  • the solvent water or a mixed solvent of water and an organic solvent is preferable from the viewpoint of solubility of the component (A).
  • ⁇ Other ingredients examples include other polymers, monovalent metal compounds, inorganic layered compounds (such as montmorillonite), and various additives.
  • the additive examples include a plasticizer, a resin, a dispersant, a surfactant, a softener, a stabilizer, an antiblocking agent, a film forming agent, an adhesive, and an oxygen absorber.
  • a plasticizer it can select from a well-known plasticizer suitably, for example.
  • Specific examples of the plasticizer include, for example, ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,3-butanediol, 2,3-butanediol, pentamethylene glycol, hexamethylene glycol, diethylene glycol, triethylene.
  • Examples include glycol, polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene oxide, sorbitol, mannitol, dulcitol, erythritol, glycerin, lactic acid, fatty acid, starch, and phthalate.
  • plasticizers may be used individually by 1 type, or may use 2 or more types together as needed.
  • polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, glycerin, and starch are preferable from the viewpoint of stretchability and gas barrier properties.
  • components may include components derived from the (B) component supply source and (D) component supply source.
  • a component derived from the polyvalent metal compound may be included.
  • the component derived from carbonate may be included.
  • the solution (1) can be prepared by, for example, dissolving the component (A) and the supply source of the component (B) (first polyvalent metal ion) in a solvent (first solvent). You may add another component as needed.
  • the order in which the component (A) and the supply source of the component (B) are dissolved in the solvent is not particularly limited.
  • the polyvalent metal is a simple substance of a polyvalent metal element having a metal ion valence of 2 or more.
  • Specific examples of the polyvalent metal include alkaline earth metals such as beryllium, magnesium and calcium, transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper and zinc, and aluminum.
  • Specific examples of the polyvalent metal compound include oxides, hydroxides, carbonates, organic acid salts, inorganic acid salts of the above polyvalent metals, ammonium complexes of the above polyvalent metals, and 2 to 4 of the polyvalent metals.
  • Organic salts include acetate, oxalate, citrate, lactate, phosphate, phosphite, hypophosphite, stearate, monoethylenically unsaturated carboxylate, etc. It is done.
  • inorganic acid salts include chlorides, sulfates and nitrates.
  • polyvalent metal alkylalkoxides can be used as the polyvalent metal compound.
  • At least 1 sort (s) selected from the group which consists of a bivalent metal and a compound of a bivalent metal is preferable, From the group which consists of alkaline-earth metal, cobalt, nickel, copper, and zinc Selected metal oxides, hydroxides, carbonates, organic acid salts (eg acetate), ammonium complexes of metals selected from the group consisting of cobalt, nickel, copper and zinc, carbonates of the complexes Is more preferable.
  • oxides, hydroxides, and carbonates of metals selected from the group consisting of magnesium, calcium, copper, and zinc, ammonium complexes of copper or zinc, and carbonates of the complexes are particularly preferable.
  • a monovalent metal compound for example, a monovalent metal salt of a polycarboxylic acid polymer is mixed with the supply source of the component (B), or
  • the source of the component (B) that contains the monovalent metal compound can be used.
  • the form of the (B) component supply source is not particularly limited. For example, solid, powder, pellets and the like can be mentioned.
  • the content of the component (B) (first polyvalent metal ion) in the solution (1) is an amount for neutralizing a part of the carboxyl group of the component (A).
  • the component (A) and the component (B) coexist in the presence of a solvent, the component (A) and the component (B) react rapidly, and the carboxyl group of the component (A) is derived from the component (B).
  • Neutralized by the polyvalent metal to form a partially neutralized product of the (A) component polyvalent metal When the degree of neutralization with a polyvalent metal is increased, the solubility in a solvent is decreased. Therefore, the content of the component (B) in the solution (1) is an amount that neutralizes a part of the carboxyl group of the component (A) and is set within a range in which the partially neutralized product is dissolved in the solvent.
  • the degree of neutralization with a polyvalent metal is a polyvalent value for all the carboxyl groups (100 mol%) of the partially neutralized product (the total number of moles of free carboxyl groups and carboxyl groups forming a salt). This is the ratio (mol%) of the number of moles of the carboxyl group salt forming the metal salt. All the carboxyl groups of the partially neutralized product are the sum of the free carboxyl group (—COOH) and the carboxyl group forming a salt (—COO ⁇ ).
  • the content of the component (B) (first polyvalent metal ion) in the solution (1) neutralizes 40 mol% or less of the carboxyl group of the component (A).
  • An amount that neutralizes 5 to 40 mol% of the carboxyl group of the component (A) is more preferable, and an amount that neutralizes 5 to 30 mol% of the carboxyl group of the component (A) is particularly preferable. If the degree of neutralization of the carboxyl group of component (A) by the polyvalent metal is 40 mol% or less, the partially neutralized product is sufficiently dissolved in the solvent.
  • the content of the component (B) in the solution (1) is 5-30% of the carboxyl group of the component (A) from the viewpoint of adjusting the solution (1).
  • An amount that neutralizes mol% is particularly preferred.
  • a source of the component (B) (second polyvalent metal ion), a component (C), and a source of the component (D) are dissolved in a solvent (second solvent).
  • a solvent second solvent
  • the order in which the (B) component, the (C) component, and the (D) component supply source are dissolved in the solvent is not particularly limited.
  • the component (B) supply source also corresponds to the component (D) supply source (for example, a polyvalent metal carbonate), and a desired amount of the component (D) can be blended only with the component (B) supply source.
  • the solution (2) may be prepared by dissolving the component (B) supply source and the component (C) in a solvent.
  • step (B) Examples of the supply source of the component include the same compounds as those described above. What is the source of the component (B) (first polyvalent metal ion) used in step (i) and the source of the component (B) (second polyvalent metal ion) used in step (ii)? , May be the same or different.
  • Examples of the supply source of component (D) include carbonates such as normal salts, acidic salts (bicarbonates), basic salts (carbonate hydroxide salts), and carbonic acid.
  • Examples of the carbonate include alkali metal and alkaline earth metal carbonates, alkali metal and alkaline earth metal hydrogen carbonates, alkali metal and alkaline earth metal ammonium carbonates, and the like.
  • Specific examples of carbonates include ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, lanthanum carbonate, lithium carbonate, magnesium carbonate, manganese carbonate, nickel carbonate, strontium carbonate, Examples thereof include aminoguanidine carbonate and guanidine carbonate.
  • anhydrous carbonates, hydrated salts, or mixtures thereof can be used.
  • the supply source of the component (D) among the above supply sources, ammonium carbonate or ammonium hydrogen carbonate is preferable from the viewpoint that the gas barrier property is not impaired, the handling is easy, and the liquid stability of the gas barrier coating liquid is more excellent.
  • These sources of component (D) may be used alone or in combination of two or more.
  • the component (D) blended in the gas barrier coating solution is all blended in the solution (2). It is preferable.
  • step (iii) In step (iii), solution (1) (first solution) obtained in step (i) and solution (2) (second solution) obtained in step (ii) are mixed. Additional solvents and other components may be added as necessary. Thereby, the gas barrier coating liquid according to the present embodiment is obtained.
  • the gas barrier coating liquid obtained as described above comprises a partially neutralized product in which a part of the carboxyl group of component (A) is neutralized with a polyvalent metal, component (B), component (C), (D) component.
  • the component (B) may react with the component (C) to form a metal complex.
  • the metal complex means a complex of a polyvalent metal (cobalt, nickel, copper, zinc, etc.) and a volatile base. Examples of the metal complex include zinc and copper tetraammonium complexes.
  • ⁇ Content of each component Content of component (B) in gas barrier coating liquid (total amount of component (B) in solution (1) and component (B) in solution (2).
  • Partial reaction with component (A) is preferably 0.2 chemical equivalents or more and 0.8 chemical equivalents or more and 10 chemical equivalents or less for all the carboxyl groups of the component (A). More preferably, it is 0.8 chemical equivalent or more and 5 chemical equivalent or less.
  • the content of the component (B) is 0.2 chemical equivalent or more, the gas barrier property and moisture resistance of the layer formed from the gas barrier coating liquid can be sufficiently improved.
  • the content of the component (B) is 0.8 chemical equivalent or more and 10 chemical equivalents or less, the gas barrier property of the layer formed from the gas barrier coating liquid is further improved. If content of (B) component is 0.8 chemical equivalent or more and 5 chemical equivalent or less, the gas barrier property of the layer formed from the coating liquid for gas barriers will improve, and transparency can be maintained.
  • the content of the component (C) in the gas barrier coating solution is preferably 1 chemical equivalent or more, more preferably 1 chemical equivalent or more and 30 chemical equivalents or less, with respect to all the carboxyl groups of the component (A). More preferably, it is not less than chemical equivalent and not more than 10 chemical equivalent.
  • the component (C) is a volatile base
  • the component (B) forms a complex with the base by adding the volatile base to the gas barrier coating solution so as to be 1 chemical equivalent or more. Thereby, it can suppress that (A) component, the partially neutralized product of (A) component, and (B) component react, and the coating liquid for gas barriers can maintain the state of a transparent and uniform solution.
  • the lower the volatile base content the better the gas barrier properties are manifested under conditions of less heat, such as low temperature drying, when the barrier layer is formed by coating and drying the gas barrier coating liquid. be able to.
  • the volatilization amount of the base is small, and the influence on the working environment (for example, an irritating odor caused by ammonia) is reduced.
  • component (C) is a volatile acid
  • the blending amount of component (C) in the step of producing the gas barrier coating liquid is the same as in the case where “(C) component is a volatile base”.
  • it is preferably 1 chemical equivalent or more, more preferably 1 chemical equivalent or more and 30 chemical equivalents or less, and more preferably 1 chemical equivalent or more and 10 chemical equivalents or less with respect to all the carboxyl groups of the component (A). preferable.
  • the content of the component (D) in the gas barrier coating liquid is 0.05 to 10 in terms of the molar ratio to the component (B) (number of moles of the component (D) / number of moles of the component (B)). Preferably, it is 1-5. If the molar ratio of component (D) to component (B) is not less than the lower limit of the above range (number of moles of component (D) / number of moles of component (B) is 0.05), all of component (A) It is easy to obtain a uniform solution containing the component (B) in an amount exceeding 1 chemical equivalent with respect to the carboxyl group.
  • the barrier layer is easily formed.
  • the molar ratio of the component (D) to the component (B) is 1 to 5, the component (B) and the component (D) are easily dissolved.
  • the blending amount of the solvent in the step of producing the gas barrier coating liquid is such that the ratio of the total amount of the component (A) and the component (B) to the total amount of the gas barrier coating liquid obtained is 0.00.
  • An amount of 1% by mass to 50% by mass is preferable.
  • the blending amount of the additive in the step of producing the gas barrier coating liquid is the ratio of the mass of the component (A) to the mass of the additive (component (A): additive). 70:30 to 99.9: 0.1 is preferable, and 80:20 to 98: 2 is more preferable.
  • the chemical equivalents of the component (B) and the component (C) for all the carboxyl groups of the component (A) in the gas barrier coating liquid can be calculated from the raw materials used for the preparation of the gas barrier coating liquid.
  • the gas barrier coating liquid may be analyzed by an analysis method such as ICP (High Frequency Inductively Coupled Plasma) emission spectroscopy or gas chromatography.
  • ICP High Frequency Inductively Coupled Plasma
  • the chemical equivalent will be described in detail by taking as an example the case where the component (A) is polyacrylic acid and the source of the component (B) is magnesium oxide.
  • the mass of polyacrylic acid is 100 g
  • the molecular weight of the monomer unit of polyacrylic acid is 72, and since it has one carboxyl group per molecule of monomer, the amount of carboxyl group in 100 g of polyacrylic acid Is 1.39 mol.
  • the gas barrier coating liquid since the component (C) is included, the partially neutralized product of the polyvalent metal (A) reacts with the component (B) in the coating liquid. It is suppressed from becoming a solid and can be applied.
  • the component (C) when the gas barrier coating liquid is applied onto a support and dried, the component (C) is removed from the coating film. By removing the component (C) from the coating film, the partially neutralized product by the polyvalent metal of the component (A) reacts with the component (B) in the coating film, and the degree of neutralization by the polyvalent metal is as described above. A layer containing a polyvalent metal salt of a polycarboxylic acid polymer higher than the partially neutralized product is formed.
  • the layer containing the polyvalent metal salt of the polycarboxylic acid polymer exhibits high oxygen barrier properties not only in a low humidity region but also in a high humidity region.
  • the gas barrier coating liquid according to this embodiment includes the component (D), and thus has excellent liquid stability.
  • the gas barrier coating liquid according to this embodiment is less likely to precipitate during storage. Therefore, the uniformity of the layer formed using the gas barrier coating liquid is excellent.
  • the content of the component (C) can be reduced as compared with the conventional case. That is, normally, in order to suppress the reaction between the component (A) and the component (B), the coating solution contains an excess of the component (C) relative to the component (B).
  • step (i) a part of the carboxyl group of component (A) is previously neutralized with a polyvalent metal, so that the amount of component (B) added thereafter (solution prepared in step (ii) ( 2) The amount of the component (B) in) is reduced. Therefore, the amount of the component (C) necessary for suppressing the reaction of the component (B) in the coating liquid is reduced.
  • the component (C) When the content of the component (C) is small, the component (C) is sufficiently removed even if the drying after coating is performed under conditions with less heat (such as low temperature drying). The reaction between the Japanese product and the component (B) proceeds satisfactorily, and excellent gas barrier properties are easily exhibited. Further, when ammonia is used as a volatile base, the amount of ammonia volatilized during drying is reduced, and a specific irritating odor can be suppressed.
  • the gas barrier packaging material according to the present embodiment is formed by drying a coating film formed from the gas barrier coating liquid according to the present embodiment manufactured by the above-described manufacturing method, and when an infrared absorption spectrum is measured.
  • the ratio of 1490cm -1 ⁇ 1659cm maximum peak height absorbance in the range of -1 and (alpha), the maximum peak height in absorbance in the range of 1660 cm -1 ⁇ 1750 cm -1 and ( ⁇ ) ( ⁇ / ⁇ ) Is a layer having 1 or more (hereinafter also referred to as “layer (I)”).
  • the partially neutralized product of the component (A) reacts with the component (B) in the coating film, and a polycarboxylic acid polymer is obtained.
  • the layer (I) contains a polyvalent metal salt of a polycarboxylic acid polymer.
  • the component (B) may form a polyvalent metal salt of a polycarboxylic acid polymer, or may form a polyvalent metal complex salt of a polycarboxylic acid polymer.
  • the unreacted component (B) may be present in the layer (I) as particles, molecules, or the like.
  • ⁇ Maximum peak height ratio ( ⁇ / ⁇ )> The ratio ( ⁇ / ⁇ ) of the maximum peak height of the absorbance in the infrared absorption spectrum will be described.
  • the maximum peak height ( ⁇ ) is the infrared absorption of the C ⁇ O stretching vibration of 1560 cm ⁇ 1 belonging to the carboxyl group forming a salt (—COO ⁇ ) (hereinafter also referred to as “carboxyl salt”). It is the maximum peak height of the absorbance of the spectrum.
  • salts of carboxyl groups (-COO -) C O stretching vibration attributable to the infrared wave number range of 1490cm -1 ⁇ 1659cm -1, an absorption peak having an absorption maximum in the vicinity of 1560 cm -1 give.
  • the absorbance when the infrared absorption spectrum of layer (I) is measured is proportional to the amount of chemical species having infrared activity present in the gas barrier packaging material. Therefore, the ratio ( ⁇ / ⁇ ) of the maximum peak height of the absorbance in the infrared absorption spectrum is the ratio between the carboxyl group polyvalent metal salt (—COO ⁇ ) and the free carboxyl group (—COOH) in the layer (I). It can be used as a scale representing the ratio of.
  • the C ⁇ O stretching vibration attributed to the monovalent metal salt of a carboxyl group (—COO ⁇ ) is , an infrared wave number range of 1490cm -1 ⁇ 1659cm -1, giving an absorption peak having an absorption maximum in the vicinity of 1560 cm -1.
  • the absorption peak of absorbance in the infrared absorption spectrum includes two C ⁇ O stretching vibrations derived from a monovalent metal salt of a carboxyl group and a polyvalent metal salt of a carboxyl group.
  • the ratio ( ⁇ / ⁇ ) of the maximum peak height of the absorbance in the infrared absorption spectrum is such that the polyvalent metal salt of a carboxyl group (—COO ⁇ ) and the free carboxyl group (—COOH) It can be used as a scale that represents the ratio of.
  • the ionization degree of the layer (I) can be determined.
  • the degree of ionization is defined by the following formula (1).
  • (Degree of ionization) Y / X (1)
  • X is the number of moles of all carbonyl carbons (assigned to free carboxyl groups and salts of carboxyl groups) of the polycarboxylic acid polymer in 1 g of layer (I).
  • Y is layer (I) It is the number of moles of carbonyl carbon attributed to the salt of the carboxyl group contained in the polycarboxylic acid polymer in 1 g.)
  • the degree of ionization is the ratio of the number of carboxyl group salts to the total number of carboxyl groups in the polycarboxylic acid polymer (the total number of free carboxyl groups and carboxyl group salts), and is the maximum absorbance peak in the infrared absorption spectrum. Compared with the height ratio ( ⁇ / ⁇ ), it can be determined as a more strict ratio of chemical species.
  • All the carboxyl groups of the polycarboxylic acid polymer means the carboxyl group of the partially neutralized product of the component (A) that was not involved in the reaction, and the partially neutralized product of the component (A) and (B) It contains a carboxyl group of a polyvalent metal salt of a polycarboxylic acid produced by a reaction with a component. From the measurement of the infrared absorption spectrum, it can be confirmed that a polyvalent metal salt of polycarboxylic acid is produced.
  • the carboxyl group of the partially neutralized product of component (A) includes a free carboxyl group and a polyvalent metal salt of a carboxyl group, and may include a monovalent metal salt of a carboxyl group.
  • the carboxyl group of the polyvalent metal salt of the polycarboxylic acid polymer includes a polyvalent metal salt of a carboxyl group, and may include a free carboxyl group or a monovalent metal salt of a carboxyl group.
  • the infrared absorption spectrum can be measured using, for example, FT-IR2000 manufactured by PERKIN-ELMER. Specifically, the infrared absorption spectrum of the sample was measured by transmission method, ATR method (attenuated total reflection method), KBr pellet method, diffuse reflection method, photoacoustic method (PAS method), etc., and 1490 cm ⁇ 1 to 1659 cm ⁇ 1. maximum peak height absorbance in the range of (alpha) and 1660 cm -1 ⁇ absorbance maximum peak height in the range of 1750 cm -1 (beta) measured, the ratio of the maximum peak height of absorbance (alpha / beta ). The infrared absorption spectrum is preferably measured by the transmission method or the ATR method from the viewpoint of simplicity.
  • Examples of the ATR method include measurement conditions using KRS-5 (thallium bromoiodide), an incident angle of 45 degrees, a resolution of 4 cm ⁇ 1 , and an integration count of 30 times.
  • KRS-5 thallium bromoiodide
  • FT-IR infrared absorption spectrum measurement method using FT-IR
  • the gas barrier packaging material comprises a support and a layer (I) formed on the support, and the support and the layer (I) There is a stack of integral, if the support does not absorb light in the optical and 1700 cm -1 vicinity of 1560 cm -1 vicinity, remains of the laminate, to measure the infrared absorption spectrum.
  • the support absorbs light of light and 1700 cm -1 vicinity of 1560 cm -1 vicinity to measure the surface of the layer (I) in the ATR method.
  • Ge germanium
  • the measurement conditions can be given at an incident angle of 45 degrees, a resolution of 4 cm ⁇ 1 , and an integration count of 30 times.
  • the ionization degree of the gas barrier packaging material can be calculated using a calibration curve prepared in advance.
  • the calibration curve used here is created by the following procedure.
  • the component (A) is neutralized with a known amount of sodium hydroxide in advance, and coated on a plastic film substrate, for example, to prepare a standard sample in the form of a coating film.
  • the C ⁇ O stretching vibration of the carbonyl carbon attributed to the free carboxyl group (—COOH) and the salt of the carboxyl group (—COO ⁇ Na + ) in the standard sample thus prepared is separated and detected by measuring the infrared absorption spectrum. be able to.
  • the component (A) is neutralized with a known amount of sodium hydroxide in advance, the molar ratio of free carboxyl group (—COOH) and carboxyl group salt (—COO ⁇ Na + ) in the polymer (Number ratio) is known. Therefore, first, several kinds of standard samples are prepared by changing the amount of sodium hydroxide, and the infrared absorption spectrum is measured. Next, a calibration curve can be created by regression analysis of the relationship between the ratio of the maximum peak height of absorbance ( ⁇ / ⁇ ) and the known molar ratio.
  • the molar ratio between the free carboxyl group (—COOH) in the sample and the polyvalent metal salt of the carboxyl group (—COO ⁇ ) is obtained from the result of infrared absorption spectrum measurement of the unknown sample. It is done. From the result, the degree of ionization can be obtained by the equation (1).
  • the infrared absorption spectrum is mainly derived from the chemical structure of the carboxyl group, and is less affected by the metal species of the salt.
  • FIG. 1 is a cross-sectional view schematically showing a gas barrier packaging material according to a first embodiment of the present invention.
  • a gas barrier packaging material 10 according to the present embodiment includes a support 1 and a barrier layer 3 laminated on one surface of the support 1.
  • Examples of the material constituting the support 1 include plastics, papers, rubbers, and the like. Among these, plastics are preferable from the viewpoint of adhesion to the support 1 and the layer formed on the support 1.
  • plastics examples include polyolefin polymers such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, poly-4-methylpentene, and cyclic polyolefin, copolymers of the above polyolefin polymers, Acid-modified products of the above-mentioned polyolefin polymers; vinyl acetate copolymers such as polyvinyl acetate, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, and polyvinyl alcohol; polyethylene terephthalate, polybutylene terephthalate Polyester polymers such as polyethylene naphthalate, poly ⁇ -caprolactone, polyhydroxybutyrate, polyhydroxyvalylate, etc., copolymers of the above polyester polymers; nylon 6, nylon 66, nylon 12, nylon 6 Polyamide polymers such as nylon 66 copolymer, nylon 6-nylon 12 copolymer, metaxylene adipamide /
  • a material in which a thin film made of an inorganic compound or a metal compound such as silicon oxide, aluminum oxide, aluminum, or silicon nitride is formed on the surface of the plastic by vapor deposition, sputtering, or ion plating is used. It may be used.
  • the form of the support 1 is not particularly limited, and examples thereof include a film, a sheet, a bottle, a cup, a tray, a tank, and a tube.
  • a film or a sheet is preferable from the viewpoint of laminating the barrier layer 3 and the like.
  • the thickness of the support 1 varies depending on the use of the support 1 and the like, but is preferably 5 ⁇ m to 5 cm. In the use of a film or sheet, the thickness of the support 1 is preferably 5 ⁇ m to 800 ⁇ m, and more preferably 5 ⁇ m to 500 ⁇ m. When the thickness of the support 1 is within the above range (5 ⁇ m to 800 ⁇ m), the workability and productivity in each application are excellent. When the thickness of the support 1 is 5 to 500 ⁇ m, the support 1 is excellent in flexibility and can easily form a uniform coating film.
  • the surface of the support 1 may be subjected to surface activation treatment such as corona treatment, flame treatment, and plasma treatment from the viewpoint of adhesion to the layer formed on the support 1.
  • surface activation treatment such as corona treatment, flame treatment, and plasma treatment from the viewpoint of adhesion to the layer formed on the support 1.
  • the barrier layer 3 is the layer (I) described above. That is, it is a layer formed by drying the coating film formed from the gas barrier coating liquid according to the present embodiment, and when the infrared absorption spectrum is measured by the transmission method, it is within the range of 1490 cm ⁇ 1 to 1659 cm ⁇ 1 .
  • maximum peak height in absorbance between (alpha) the ratio between the maximum peak height absorbance in the range of 1660cm -1 ⁇ 1750cm -1 ( ⁇ ) ( ⁇ / ⁇ ) is one or more layers.
  • the ratio ( ⁇ / ⁇ ) of the maximum peak height is 1 or more, the ratio of carboxyl groups that are polyvalent metal salts is sufficiently large among all the carboxyl groups of the polycarboxylic acid polymer, and the barrier The layer 3 exhibits a high oxygen barrier property not only in a low humidity region but also in a high humidity region. That is, since the free carboxyl group having high water absorption is cross-linked with a polyvalent metal, the molecular chain of the polycarboxylic acid polymer is difficult to spread even in a high humidity region, and the oxygen barrier property is not easily lowered.
  • the thickness of the barrier layer 3 is not particularly limited, but is preferably 0.001 ⁇ m to 1 mm, more preferably 0.01 ⁇ m to 100 ⁇ m, and further preferably 0.1 ⁇ m to 10 ⁇ m. If the thickness of the barrier layer 3 is not less than the lower limit (0.001 ⁇ m) of the above range, the barrier layer 3 tends to be a uniform film. If the barrier layer 3 is a uniform film, adhesion to a layer adjacent to the barrier layer 3 is excellent. If the thickness of the barrier layer 3 is less than or equal to the upper limit of the above range (1 mm), the ionic cross-linking by the polyvalent metal is rapidly formed even when the barrier layer 3 is formed even under conditions with a small amount of heat such as low temperature drying. Excellent oxygen gas barrier properties. From the viewpoint of barrier properties and flexibility, the thickness of the barrier layer 3 is more preferably 0.01 to 100 ⁇ m. A thickness of the barrier layer 3 of 0.1 to 10 ⁇ m is particularly preferable because the barrier property and flexibility are further improved.
  • the gas barrier packaging material 10 generally has an oxygen permeability of 30 cm 3 and a relative humidity of 70% of 300 cm 3 (STP) / (m 2 ⁇ day ⁇ MPa) or less, preferably 200 cm 3 (STP) / ( m 2 ⁇ day ⁇ MPa) or less, more preferably 100 cm 3 (STP) / (m 2 ⁇ day ⁇ MPa) or less, particularly preferably 50 cm 3 (STP) / (m 2 ⁇ day ⁇ MPa) or less. It is.
  • the gas barrier packaging material 10 can be manufactured, for example, by a manufacturing method including the following step ( ⁇ 1).
  • the coating method of the gas barrier coating liquid according to the present embodiment is not particularly limited, and examples thereof include a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, and a kit. Examples thereof include a coating method, a die coating method, a metering bar coating method, a chamber doctor combined coating method, and a curtain coating method.
  • the formed coating film is dried to remove the solvent, whereby the barrier layer 3 is formed.
  • the temperature, time, and the like are set so that the maximum peak height ratio ( ⁇ / ⁇ ) is 1 or more.
  • a drying method of a coating film For example, methods, such as a hot-air drying method, a hot roll contact method, an infrared heating method, a microwave heating method, are mentioned. These drying methods may be performed alone or in combination.
  • the drying temperature of the coating film is not particularly limited, but when water or a mixed solvent of water and an organic solvent is used as a solvent, it is usually preferably 40 ° C. to 160 ° C.
  • the pressure during drying of the coated film is usually preferably normal pressure or reduced pressure, and preferably from normal pressure from the viewpoint of facility simplicity.
  • FIG. 2 is a cross-sectional view schematically showing a gas barrier packaging material according to a second embodiment of the present invention.
  • the gas barrier packaging material 20 includes a support 1, an anchor coat layer 5 laminated on one surface of the support 1, and a barrier layer 3 laminated on the anchor coat layer 5.
  • the gas barrier packaging material 20 is the same as the gas barrier packaging material 10 according to the first embodiment except that an anchor coat layer 5 is further provided between the support 1 and the barrier layer 3.
  • the anchor coat layer 5 is provided to improve the adhesion between the support 1 and the barrier layer 3.
  • various resins can be used as a material constituting the anchor coat layer 5.
  • the resin include alkyd resin, melamine resin, acrylic resin, polyurethane resin, polyester resin, phenol resin, amino resin, fluororesin, epoxy resin, aqueous polyurethane resin, polyvinyl alcohol polymer and derivatives thereof, carboxymethyl cellulose, hydroxy Cellulose derivatives such as ethyl cellulose, starches such as oxidized starch, etherified starch, dextrin, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid or esters thereof, salts and copolymers thereof, aqueous polyester resin, polyhydroxyethyl methacrylate and Examples thereof include vinyl polymers such as copolymers, and functional group-modified polymers such as carboxyl groups of these various polymers.
  • the material constituting the anchor coat layer 5 is preferably a polyurethane resin, a polyester resin, a mixture of an aqueous polyurethane resin and a polyvinyl alcohol polymer, or an aqueous polyester resin.
  • a curing agent is blended in the resin.
  • the curing agent is not particularly limited as long as it is a compound reactive with the compounded resin.
  • a water dispersible polyisocyanate curing agent or the like is preferably used.
  • the thickness of the anchor coat layer 5 is not particularly limited as long as a uniform coating film can be formed, but is preferably 0.01 ⁇ m to 10 ⁇ m, and more preferably 0.05 ⁇ m to 5 ⁇ m. If the thickness of the anchor coat layer 5 is not less than the lower limit (0.01 ⁇ m) of the above range, a uniform film can be easily obtained, which is excellent in terms of adhesion to the support 1. If the thickness of the anchor coat layer 5 is not more than the upper limit (10 ⁇ m) of the above range, the anchor coat layer 5 has good flexibility (flexibility) and there is no possibility that the coating film will crack due to external factors. . From the viewpoint of adhesion and flexibility, the thickness of the anchor coat layer 5 is more preferably 0.05 to 5 ⁇ m.
  • the gas barrier packaging material 10 can be manufactured, for example, by a manufacturing method including the following steps ( ⁇ 1) and ( ⁇ 2).
  • ⁇ 1 A step of forming the anchor coat layer 5 by applying a coating liquid containing a resin on one surface of the support 1 and drying it.
  • ⁇ 2 A step of forming the barrier layer 3 by applying the coating liquid for gas barrier according to the present embodiment on the surface of the support 1 on which the anchor coat layer 5 is formed and drying it. If there is a commercial product in which the anchor coat layer 5 is formed on one surface, there is no problem even if it is used, and the step ( ⁇ 1) may be omitted.
  • the coating liquid (hereinafter also referred to as “coating liquid A”) used for forming the anchor coat layer 5 includes a resin and a solvent. You may include a hardening
  • the resin used for the coating liquid A is the same as the resin mentioned as the material constituting the anchor coat layer 5.
  • the solvent used in the coating liquid A is not particularly limited, and examples thereof include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, and dimethyl form.
  • the solid content concentration of the coating liquid A is preferably 0.5 to 50% by mass with respect to the total amount (100% by mass) of the coating liquid A from the viewpoint of coating suitability.
  • the various coating methods quoted by the above-mentioned process ((alpha) 1) can be used.
  • It does not specifically limit as a drying method For example, the various drying methods quoted at the above-mentioned process ((alpha) 1) can be used.
  • the drying temperature is not particularly limited, but when water or a mixed solvent of water and an organic solvent is used as a solvent, it is usually preferably 40 ° C. to 160 ° C.
  • the drying pressure is usually preferably normal pressure or reduced pressure, and preferably normal pressure from the viewpoint of facility simplicity.
  • Step ( ⁇ 2) The step ( ⁇ 2) can be performed in the same manner as the step ( ⁇ 1) in the first embodiment.
  • the step ( ⁇ 2) may be performed continuously from the step ( ⁇ 1), or may be performed discontinuously through a winding step and a curing step.
  • FIG. 3 is a cross-sectional view schematically showing a gas barrier packaging material according to a third embodiment of the present invention.
  • the gas barrier packaging material 30 according to the present embodiment includes a support 1, a lower barrier layer 7 stacked on one surface of the support 1, and an upper barrier layer 9 stacked on the lower barrier layer 7.
  • the upper barrier layer 9 is the same as the barrier layer 3 according to the first embodiment. That is, the gas barrier packaging material 20 is the same as the gas barrier packaging material 10 according to the first embodiment except that the lower barrier layer 7 is further provided between the support 1 and the barrier layer 3.
  • the lower barrier layer 7 may be the same as the upper barrier layer 9 or may be another barrier layer different from the upper barrier layer 9.
  • barrier layers include a layer formed by an evaporation method, a layer formed by a coating method such as the upper barrier layer 9, and the like.
  • the inorganic vapor deposition layer is mentioned as an example of the barrier layer formed by the vapor deposition method.
  • the inorganic vapor deposition layer is a layer of an inorganic material formed by a vapor deposition method.
  • the inorganic vapor-deposited layer is preferable for enhancing the gas barrier properties of the gas barrier packaging material 30, such as oxygen barrier properties, water vapor barrier properties, etc., in particular, water vapor barrier properties.
  • an inorganic material capable of constituting an inorganic vapor deposition layer for imparting gas barrier properties such as oxygen barrier properties and water vapor barrier properties is appropriately selected. Examples thereof include aluminum, aluminum oxide, magnesium oxide, silicon oxide, and tin oxide.
  • An inorganic material is used combining 1 type (s) or 2 or more types as needed.
  • the inorganic material is preferably at least one selected from the group consisting of aluminum, aluminum oxide, magnesium oxide and silicon oxide from the viewpoint of high gas barrier properties.
  • an aluminum oxide vapor deposition layer is formed by reactive vapor deposition, reactive sputtering, reactive ion plating, etc. in which a thin film is formed in the presence of a mixed gas of oxygen, carbon dioxide gas, and inert gas, using aluminum as a vapor deposition material. Can be formed.
  • Al: O 1: Should be 1.5.
  • the aluminum oxide vapor deposition layer becomes dense.
  • the aluminum oxide vapor deposition layer tends to be colored black and the light transmission amount tends to be low.
  • the gas barrier property is poor (because the density of the aluminum oxide vapor deposition layer is low), the light transmission amount is high and transparent. Silicon oxide is preferably used particularly when the inorganic vapor deposition layer requires water resistance.
  • the thickness of the inorganic vapor deposition layer varies depending on the use of the gas barrier packaging material 30 and the thickness of the second barrier layer 9, but is preferably 5 to 300 nm, and more preferably 10 to 50 nm.
  • the thickness of the inorganic vapor deposition layer is not less than the lower limit (5 nm) of the above range, the continuity of the inorganic vapor deposition layer is good and the gas barrier property is excellent.
  • the thickness of the inorganic vapor-deposited layer is not more than the upper limit (300 nm) of the above range, the inorganic vapor-deposited layer is excellent in flexibility (flexibility) and hardly cracks due to external factors such as bending and pulling.
  • the thickness of the inorganic vapor deposition layer is more preferably 10 to 50 nm.
  • the thickness of the inorganic vapor deposition layer can be calculated from the result of a calibration curve obtained by measuring a similar sample in advance with a transmission electron microscope (TEM) using, for example, a fluorescent X-ray analyzer.
  • TEM transmission electron microscope
  • barrier layers formed by the coating method examples include layers formed by coating a coating liquid containing a barrier resin and a solvent.
  • the coating liquid may contain a curing agent or the like as necessary.
  • barrier resins can be used as the barrier resin, and examples thereof include polyvinylidene chloride (PVDC) and polyvinyl alcohol (PVA).
  • the solvent is not particularly limited, and for example, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, toluene , Hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate and the like.
  • the solid content concentration of the coating liquid is preferably 0.5 to 50% by mass with respect to the total amount of the coating liquid (100% by mass).
  • the gas barrier packaging material 30 can be manufactured, for example, by a manufacturing method including the following steps ( ⁇ 1) and ( ⁇ 2).
  • ⁇ 1 A step of forming the lower barrier layer 7 on one surface of the support 1.
  • ⁇ 2 A process of forming the upper barrier layer 9 by applying the gas barrier coating liquid according to this embodiment on the surface of the support 1 on which the lower barrier layer 7 is formed and drying it.
  • Step ( ⁇ 1) When the lower barrier layer 7 is the same as the upper barrier layer 9, the step ( ⁇ 1) can be performed in the same manner as the step ( ⁇ 1) in the first embodiment.
  • the lower barrier layer 7 is another barrier layer different from the upper barrier layer 9, the other barrier layer can be formed by a known method. If the lower barrier layer 7 is another barrier layer and there is a commercially available product in which the lower barrier layer 7 is formed on one surface, there is no problem, and the step ( ⁇ 1) may be omitted.
  • the other barrier layer is a layer formed by a vapor deposition method (such as an inorganic vapor deposition layer)
  • various known vapor deposition methods can be used for the formation.
  • a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, and the like can be given.
  • the heating means (heating method) of the vacuum evaporation apparatus by the vacuum evaporation method an electron beam heating method, a resistance heating method, an induction heating method, or the like is preferably used.
  • a plasma assist method or an ion beam assist method can be used in addition to the above heating method.
  • reactive vapor deposition may be performed by blowing oxygen gas or the like.
  • a coating liquid for forming the barrier layer (for example, a coating liquid containing the above-described barrier resin and solvent) is applied onto the support 1 and dried. Can be formed. It does not specifically limit as a coating method of a coating liquid, For example, the various coating methods quoted by the above-mentioned process ((alpha) 1) can be used. It does not specifically limit as a drying method, For example, the various drying methods quoted at the above-mentioned process ((alpha) 1) can be used.
  • the drying temperature is not particularly limited, but when water or a mixed solvent of water and an organic solvent is used as a solvent, it is usually preferably 40 ° C. to 160 ° C.
  • the drying pressure is usually preferably normal pressure or reduced pressure, and preferably normal pressure from the viewpoint of facility simplicity.
  • the step ( ⁇ 2) can be performed in the same manner as the step ( ⁇ 1) in the first embodiment.
  • the gas barrier packaging material according to the present embodiment has been described with reference to the first to third embodiments, but the present invention is not limited to these embodiments.
  • Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other modifications of the configuration can be made without departing from the spirit of the present invention.
  • the barrier layer 3 may be laminated on both surfaces of the support 1.
  • the barrier layer 3 laminated on one surface and the barrier layer 3 laminated on the other surface may be the same or different.
  • the composition of the gas barrier coating solution used for each barrier layer, the thickness of each barrier layer, and the like may be different.
  • the anchor coat layer 5 in the second embodiment and the first barrier layer 7 and the second barrier layer 9 in the third embodiment may be laminated on both surfaces of the support 1.
  • the gas barrier packaging material according to the embodiment of the present invention may be composed of only the barrier layer 3.
  • the gas barrier packaging material according to the embodiment of the present invention may be laminated with other base materials for the purpose of imparting strength, providing sealing properties, providing easy opening at the time of sealing, providing design properties, providing light blocking properties, and the like. .
  • Other substrates are appropriately selected according to the purpose, but usually plastic films and papers are preferably used. Further, such plastic films and papers may be used alone, in a laminate of two or more, or may be used by laminating plastic films and papers.
  • a form of another base material For example, forms, such as a film, a sheet
  • these base materials from the viewpoint of laminating gas barrier packaging materials, films and sheets are preferable, and sheets before cup molding and flattened tubes are also preferable.
  • Examples of a method for laminating the gas barrier packaging material according to the present embodiment and another base material include a method of laminating by an laminating method using an adhesive. Specific examples of the laminating method include a dry laminating method, a wet laminating method, and an extrusion laminating method.
  • a printing layer or a vapor deposition layer of a metal or a silicon compound may be laminated from the viewpoints of designability, light blocking, moisture resistance, and the like.
  • the laminated surface of the gas barrier packaging material is preferably not disposed in the outermost layer of the laminate from the viewpoint of gas barrier properties. If the laminated surface of the gas barrier packaging material is disposed in the outermost layer of the laminate, the barrier layer and the like are scraped, causing a reduction in gas barrier properties.
  • the gas barrier packaging material according to the embodiment of the present invention, by providing the layer (I) (barrier layer 3) formed using the gas barrier coating liquid according to the present embodiment, the gas barrier packaging material is high even in a low humidity region. Excellent oxygen barrier properties even in a humidity range. That is, it is known that the polycarboxylic acid polymer exhibits a high oxygen barrier property in a low humidity region, but in a high humidity region, the molecular chain expands due to moisture absorption and the oxygen barrier property decreases.
  • the polycarboxylic acid polymer is a polyvalent metal salt (the polycarboxylic acid polymer is ion-crosslinked with a polyvalent metal), the molecular chain is difficult to expand, and the high humidity region But it shows excellent oxygen barrier properties.
  • the layer (I) can be formed by a simple process of applying a gas barrier coating liquid and drying. Therefore, a gas barrier packaging material can be manufactured with a general-purpose coating apparatus without performing a special process (for example, high-temperature and high-pressure processing such as retort processing). Moreover, since oxygen barrier property is expressed by one layer (I), a gas barrier packaging material can be manufactured in one step. Therefore, a gas barrier packaging material can be manufactured at low cost. Further, in the present embodiment, as described above, the content of the component (C) in the gas barrier coating liquid can be reduced as compared with the prior art, and the amount of heat required for drying in the manufacturing process of the gas barrier packaging material. Can be suppressed. Moreover, when ammonia is used as the volatile base, the irritating odor peculiar to ammonia in the production process can be suppressed by reducing the ammonia content.
  • the gas barrier packaging material according to this embodiment is susceptible to deterioration due to the influence of oxygen, etc., and the gas barrier packaging material for precision metal parts such as food, beverages, medicines, pharmaceuticals, and electronic parts Is preferably used.
  • Coating liquid A1 was prepared by the following procedure. Polyvinyl alcohol, a water-based polyurethane resin, a curing agent, and 2-propanol were blended so as to have the mass and solid content concentration shown in Table 1 to prepare a coating liquid A1.
  • As the polyvinyl alcohol Poval PVA117 (saponification degree 98% to 99%, polymerization degree 1700) manufactured by Kuraray Co., Ltd. was used.
  • As the aqueous polyurethane resin polyurethane dispersion Takelac WPB341 manufactured by Mitsui Chemicals, Inc. was used.
  • Takenate A56 diisocyanate
  • 2-propanol 2-propanol manufactured by Tokyo Chemical Industry Co., Ltd. was used.
  • Coating liquid A2 was prepared by the following procedure.
  • a water-based polyester resin, a curing agent and 2-propanol were blended so as to have the mass and solid content concentration shown in Table 2 to prepare a coating liquid A2.
  • As the water-based polyester resin pesresin A-647GEX solid content 20% by weight manufactured by Takamatsu Yushi Co., Ltd.) was used.
  • As a curing agent Duranate WT30-100 manufactured by Asahi Kasei Chemicals Corporation was used.
  • 2-propanol 2-propanol manufactured by Tokyo Chemical Industry Co., Ltd. was used.
  • Example 1 Polycarboxylic acid, zinc oxide, distilled water and 2-propanol were mixed at a blending ratio shown in Table 3 to prepare a coating liquid B1-1.
  • the blending amount of zinc oxide in the coating liquid B1-1 is such that the degree of neutralization of the polycarboxylic acid with zinc is 30 mol%.
  • Zinc oxide, aqueous ammonia, and ammonium hydrogen carbonate were mixed at a blending ratio shown in Table 4 to prepare a coating liquid B1-2.
  • Coating liquid B1-1 and coating liquid B1-2 were mixed to prepare coating liquid B1.
  • polycarboxylic acid polyacrylic acid (number average molecular weight 5,000, Wako first grade) manufactured by Wako Pure Chemicals was used.
  • As zinc oxide zinc oxide manufactured by Tokyo Chemical Industry Co., Ltd. was used.
  • As ammonia water ammonia water (25%, Wako first grade) manufactured by Wako Pure Chemical Industries, Ltd. was used.
  • As the ammonium hydrogen carbonate ammonium hydrogen carbonate (special grade reagent) manufactured by Wako Pure Chemical Industries, Ltd. was used.
  • As 2-propanol 2-propanol manufactured by Tokyo Chemical Industry Co., Ltd. was used.
  • Example 2 Polycarboxylic acid, zinc oxide, distilled water and 2-propanol were mixed at the blending ratio shown in Table 5 to prepare coating solution B2-1.
  • the blending amount of zinc oxide in the coating liquid B2-1 is such that the degree of neutralization of the polycarboxylic acid with zinc is 10 mol%.
  • Zinc oxide, aqueous ammonia and ammonium hydrogen carbonate were mixed at the blending ratio shown in Table 6 to prepare a coating liquid B2-2.
  • Coating liquid B2-1 and coating liquid B2-2 were mixed to prepare coating liquid B2.
  • the same materials as in Example 1 were used for polycarboxylic acid, zinc oxide, aqueous ammonia, ammonium hydrogen carbonate, and 2-propanol.
  • Example 1 Polycarboxylic acid, distilled water and 2-propanol were mixed at a blending ratio shown in Table 7 to prepare a coating liquid B3-1. Zinc oxide, aqueous ammonia and ammonium hydrogen carbonate were mixed at the blending ratio shown in Table 8 to prepare a coating liquid B3-2. Coating liquid B3-1 and coating liquid B3-2 were mixed to prepare coating liquid B3. The same materials as in Example 1 were used for polycarboxylic acid, zinc oxide, aqueous ammonia, ammonium hydrogen carbonate, and 2-propanol.
  • Example 2 Polycarboxylic acid, distilled water and 2-propanol were mixed at a blending ratio shown in Table 9 to prepare a coating liquid B4-1. Zinc oxide, aqueous ammonia, and ammonium hydrogen carbonate were mixed at a blending ratio shown in Table 10 to prepare a coating liquid B4-2. Coating liquid B4-1 and coating liquid B4-2 were mixed to prepare coating liquid B4. The same materials as in Example 1 were used for polycarboxylic acid, zinc oxide, aqueous ammonia, ammonium hydrogen carbonate, and 2-propanol.
  • Example 3 Polycarboxylic acid, sodium hydroxide, distilled water, and 2-propanol were mixed at a blending ratio shown in Table 11 to prepare a coating solution B5-1.
  • the blending amount of sodium hydroxide in the coating liquid B5-1 is such that the degree of neutralization of the polycarboxylic acid with sodium is 30 mol%.
  • Zinc oxide, aqueous ammonia, and ammonium hydrogen carbonate were mixed at a blending ratio shown in Table 12 to prepare a coating liquid B5-2.
  • Coating liquid B5-1 and coating liquid B5-2 were mixed to prepare coating liquid B5.
  • the same materials as in Example 1 were used for polycarboxylic acid, zinc oxide, aqueous ammonia, ammonium hydrogen carbonate, and 2-propanol.
  • Example 3 As a substrate, a biaxially stretched polypropylene film U-1 (thickness 20 ⁇ m) manufactured by Mitsui Chemicals, Inc. Toro Cello was used.
  • the coating liquid A1 was applied to one surface of the substrate with a bar coater (wet 6 ⁇ m) and dried in an oven at 80 ° C. for 1 minute to form an anchor coat layer (A1 layer) having a thickness of 0.2 ⁇ m.
  • the coating liquid B1 is applied by a bar coater (wet 12 ⁇ m) and dried in an oven at 80 ° C. for 1 minute, and a barrier layer having a thickness of 0.6 ⁇ m (B1 layer) was formed, and the gas barrier packaging material of Example 3 was obtained, which was laminated in the order of base material / anchor coat layer / barrier layer.
  • Example 4 The gas barrier packaging material of Example 3 was laminated with a polypropylene film through an adhesive using Multicoater TM-MC manufactured by HIRANO TECSEED, and laminated in the order of gas barrier packaging material / adhesive / polypropylene film.
  • a laminate film of Example 4 was obtained. Here, it arrange
  • a two-component curable adhesive Takelac A620 (main agent) / Takenate A65 (curing agent) manufactured by Mitsui Chemicals Polyurethanes was used.
  • polypropylene film polypropylene film Treffan ZK93KM (thickness 60 ⁇ m) manufactured by Toray Film Processing Co., Ltd. was used.
  • Example 5 A gas barrier packaging material of Example 5 was obtained in the same manner as Example 3 except that the coating liquid A2 was used instead of the coating liquid A1 and the coating liquid B2 was used instead of the coating liquid B1.
  • Example 6 Implemented except that a biaxially stretched polyethylene terephthalate film Lumirror P60 (thickness 12 ⁇ m) manufactured by Toray Industries, Inc. was used instead of the biaxially stretched polypropylene film U-1 (thickness 20 ⁇ m) manufactured by Mitsui Chemicals Tosero Co., Ltd. In the same manner as in Example 3, the gas barrier packaging material of Example 6 was obtained.
  • Example 7 Example 3 except that instead of a biaxially stretched polypropylene film U-1 (thickness 20 ⁇ m) manufactured by Mitsui Chemicals Tosero Co., Ltd., a stretched nylon film emblem ONMB (thickness 15 ⁇ m) manufactured by Unitika was used as the substrate. Similarly, the gas barrier packaging material of Example 7 was obtained.
  • Example 8 As the base material, instead of the biaxially stretched polypropylene film U-1 (thickness 20 ⁇ m) manufactured by Mitsui Chemicals Tosero, a biaxially stretched polyethylene terephthalate film Lumirror P60 (thickness 12 ⁇ m) manufactured by Toray is used, and the anchor coat layer is used.
  • a gas barrier packaging material of Example 8 was obtained in the same manner as in Example 3 except that the (A1 layer) was not formed and the barrier layer (B1 layer) was formed directly on the substrate.
  • Example 9 A laminate film of Example 9 was obtained in the same manner as in Example 4 except that the gas barrier packaging material described in Example 8 was used instead of the gas barrier packaging material of Example 3.
  • Example 10 As the base material, instead of the biaxially stretched polypropylene film U-1 (thickness 20 ⁇ m) manufactured by Mitsui Chemicals Tosero, a biaxially stretched polyethylene terephthalate film Lumirror P60 (thickness 12 ⁇ m) manufactured by Toray is used, and the anchor coat layer is used.
  • Example 10 is the same as Example 3 except that the (A1 layer) is not formed and the barrier layer (B2 layer) is formed directly on the substrate using the coating liquid B2 instead of the coating liquid B1. A gas barrier packaging material was obtained.
  • Example 11 Polyethylene film TUX-TCS (thickness 60 ⁇ m) made by Mitsui Chemicals Tosero Co., Ltd. was used instead of polypropylene film Treffan ZK93KM (thickness 60 ⁇ m) made by Toray Film Processing Co., Ltd., instead of the gas barrier packaging material of Example 3
  • a laminate film of Example 11 was obtained in the same manner as in Example 4 except that the gas barrier packaging material of Example 10 was used.
  • Comparative Example 4 A gas barrier packaging material of Comparative Example 4 was obtained in the same manner as in Example 3 except that the coating liquid B3 was used instead of the coating liquid B1.
  • Comparative Example 5 A laminated film of Comparative Example 5 was obtained in the same manner as in Example 4 except that the gas barrier packaging material described in Comparative Example 4 was used instead of the gas barrier packaging material of Example 3.
  • Comparative Example 6 A gas barrier packaging material of Comparative Example 6 was obtained in the same manner as in Example 3 except that the coating liquid B4 was used instead of the coating liquid B1.
  • Comparative Example 7 A gas barrier packaging material of Comparative Example 7 was obtained in the same manner as in Example 8 except that the coating liquid B5 was used instead of the coating liquid B1.
  • Comparative Example 8 A laminated film of Comparative Example 8 was obtained in the same manner as Example 11 except that the gas barrier packaging material described in Comparative Example 7 was used instead of the gas barrier packaging material of Example 3.
  • the oxygen permeability of the obtained gas barrier packaging material and laminate film was measured under the conditions of a temperature of 30 ° C. and a relative humidity of 70% using an oxygen permeation tester OXTRAN (registered trademark) 2/20 manufactured by Modern Control. did. The results are shown in Table 14. The measuring method was based on ASTM F1927-98 (2004), and the measured value was expressed in the unit cm 3 (STP) / (m 2 ⁇ day ⁇ MPa).
  • STP means standard conditions (0 ° C., 1 atm) for defining the volume of oxygen.
  • the coating liquids B1 and B2 obtained in Examples 1 and 2 were excellent in liquid stability. Further, the gas barrier packaging materials and laminate films of Examples 3 to 11 obtained using these coating liquids have lower oxygen permeability and gas barrier properties than the gas barrier packaging materials of Comparative Examples 4 to 8. It was excellent.
  • the coating liquid B4 of Comparative Example 2 in which partial neutralization of the polycarboxylic acid was not performed in advance had poor liquid stability.
  • the gas barrier packaging material of Comparative Example 6 obtained using the coating liquid B4 had a very high oxygen permeability.
  • the coating liquid B5 of Comparative Example 3 in which the polycarboxylic acid was partially neutralized using sodium hydroxide instead of zinc oxide had good liquid stability, the comparison obtained using the coating liquid B5
  • the gas barrier packaging material of Example 7 and the laminate film of Comparative Example 8 had very high oxygen permeability and low gas barrier properties.
  • the coating liquid B3 of Comparative Example 1 containing the most ammonia water had good liquid stability. However, it is not preferable that the content of ammonia is large because of the influence on the working environment described above. Further, the gas barrier properties of the gas barrier packaging material of Comparative Example 4 and the laminate film of Comparative Example 5 obtained using the coating liquid B3 were inferior to those of Examples 4 to 8.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

La présente invention concerne un procédé de fabrication d'une barrière contre les gaz, dans lequel : une première solution comprend un polymère à base d'acide polycarboxylique, un premier ion de métal polyvalent et un premier solvant et est préparée de sorte que la teneur en premier ion de métal polyvalent est une quantité qui neutralise une partie du groupe carboxyle du polymère à base d'acide polycarboxylique ; une seconde solution comprend un second ion de métal polyvalent, une base ou un acide volatil à l'exclusion de l'acide carbonique, un ion carbonate et un second solvant ; et la première solution et la seconde solution sont mélangées afin d'obtenir un liquide de revêtement formant barrière contre les gaz.
PCT/JP2015/084391 2014-12-08 2015-12-08 Procédé de fabrication d'un liquide de revêtement formant barrière contre les gaz et matériau d'emballage formant barrière contre les gaz WO2016093225A1 (fr)

Applications Claiming Priority (2)

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JP2014-247718 2014-12-08
JP2014247718A JP6497052B2 (ja) 2014-12-08 2014-12-08 ガスバリア用塗液の製造方法、ガスバリア用塗液およびガスバリア性包装材料

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003091317A1 (fr) * 2002-04-23 2003-11-06 Kureha Chemical Industry Company, Limited Film et procede de production
JP2005126539A (ja) * 2003-10-22 2005-05-19 Kureha Chem Ind Co Ltd 高防湿性フィルム、及びその製造方法
JP2006219518A (ja) * 2005-02-08 2006-08-24 Toyo Ink Mfg Co Ltd ガスバリア性塗料及び該塗料を用いてなるガスバリア性積層体
JP2009006707A (ja) * 2007-05-29 2009-01-15 Kureha Corp ガスバリア性前駆積層体、ガスバリア性積層体およびこれらの製造方法
WO2014073482A1 (fr) * 2012-11-07 2014-05-15 凸版印刷株式会社 Liquide de revêtement pour une barrière contre les gaz, article stratifié de barrière contre les gaz, matière d'emballage, et matière d'emballage pour thermostérilisation
WO2015174492A1 (fr) * 2014-05-15 2015-11-19 凸版印刷株式会社 Matériau d'emballage formant barrière contre les gaz

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003091317A1 (fr) * 2002-04-23 2003-11-06 Kureha Chemical Industry Company, Limited Film et procede de production
JP2005126539A (ja) * 2003-10-22 2005-05-19 Kureha Chem Ind Co Ltd 高防湿性フィルム、及びその製造方法
JP2006219518A (ja) * 2005-02-08 2006-08-24 Toyo Ink Mfg Co Ltd ガスバリア性塗料及び該塗料を用いてなるガスバリア性積層体
JP2009006707A (ja) * 2007-05-29 2009-01-15 Kureha Corp ガスバリア性前駆積層体、ガスバリア性積層体およびこれらの製造方法
WO2014073482A1 (fr) * 2012-11-07 2014-05-15 凸版印刷株式会社 Liquide de revêtement pour une barrière contre les gaz, article stratifié de barrière contre les gaz, matière d'emballage, et matière d'emballage pour thermostérilisation
WO2015174492A1 (fr) * 2014-05-15 2015-11-19 凸版印刷株式会社 Matériau d'emballage formant barrière contre les gaz

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