WO2021157557A1 - Film barrière contre les gaz, film stratifié et emballage - Google Patents

Film barrière contre les gaz, film stratifié et emballage Download PDF

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Publication number
WO2021157557A1
WO2021157557A1 PCT/JP2021/003684 JP2021003684W WO2021157557A1 WO 2021157557 A1 WO2021157557 A1 WO 2021157557A1 JP 2021003684 W JP2021003684 W JP 2021003684W WO 2021157557 A1 WO2021157557 A1 WO 2021157557A1
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Prior art keywords
layer
gas barrier
film
test
acid
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PCT/JP2021/003684
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English (en)
Japanese (ja)
Inventor
龍之介 塩田
竜之 小市
秀成 金高
明子 天野
将徳 澤田
大滝　浩幸
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大日本印刷株式会社
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Priority to JP2021575797A priority Critical patent/JPWO2021157557A1/ja
Publication of WO2021157557A1 publication Critical patent/WO2021157557A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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

Definitions

  • the present invention relates to a gas barrier film, a laminated film, and a package.
  • Materials and films are required.
  • food packaging materials are required to have a function of suppressing deterioration of contents due to oxidation, maintaining freshness and maintaining aroma.
  • pharmaceutical packaging materials a function of preventing deterioration of the active ingredient of the contents is required.
  • precision electronic parts in order to suppress corrosion of metal parts and prevent insulation defects, a function of preventing the influence of oxygen permeating the packaging material is required. Factors that cause these alterations and deterioration include oxygen, moisture, light, and heat, but the most important factor is oxidative deterioration due to oxygen.
  • an inorganic oxide such as silicon oxide or aluminum oxide is formed on a film substrate by a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, or the like.
  • Transparent gas barrier films are attracting attention.
  • a transparent gas barrier film is generally a film in which an inorganic oxide is vapor-deposited on a substrate surface made of a biaxially stretched polyester film having excellent transparency and rigidity.
  • the inorganic oxide layer may crack due to rubbing or stretching during post-processing printing or laminating, filling of the contents, or due to bending during processing or transportation. There was a problem that the gas barrier performance became unstable.
  • a layer (A) containing an alkaline compound of a polyvalent metal is formed on at least one surface of a plastic base material, and then a polycarboxylic acid-based polymer is contained in a solvent containing at least water.
  • the dissolved solution (b) is applied to the layer (A) containing the alkaline compound of the polyvalent metal, and then heat treatment is performed to remove the solvent, so that the solution (b) is composed of polyvalent metal ions.
  • a method for producing a gas barrier laminate which comprises forming a metal ion crosslinked structure between the carboxy groups in the medium, is described.
  • a polyvalent metal compound-containing layer (B) is provided on one or both sides of a polymer layer (A) containing a carboxy group-containing polymer and a polyvalent metal salt of the carboxy group-containing polymer.
  • a multilayer film having an adjacent layer structure (1) the polymer layer (A) does not contain polyalcohols, and the polymer constituting the polymer layer (A) contains a carboxy group. It is only a polymer, and (2) the polymer layer (A) is adjacent to the polyvalent metal compound-containing layer (B) in which the concentration of the carboxy group-containing polymer polyvalent metal salt in the polymer layer (A) is high.
  • the oxygen permeability of the multilayer film is 30 ° C. and 0 relative humidity. %, And a gas barrier multilayer film having a temperature of 30 ° C. and a relative humidity of 80% or less of 500 cm 3 (STP) / (m2 ⁇ day ⁇ MPa) or less has been described.
  • the gas barrier laminate produced by the production method of Patent Document 1 is obtained by laminating a polyurethane layer (white) in which basic fine particles are dispersed and a polycarboxylic acid layer (colorless and transparent) in the production method. A neutralization reaction occurs at the interface between the two layers, making the laminate transparent, but some white remains due to uneven layer thickness, and heat shrinkage due to the heat of neutralization is likely to occur, causing transparency and wrinkles. There is a problem in.
  • the gas barrier laminate produced by the production method of Patent Document 1 has a problem that the gas barrier property is significantly deteriorated after the bending test (Gelboflex test).
  • the gas barrier multilayer film of Patent Document 2 has a problem that the gas barrier property at the initial stage of production is insufficient and the gas barrier property is significantly deteriorated after the bending test (Gelboflex test).
  • the present invention has been made in view of the above circumstances, and has high gas barrier properties and transparency from the initial stage of production, and the gas barrier properties are unlikely to deteriorate even after a wet heat treatment and a gelboflex test after the wet heat treatment.
  • a primary object is to provide a gas barrier film, a laminated film, and a package provided with the laminated film.
  • the gas barrier film of the present invention has a base material and A layer (A) containing a cured product of an epoxy resin having four or more epoxy groups in one molecule, and Adjacent to the layer (A), there is a layer (B) containing a polycarboxylic acid-based polymer and a magnesium salt of the polycarboxylic acid-based polymer.
  • the layer thickness of the layer (B) is 120 nm or more and 240 nm or less.
  • the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% is preferably 1.00 cc / m 2 ⁇ day ⁇ atm or less from the viewpoint of having high gas barrier properties from the initial stage of production. ..
  • the first laminated film of the present invention comprises a base material, a layer (A) containing a cured product of an epoxy resin having four or more epoxy groups in one molecule, and a layer (A) adjacent to the layer (A).
  • a gas barrier film having a layer (B) containing a polycarboxylic acid-based polymer and a magnesium salt of the polycarboxylic acid-based polymer, and having a layer thickness of 120 nm or more and 240 nm or less. When, It has a sealant layer.
  • the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% after the boiling test is 1.00 cc / m 2 ⁇ day ⁇ atm or less
  • the gelboflex test was performed under the conditions of ASTM F392-compliant temperature of 23 ° C. and relative humidity of 50%, and then the oxygen permeability at a temperature of 23 ° C. and relative humidity of 60% was 1.00 cc / m. It is preferably 2 ⁇ day ⁇ atm or less from the viewpoint that the gas barrier property does not easily deteriorate even after the wet heat treatment and the gelboflex test after the wet heat treatment.
  • the peel strength after the boil test is 3.0 N / 15 mm or more and is 3.0 N / 15 mm or more in the T-shaped peel test based on JIS K6854-3.
  • the peel strength measured by adhering water to the peel surface is preferably 3.0 N / 15 mm or more in the T-shaped peel test based on JIS K6854-3 from the viewpoint of durability.
  • the second laminate film of the present invention comprises a base material, a layer (A') containing a cured product of an epoxy resin, and a polycarboxylic acid-based polymer and the polycarboxylic acid adjacent to the layer (A').
  • a gas barrier film having a layer (B') containing a polyvalent metal salt of an acid polymer and having a layer thickness of 120 nm or more and 240 nm or less. Has a sealant layer and After the boil test, the oxygen permeability at a temperature of 23 ° C.
  • a relative humidity of 60% is 1.00 cc / m 2 ⁇ day ⁇ atm or less
  • the gelboflex test was performed under the conditions of ASTM F392-compliant temperature of 23 ° C. and relative humidity of 50%, and then the oxygen permeability at a temperature of 23 ° C. and relative humidity of 60% was 1.00 cc / m. 2 ⁇ day ⁇ atm or less
  • the peel strength after the boil test is 3.0 N / 15 mm or more and is 3.0 N / 15 mm or more in the T-shaped peel test based on JIS K6854-3.
  • the peel strength measured by adhering water to the peel surface is 3.0 N / 15 mm or more in the T-shaped peel test based on JIS K6854-3.
  • the package of the present invention is characterized by including the first laminated film of the present invention or the second laminated film.
  • the present invention has high gas barrier properties and transparency from the initial stage of production, and the gas barrier properties are unlikely to deteriorate even after a wet heat treatment and a gelboflex test. Can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of the gas barrier film of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of a laminated film containing the gas barrier film of the present invention.
  • FIG. 3 is a schematic cross-sectional view illustrating a method of a peeling test of a laminated film.
  • FIG. 4 is a schematic cross-sectional view illustrating a method of a peeling test of a laminated film.
  • FIG. 5 is a diagram showing changes in tensile stress with respect to the interval S between the grippers 31 and 32 during the peeling test of the laminated film.
  • FIG. 6 shows the result of element distribution analysis by EDX (Energy Dispersive X-ray Analysis) of Example 3.
  • the gas barrier film of the present invention has a base material and A layer (A) containing a cured product of an epoxy resin having four or more epoxy groups in one molecule, and Adjacent to the layer (A), there is a layer (B) containing a polycarboxylic acid-based polymer and a magnesium salt of the polycarboxylic acid-based polymer.
  • the layer thickness of the layer (B) is 120 nm or more and 240 nm or less.
  • FIG. 1 is a schematic cross-sectional view showing an example of the gas barrier film of the present invention.
  • the gas barrier film 10 of the present invention has a base material 11, the layer (A) 12, and the layer (B) 13 adjacent to the layer (A) 12.
  • the layer thickness of the layer (B) 13 is within the specific range.
  • the gas barrier film of the present invention has a layer (A) containing a cured product of an epoxy resin having four or more epoxy groups in one molecule, and a polycarboxylic acid-based polymer adjacent to the layer (A). It has a layer (B) containing the polycarboxylic acid polymer and a magnesium salt of the polycarboxylic acid polymer, and the layer thickness of the layer (B) is 120 nm or more and 240 nm or less, so that a high gas barrier property is obtained from the initial stage of production. As a laminated film, the gas barrier property is unlikely to deteriorate even after a wet heat treatment and a gelboflex test.
  • the layer (A) used in the present invention contains a cured product of an epoxy resin having four or more epoxy groups in one molecule, so that the crosslink density is increased and the gas barrier property is improved.
  • the layer (B) used in the present invention has a specific layer thickness and contains a magnesium salt of a polycarboxylic acid-based polymer, so that the polycarboxylic acid-based polymer has a crosslinked structure with magnesium. The gas barrier property is improved by the existence.
  • the epoxy group of the epoxy resin having four or more epoxy groups in one molecule of the layer (A) and the carboxy group of the polycarboxylic acid-based polymer of the layer (B) are formed in the layer (A) and the layer (A).
  • the interfacial adhesion between the layer (A) and the layer (B) is improved, and the cross-linking density at the interface is increased to improve the gas barrier property. It is estimated that the gas barrier property is unlikely to deteriorate even after the flex test. If the layer thickness of the layer (B) is smaller than the specific range, the gas barrier property of the layer becomes insufficient, and if the layer thickness of the layer (B) is larger than the specific range, moisture absorption becomes easy and the layer becomes easy to absorb.
  • the gas barrier property deteriorates due to insufficient density, the gas barrier property deteriorates after the Gelboflex test, and the interfacial adhesion between the layers (A) and (B) becomes insufficient, resulting in wet heat treatment. It is presumed that the layer (B) will be easily peeled off later.
  • the layer (A) and the layer (B) having a specific layer thickness adjacent to each other, high gas barrier properties are obtained from the initial stage of production due to the synergistic effect of each of these layers and the interface between the layers. It is presumed that the gas barrier property, which is hard to deteriorate even after the wet heat treatment and the gelboflex test, was realized.
  • the magnesium salt of the polycarboxylic acid polymer can be formed in advance, unevenness and heat shrinkage are unlikely to occur in the laminating process, and the film is a thin film, so that the gas barrier There is also an advantage that the appearance tends to be good without impairing the transparency of the sex film, the laminated film, and the packaging body provided with the laminated film.
  • the base material, each layer, and the like contained in the gas barrier film of the present invention will be described in order.
  • the base material used for the gas barrier film of the present invention is a resin film or sheet resin that satisfies the mechanical, physical, chemical strength, heat resistance, and texture required for the packaging material of the contents to be filled and packaged.
  • the base material can be arbitrarily selected.
  • polyolefin resins such as polyethylene resins, polypropylene resins, cyclic polyolefin resins, fluorine resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), and acrylonitrile-butadiene-styrene copolymers.
  • Polyester resins such as (ABS resin), polyvinyl chloride resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, polyethylene furanolate, etc., various nylons Polyamide resin, polyimide resin, polyamideimide resin, polyarylphthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose type Various resin films or sheets such as resins and mixtures thereof can be used.
  • the base material may have a single-layer structure or, for example, a laminated structure of two or more layers by simultaneous melt extrusion or other lamination.
  • a film or sheet of a polyamide resin such as various nylons, a polyester resin, or a polyolefin resin is preferably used from the viewpoint of gas barrier property, durability, and versatility.
  • various resin films or sheets used for the base material may contain pigments, antioxidants, antistatic agents, ultraviolet absorbers, lubricants, plasticizers, color inhibitors, matting agents, and erasing agents, if necessary. It may contain one or more additives such as odorants, flame retardants, weather resistant agents, thread friction reducing agents, mold release agents, ion exchangers, inorganic compounds such as inorganic oxides, and inorganic layered compounds. ..
  • the thickness of the various resin films or sheets used for the base material may be appropriately selected depending on the packaging material of the contents to be filled and packaged, and is not particularly limited, but is usually 3 to 200 ⁇ m, preferably 9. It is ⁇ 100 ⁇ m.
  • the layer (A) contains a cured product of an epoxy resin having four or more epoxy groups in one molecule. That is, the layer (A) contains a reaction product of an epoxy resin having four or more epoxy groups in one molecule and an epoxy resin curing agent.
  • Epoxy resins having four or more epoxy groups in one molecule include saturated or unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, heterocyclic compounds, or combinations thereof.
  • the epoxy group may be included, for example, as a glycidyl group, an alicyclic epoxy group such as 3,4-epoxycyclohexyl, or an epoxy group directly bonded to an alicyclic skeleton.
  • Examples of the epoxy resin having four or more epoxy groups in one molecule include saturated or unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, heterocyclic compounds, and combinations thereof.
  • an epoxy resin having a glycidylamine moiety derived from xylylene diamine such as metaxylylene diamine an epoxy resin having a glycidylamine moiety derived from 1,3-bis (aminomethyl) cyclohexane, and diamino.
  • an aliphatic polyvalent carboxylic acid such as an epoxy resin having an ether moiety, tetra (3,4-epoxycyclohexylmethyl) modified ⁇ -caprolactone, and tetra (3,4-epoxycyclohexylmethyl) ethanetetracarboxylate.
  • Compound with 3,4-epoxycyclohexylmethyl moiety; 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol eg, EHPE3150: Dicel
  • the average number of epoxy groups in one molecule is 15); and a polymer containing an epoxy group in a repeating unit can be mentioned.
  • an epoxy resin containing an aromatic ring or an aliphatic ring in the molecule is preferable, and an epoxy resin containing an aromatic ring in the molecule has improved gas barrier properties. It is more preferable from the viewpoint of Specifically, for example, N, N, N', N'-tetraglycidyl metaxylylenediamine, N, N, N', N'-tetraglycidyl-4,4'-aminodiphenylmethane, N, N, N' , N'-tetraglycidyl-4,4- (4-aminophenyl) -p-diisopyrbenzene, 1,1,2,2- (tetraglycidyloxyphenyl) ethane, 1,1,2,2-tetrabis (Hydroxyphenyl) ethanetetraglycidyl ether, tetraglycidyl-1,3-bisaminomethylcyclohexan
  • the epoxy resin used for the layer (A) of the present invention includes an epoxy resin having a glycylylenediamine-derived glycylylenediamine moiety and 1,3-bis (aminomethyl) from the viewpoint of improving gas barrier properties. It is preferable to contain at least one selected from the group consisting of epoxy resins having a glycidylamine moiety derived from cyclohexane as a main component, and further, an epoxy resin having a glycylylenediamine moiety derived from m-xylylenediamine.
  • the content as the main component means that the epoxy resin contained in the layer (A) is contained in an amount of 50% by mass or more, preferably 70% by mass or more, and 90% by mass or more. It is more preferable, and it may be 100% by mass.
  • the epoxy resin contained in the layer (A) preferably contains an epoxy resin having four or more epoxy groups in one molecule as a main component, preferably 70% by mass or more, and 90% by mass or more. Is more preferable, and may be 100% by mass.
  • the epoxy resin contained in the layer (A) may contain an epoxy resin having three or less epoxy groups in one molecule as long as the effects of the present invention are not impaired.
  • the epoxy resin having three or less epoxy groups in one molecule may be an epoxy resin having two or more epoxy groups in one molecule.
  • a conventionally known epoxy resin can be appropriately selected and used.
  • an epoxy resin having a glycidylamine moiety and / or a glycidyl ether moiety derived from paraaminophenol an epoxy resin having a glycidyl ether moiety derived from bisphenol A
  • an epoxy resin having a glycidyl ether moiety derived from bisphenol F examples thereof include an epoxy resin having a glycidyl ether moiety derived from resorcinol.
  • the epoxy resin used in the present invention can be produced by a conventionally known production method, and is obtained by reacting various alcohols, phenols and amines with epihalohydrin.
  • an epoxy resin having a glycidylamine moiety derived from m-xylylenediamine can be obtained by adding epichlorohydrin to m-xylylenediamine.
  • a commercially available product may be appropriately selected and used.
  • the epoxy resin curing agent used for curing the epoxy resin may be any of an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound or a combination thereof, and polyamines, etc.
  • Commonly used epoxy resin curing agents such as phenols, acid anhydrides or carboxylic acids can be used.
  • aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine
  • aliphatic amines having an aromatic ring such as m-xylylenediamine and paraxylylenediamine
  • 1,3- Examples thereof include alicyclic amines such as bis (aminomethyl) cyclohexane, isophoronediamine and norbornenediamine, and aromatic amines such as diaminodiphenylmethane and metaphenylenediamine.
  • a modified reaction product with an epoxy resin or a monoglycidyl compound using these polyamines as a raw material, an addition reaction product with epichlorohydrin, and a reaction with these polyamines can form an amide group moiety to form an oligomer, at least.
  • Reaction products with at least one valent carboxylic acid and carboxylic acid derivative can be used.
  • phenols include polysubstituted monomers such as catechol, resorcinol and hydroquinone, and resor-type phenol resins.
  • acid anhydrides or carboxylic acids include aliphatic acid anhydrides such as dodecenyl succinic anhydride and polyadipic anhydride, and alicyclic acid anhydrides such as (methyl) tetrahydrophthalic anhydride and (methyl) hexahydrophthalic anhydride.
  • Aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and carboxylic acids thereof can be used.
  • an epoxy resin curing agent containing an aromatic ring in the molecule is preferable, and an epoxy resin curing agent containing the skeleton structure represented by the chemical formula (1) in the molecule is more preferable.
  • reaction products of (I) and (II) or reaction products of (I), (II) and (III) are produced. It is particularly preferable to use a thing.
  • a polyfunctional compound having at least one acyl group capable of forming an amide group moiety and forming an oligomer by reaction with a metaxylylene diamine or a paraxylylene diamine (II) polyamine (III) having 1 to 1 carbon atoms. At least one of 8 monovalent carboxylic acids and carboxylic acid derivatives
  • Examples of the polyfunctional compound having at least one acyl group capable of forming an amide group moiety and forming an oligomer by the reaction with the polyamine (II) described above include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and succinic acid.
  • Carboxylic acids such as malic acid, tartaric acid, adipic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid and their derivatives such as esters, amides, acid anhydrides, acidified compounds and the like, especially acrylic acids.
  • Methacrylic acid and derivatives thereof are preferred.
  • Examples of the monovalent carboxylic acid having 1 to 8 carbon atoms in (III) include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, benzoic acid and the like, and derivatives thereof, for example, esters. , Amides, acid anhydrides, acidifieds and the like can also be used. These may be reacted with a polyamine (methoxylylenediamine or paraxylylenediamine) in combination with the above-mentioned polyfunctional compound.
  • a polyamine methoxylylenediamine or paraxylylenediamine
  • the reaction ratio in the reaction for synthesizing the epoxy resin curing agent is preferably adjusted in terms of the content of the amide group from the viewpoint of gas barrier property and adhesiveness, and the molar of the polyfunctional compound with respect to the polyamine component.
  • the ratio is preferably in the range of 0.3 to 0.95.
  • the mixing ratio of the epoxy resin forming the layer (A) of the present invention and the epoxy resin curing agent may be appropriately adjusted, and will be described in detail in the production method described later.
  • the epoxy group contained in the layer (A) of the present invention undergoes a cross-linking reaction with the carboxy group contained in the layer (B) at the interface adjacent to the layer (B), at least the layer (A) It is preferable to add an epoxy resin curing agent so that the epoxy group remains at the interface of the above.
  • the layer (A) of the present invention may contain 80% by mass or more of the reaction product of the epoxy resin and the epoxy resin derived from the epoxy resin curing agent and the epoxy resin curing agent with respect to the entire layer (A). It is preferably contained in an amount of 90% by mass or more, more preferably 90% by mass or more.
  • the layer (A) of the present invention may further contain other components as long as the effects of the present invention are not impaired.
  • Other components include, for example, other resins such as surfactants, inorganic fillers, antioxidants, tackifier resins, silane coupling agents, oxygen absorbers, deodorants, flame retardants, UV absorbers, weather resistant agents. , Light retardants, antibacterial / bactericidal agents, etc.
  • the layer (A) of the present invention basically does not need to contain magnesium ions or magnesium compounds contained in the layer (B), and magnesium ions to be formed except in the vicinity of the interface with the layer (B). Magnesium compounds need not be included.
  • the layer (A) of the present invention may contain an anion derived from a magnesium compound used for forming the magnesium salt contained in the layer (B). Anions derived from magnesium compounds can be removed during production but can remain. Examples of the anion derived from the magnesium compound include chloride ion, nitrate ion, sulfate ion, carbonate ion, acetate ion, phosphate ion and the like. Further, an ion scavenger for capturing anions derived from these magnesium compounds may be further contained.
  • the layer thickness of the layer (A) has a high gas barrier property from the initial stage of production, and the gas barrier property deteriorates even after the wet heat treatment and further after the gelboflex test, and the layer peeling after the wet heat treatment is suppressed.
  • the lower limit is preferably 250 nm or more, and more preferably 300 nm or more.
  • the upper limit is preferably 3000 nm or less, more preferably 2500 nm or less, and may be 900 nm or less.
  • the layer (B) is located adjacent to the layer (A) and contains a polycarboxylic acid-based polymer and a magnesium salt of the polycarboxylic acid-based polymer.
  • the polycarboxylic acid-based polymer used in the present invention is a polymer having two or more carboxy groups in the molecule. Since the layer (B) is located adjacent to the layer (A), the carboxy group of the polycarboxylic acid polymer in the layer (B) and the tetrafunctional or higher functional epoxy resin in the layer (A). The epoxy group undergoes a three-dimensional cross-linking reaction at the interface between the layer (B) and the layer (A) to improve the interlayer adhesion and the gas barrier property. Further, in the layer (B), since the polycarboxylic acid-based polymer is crosslinked with magnesium ions, the gas barrier property is improved.
  • polycarboxylic acid-based polymer examples include a homopolymer of a carboxy group-containing unsaturated monomer, a copolymer of a carboxy group-containing unsaturated monomer, a carboxy group-containing unsaturated monomer and other polymerizable single amounts. Typical examples are copolymers with the body and polysaccharides containing a carboxy group in the molecule (also referred to as "acidic polysaccharides").
  • the carboxy group includes not only a free carboxy group but also an acid anhydride group (specifically, a dicarboxylic acid anhydride group).
  • the acid anhydride group may be partially ring-opened to form a carboxy group.
  • Some of the carboxy groups may be neutralized with alkali. In this case, the degree of neutralization is preferably 20% or less.
  • a graft polymer obtained by graft-polymerizing a carboxy group-containing unsaturated monomer to a carboxy group-free polymer such as polyolefin can also be used as a polycarboxylic acid-based polymer.
  • a polymer having a hydrolyzable ester group such as an alkoxycarbonyl group (for example, a methoxycarbonyl group) can be hydrolyzed and converted into a carboxy group, and the polymer can be used as a polycarboxylic acid-based polymer.
  • the polycarboxylic acid-based polymer includes a homopolymer of ⁇ , ⁇ -monoethylene unsaturated carboxylic acid, a copolymer of two or more kinds of ⁇ , ⁇ -monoethylene unsaturated carboxylic acid, and ⁇ , It contains a copolymer of a ⁇ -monoethylene unsaturated carboxylic acid and another polymerizable monomer.
  • the other polymerizable monomer an ethylenically unsaturated monomer is typical.
  • Examples of the ⁇ , ⁇ -monoethyl unsaturated carboxylic acid include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; and maleic anhydride.
  • unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid
  • unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid
  • maleic anhydride such as itaconic anhydride
  • At least one ⁇ , ⁇ -monoethyl unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid is preferable, and acrylic acid and methacrylic acid are preferable.
  • At least one ⁇ , ⁇ -monoethyl unsaturated carboxylic acid selected from the group consisting of acid and maleic acid is more preferable.
  • polymerizable monomers copolymerizable with ⁇ , ⁇ -monoethylous unsaturated carboxylic acids especially ethylenically unsaturated monomers
  • ethylene propylene, 1-butene, 1-pentene, 1 - ⁇ -olefins such as hexene and 1-octene
  • saturated carboxylic acid vinyl esters such as vinyl acetate
  • alkyl acrylate esters such as methyl acrylate and ethyl acrylate
  • alkyl methacrylates such as methyl methacrylate and ethyl methacrylate.
  • Chlorine-containing vinyl monomers such as vinyl chloride and vinylidene chloride
  • Fluorine-containing vinyl monomers such as vinyl fluoride and vinylidene fluoride
  • Unsaturated nitriles such as acrylonitrile and methacrylonitrile
  • Styrene and ⁇ -methyl Aromatic vinyl monomers such as styrene; alkyl esters of itaconic acids; and the like can be mentioned.
  • These ethylenically unsaturated monomers can be used alone or in combination of two or more.
  • the polycarboxylic acid-based polymer is a copolymer of ⁇ , ⁇ -monoethylene unsaturated carboxylic acid and saturated carboxylic acid vinyl esters such as vinyl acetate
  • the copolymer is saponified and saturated.
  • a copolymer obtained by converting a carboxylic acid vinyl ester unit into a vinyl alcohol unit can also be used.
  • carboxy group-containing polysaccharide examples include acidic polysaccharides having an intramolecular carboxy group such as alginic acid, carboxymethyl cellulose, and pectin. These acidic polysaccharides can be used alone or in combination of two or more. In addition, acidic polysaccharides can also be used in combination with (co) polymers of ⁇ , ⁇ -monoethylene unsaturated carboxylic acids.
  • the polycarboxylic acid-based polymer used in the present invention is a copolymer of ⁇ , ⁇ -monoethylene unsaturated carboxylic acid and other ethylenically unsaturated monomers
  • the gas barrier property of the obtained film From the viewpoint of heat resistance and water vapor resistance, the copolymer composition thereof preferably has an ⁇ , ⁇ -monoethylene unsaturated carboxylic acid monomer composition of 60 mol% or more, preferably 80 mol% or more. Is more preferable, and 90 mol% or more is particularly preferable.
  • the polycarboxylic acid-based polymer has excellent gas barrier properties, moisture resistance, water resistance, heat resistance, and water vapor resistance, and it is easy to obtain a film having excellent gas barrier properties under high humidity conditions. It is preferably a homopolymer or a copolymer obtained by polymerizing only a monoethylenically unsaturated carboxylic acid.
  • the polycarboxylic acid-based polymer is a (co) polymer consisting only of ⁇ , ⁇ -monoethyl unsaturated carboxylic acid, preferred specific examples thereof are acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and the like.
  • homopolymers and copolymers of at least one ⁇ , ⁇ -monoethyl unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, and maleic acid are more preferable.
  • polycarboxylic acid-based polymer polyacrylic acid, polymethacrylic acid, maleic acid polymer, and a mixture of two or more of these are particularly preferable.
  • acidic polysaccharide an alginic acid polymer is preferable.
  • polyacrylic acid is particularly preferable because it is relatively easy to obtain and it is easy to obtain a film having excellent various physical characteristics.
  • the molecular weight of the polycarboxylic acid-based polymer is not particularly limited, but from the viewpoint of film formability and film physical characteristics, the number average molecular weight may be in the range of 2,000 to 10,000,000, and 5,000 to 1. It may be in the range of ⁇ 1,000,000 and may be in the range of 10,000 to 500,000. Further, from the viewpoint of enhancing the gas barrier property after the wet heat treatment, the weight average molecular weight of the polycarboxylic acid polymer is preferably in the range of 20,000 to 5 million, and preferably in the range of 200,000 to 1,000,000. Is more preferable.
  • the number average molecular weight and the weight average molecular weight can be measured by gel permeation chromatography (GPC). In GPC measurement, the number average molecular weight and the weight average molecular weight of the polymer are generally measured in terms of standard polystyrene.
  • the polymer constituting the layer (B) in addition to the polycarboxylic acid-based polymer, other polymers are mixed as long as the properties such as gas barrier property, heat resistance and water vapor resistance of the film are not impaired. Can be used. Above all, as the polymer constituting the layer (B), it is preferable to contain only a polycarboxylic acid-based polymer.
  • the polycarboxylic acid-based polymer used as a raw material has an oxygen permeability of preferably 150 cc / m 2 ⁇ day ⁇ atm or less at a temperature of 23 ° C. and a relative humidity of 60% for a dry coating film formed by using it alone. It is more preferably 50 cc / m 2 ⁇ day ⁇ atm or less, and particularly preferably 10 cc / m 2 ⁇ day ⁇ atm or less from the viewpoint of gas barrier property.
  • the oxygen permeability of the dry coating film formed by using the polycarboxylic acid-based polymer used as a raw material alone can be determined by the following method.
  • a polycarboxylic acid-based polymer is dissolved in water to prepare an aqueous solution having a concentration of 10% by mass.
  • This aqueous solution is applied to a plastic film base material having a relatively large oxygen permeability (for example, a nylon film having a thickness of 15 ⁇ m) using a bar coater, and dried to obtain a dry polycarboxylic acid having a thickness of 1 ⁇ m.
  • a coating film having a dry coating film of the system polymer is produced.
  • the oxygen permeability of the obtained coating film is measured at a temperature of 23 ° C.
  • the oxygen permeability of the coating film having the dry coating film of the obtained polycarboxylic acid-based polymer is 1/10 or less of the oxygen permeability of the plastic film used as the base material alone, the oxygen thereof.
  • the measured value of permeability can be regarded as the oxygen permeability of a dry coating film formed by substantially using a polycarboxylic acid-based polymer alone.
  • the layer (B) contains a magnesium salt of the polycarboxylic acid-based polymer.
  • the total amount of Mg 2+ in the layer (B) is preferably 0.2 chemical equivalent or more with respect to the total number of carboxy groups of the polycarboxylic acid-based polymer in the layer (B). , 0.4 chemical equivalent or more is more preferable, and 0.5 chemical equivalent or more is further preferable.
  • Mg 2+ in the layer (B) has a gas barrier property and suppresses deterioration of the adhesiveness, so that the Mg 2+ in the layer (B) has a relative value to the total carboxy group of the polycarboxylic acid polymer in the layer (B).
  • the total of the carboxy groups of the polycarboxylic acid-based polymer is the carboxy group (-COOH) of the polycarboxylic acid-based polymer that does not form a salt and the polycarboxylic acid-based polymer that forms a salt. It refers to the sum of - included carboxymethyl ion (-COO).
  • the total and the of Mg 2+ in the layer (B), referred to the Mg 2+ forming the polycarboxylic acid polymer and a salt the total of the Mg 2+ contained in the magnesium compound.
  • the layer (B) may contain a magnesium compound that does not form a salt with the polycarboxylic acid-based polymer.
  • the magnesium compound may be a compound that is easily dissolved in water because the magnesium salt of the polycarboxylic acid-based polymer in the layer (B) is dispersed in the layer (B) and the barrier property is improved.
  • magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium acetate and the like are preferably used.
  • magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium phosphate, and other water-insoluble magnesium compounds can be added under acidic conditions such as in the presence of hydrochloric acid, magnesium nitrate, and sulfuric acid. It can also be prepared by dissolving.
  • the layer (B) may contain an anion such as a chloride ion derived from a magnesium compound or an anion such as a nitrate ion, but the anion derived from the magnesium compound when forming a magnesium salt in the layer (B) is used. , Tend to remain in layer (A) rather than layer (B).
  • the anion derived from the magnesium compound is preferably contained in the layer (A) more than the layer (B), and is further opposite to the outermost surface of the layer (B) (opposite to the surface of the layer (B) having the layer (A)). It is preferable that it does not exist on the side surface).
  • magnesium compound-derived anions include, for example, element distribution analysis by EDX (energy dispersive X-ray analysis), depth direction analysis by XPS (X-ray photoelectron spectroscopy), and TOF-SIMS (time-of-flight secondary ion). It can be analyzed by mass spectrometry) or the like.
  • the layer (B) of the present invention preferably contains an anion derived from a polycarboxylic acid polymer, a magnesium ion, and a magnesium compound in an amount of 80% by mass or more, preferably 90% by mass, based on the entire layer (B). It is more preferable to contain the above.
  • the layer (B) may contain other components as long as the effects of the present invention are not impaired.
  • Other components include, for example, other resins such as surfactants, inorganic fillers, antioxidants, tackifier resins, silane coupling agents, ion scavengers, oxygen absorbers, deodorants, flame retardants, and UV absorption. Examples include agents, weather resistant agents, light resistant agents, antibacterial / bactericidal agents, and the like.
  • the layer thickness of the layer (B) has a high gas barrier property from the initial stage of production, and the gas barrier property deteriorates even after the wet heat treatment and further after the gelboflex test, and the layer peeling after the wet heat treatment is suppressed. It is 120 nm or more and 240 nm or less. Above all, from the viewpoint of initial barrier property, the layer thickness of the layer (B) is preferably 140 nm or more, and preferably 200 nm or less.
  • the gas barrier film of the present invention may further contain other layers. Since the gas barrier film of the present invention has the specific layer (B) having a specific layer thickness in combination adjacent to the specific layer (A), the gas barrier property is improved. It does not have to contain an inorganic oxide layer such as a vapor-deposited film of an inorganic oxide. Therefore, the layer (A) may be located adjacent to the substrate. However, the gas barrier film of the present invention does not prevent, for example, an embodiment in which an inorganic oxide layer is further provided between the base material and the layer (A).
  • Examples of other layers include a layer made of a metal foil obtained by rolling a metal, an adhesive layer, a printing layer, a resin layer obtained by coextrusion with a base material, a metal vapor deposition layer, and the like.
  • the other layers may be a surface opposite to the surface having the layer (A) and the layer (B) of the base material, between the base material and the layer (A), or the layer (A) of the layer (B). It can be held on one or more of the surfaces opposite to the surface to be held.
  • a conventionally known layer can be appropriately selected and used.
  • the inorganic oxide layer a vapor-deposited film of an inorganic oxide such as silicon oxide or alumina can also be used.
  • the thickness of the vapor-deposited film of the inorganic oxide varies depending on the type of the inorganic oxide used and the like, but from the viewpoint of gas barrier performance, for example, it is arbitrarily selected within the range of 20 to 2000 ⁇ , preferably 50 to 500 ⁇ . Can be done.
  • the metal foil a conventionally known metal foil can be used. Aluminum foil or the like is preferable from the viewpoints of oxygen barrier property and water vapor barrier property, light blocking property that blocks the transmission of visible light and ultraviolet rays, and gloss design.
  • the print layer can be formed by a conventionally known method using a conventionally known pigment or dye.
  • the adhesive layer is an adhesive layer formed for laminating any two layers.
  • the adhesive for laminating include one-component or two-component curable or non-curable vinyl-based, (meth) acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, and rubber-based adhesives.
  • Other solvent-based, water-based, or emulsion-type laminating adhesives can be used.
  • the layer thickness of the adhesive layer can be arbitrarily selected within the range of, for example, 0.1 to 5 ⁇ m, preferably 0.5 to 3 ⁇ m.
  • the gas barrier film of the present invention preferably has an oxygen permeability of 1.00 cc / m 2 ⁇ day ⁇ atm or less at a temperature of 23 ° C. and a relative humidity of 60% from the viewpoint of having high gas barrier properties from the initial stage of production. More preferably 0.90cc / m is 2 ⁇ day ⁇ atm or less, and still more preferably more or less 0.80cc / m 2 ⁇ day ⁇ atm .
  • the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% can be specifically measured by the method described in Examples described later.
  • the method for producing the gas barrier film of the present invention is not particularly limited as long as the gas barrier film of the present invention can be produced, but for example, the following production method is preferably used.
  • a method for producing the gas barrier film of the present invention The process of preparing the base material and A step of preparing a curable composition for forming a layer (A) containing an epoxy resin having four or more epoxy groups in one molecule and an epoxy resin curing agent.
  • a step of preparing a composition for forming a layer (B) containing a polycarboxylic acid-based polymer and a magnesium compound, and An epoxy having four or more epoxy groups in one molecule is obtained by applying the curable composition for forming the layer (A) onto the base material, and then drying and heating the coating film as necessary.
  • a step of forming a layer (B) containing an acid-based polymer and a magnesium salt of the polycarboxylic acid-based polymer with a layer thickness of 120 nm or more and 240 nm or less.
  • the process of preparing the base material is a resin film or sheet that satisfies the mechanical, physical, chemical strength, heat resistance, and texture required for the packaging material of the contents to be filled and packaged. Can be arbitrarily selected to prepare the base material.
  • the curable composition for forming the layer (A) includes the above-mentioned epoxy resin having four or more epoxy groups in one molecule, the above-mentioned epoxy resin curing agent, and if necessary, a solvent and other components. It can be prepared by mixing and preparing.
  • a solvent in which the epoxy resin and the epoxy resin curing agent are dissolved may be appropriately selected, and an organic solvent is preferable. For example, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, etc.
  • Glycol ethers such as 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propanol-2-propanol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and the like.
  • Examples thereof include aprotonic polar solvents such as alcohols, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone, and water-insoluble solvents such as toluene, xylene and ethyl acetate.
  • Methanol, ethyl acetate and other solvents with a relatively low boiling point are more preferred.
  • the mixing ratio of the epoxy resin and the epoxy resin curing agent in the curable composition for forming the layer (A) may be appropriately adjusted, but is specific from the viewpoint of improving the gas barrier property and the adhesiveness.
  • the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is preferably 0.1 to 5.0, and more preferably 0.2 to 3.0. , 0.3 to 1.5, more preferably less than 1.
  • the layer (B) forming composition can be prepared by mixing the polycarboxylic acid-based polymer, the magnesium compound, a solvent, and if necessary, other components.
  • the solvent is preferably a solvent that dissolves the polycarboxylic acid-based polymer and the magnesium compound, and is preferably water, alcohols such as methyl alcohol and isopropyl alcohol, dimethyl sulfoxide, N, N-dimethylformamide, and the like. Examples thereof include polar organic solvents such as N and N-dimethylacetamide, and these solvents may be used alone or in admixture of two or more.
  • the solvent preferably contains water.
  • the magnesium compound it is preferable to use it by dissolving it in a solvent from the viewpoint of advancing the cross-linking reaction of the polycarboxylic acid-based polymer with magnesium ions in the entire layer, and as described above, magnesium chloride, magnesium nitrate, magnesium sulfate, etc. It is preferable to use the water-soluble magnesium compound of.
  • a magnesium compound such as magnesium hydroxide, which is sparingly soluble in water, it is preferably dissolved in an acidic aqueous solution in the presence of hydrochloric acid, nitric acid, or sulfuric acid.
  • the curable composition for forming the layer (B) it is preferable to prepare an aqueous solution of the polycarboxylic acid-based polymer and the magnesium compound.
  • the magnesium salt of the polycarboxylic acid-based polymer can be formed before the layer is formed, so that salt formation such as a neutralization reaction can be performed after the layer formation. Unlike the case where this is done, unevenness and heat shrinkage are less likely to occur in the layer, and the appearance tends to be good.
  • the total of Mg 2+ in the layer (B) is the total of the carboxy groups of the polycarboxylic acid-based polymer.
  • the composition for forming the layer (B) preferably contains a solvent so that the solid content is 1.5 to 9.5% by mass and further 2.0 to 9.0% by mass.
  • the solid content refers to all components other than the solvent, and also includes liquid resins and other components.
  • Step of forming layer (A) The curable composition for forming the layer (A) is coated on the base material. If it is on a base material, it is not necessary to apply it directly on the base material, and if another layer is present on the base material, the layer (A) is formed directly on the other layer.
  • the curable composition is applied to form a coating film.
  • the coating film is provided by adjusting the coating amount so that the thickness of the curable composition for forming the layer (A) after curing falls within the range of the layer thickness.
  • a known coating method can be appropriately selected and used. For example, various coating methods such as a roll coating method, a bar coating method, a gravure coating method, and a slit coating method can be used. ..
  • a layer (A) containing a cured product of an epoxy resin having four or more epoxy groups in one molecule is formed.
  • the drying temperature may be appropriately selected depending on the solvent used, for example, 50 to 170 ° C., and the drying time is, for example, 1 to 30 minutes.
  • the heating temperature may be appropriately selected depending on the epoxy resin and the epoxy curing agent used, and examples thereof include 50 to 170 ° C. and heating times of 0.5 to 120 hours.
  • the drying or heating may be performed at the same time, and a known means can be appropriately selected and used as the drying and heating means.
  • Step of forming layer (B) The composition for forming the layer (B) is directly applied onto the layer (A) to form a coating film.
  • the coating film is used for forming the layer (B) so that the thickness of the composition for forming the layer (B) after drying and reaction falls within the range of the layer thickness of 120 nm or more and 240 nm or less of the layer (B). It is provided by adjusting the solid content content in the composition and the coating amount.
  • the coating method a known coating method can be appropriately selected and used, and the same method as described above can be mentioned.
  • the coating film is dried and heated as necessary.
  • the carboxy group of the polycarboxylic acid-based polymer and the magnesium ion are crosslinked to form a magnesium salt of the polycarboxylic acid-based polymer.
  • the epoxy group existing at the interface of the layer (A) and the carboxy group of the polycarboxylic acid-based polymer undergo a cross-linking reaction.
  • a layer (B) containing the polycarboxylic acid-based polymer and the magnesium salt of the polycarboxylic acid-based polymer is formed adjacent to the layer (A). Drying or heating may be performed at the same time.
  • the drying to heating temperature may be appropriately selected depending on the solvent used, for example, 50 to 170 ° C., and the drying to heating time may be, for example, 1 to 30 minutes.
  • the first laminated film of the present invention comprises a base material, a layer (A) containing a cured product of an epoxy resin having four or more epoxy groups in one molecule, and a layer (A) adjacent to the layer (A).
  • a gas barrier film having a layer (B) containing a polycarboxylic acid-based polymer and a magnesium salt of the polycarboxylic acid-based polymer, and having a layer thickness of 120 nm or more and 240 nm or less.
  • FIG. 2 is a schematic cross-sectional view showing an example of the laminated film of the present invention.
  • the laminate film 20 of the present invention includes the base material 11, the layer (A) 12, the layer (B) 13 adjacent to the layer (A) 12, and the sealant layer 14. In this order.
  • the laminated film 20 of the present invention may further have an adhesive layer (not shown) between the layer (B) 13 and the sealant layer 14.
  • the first laminated film of the present invention is provided with the above-mentioned gas barrier film of the present invention, and further has a sealant layer, so that it has a high gas barrier property from the initial stage of production by the same action as the above-mentioned gas barrier film of the present invention. It is a laminated film having a gas barrier property that does not easily deteriorate even after a wet heat treatment and a gelboflex test after the wet heat treatment.
  • the laminated film of the present invention further has at least a heat-sealable sealant layer on the above-mentioned gas barrier film of the present invention, and heat-sealing property is imparted by using the sealant layer as the innermost layer.
  • the base material, the layer (A), and the layer (B) may be the same as the gas barrier film of the present invention, and thus the description thereof will be omitted here.
  • the heat-sealing resin constituting the sealant layer may be any resin that can be melted by heat and fused to each other.
  • low-density polyethylene low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low Density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene
  • a polyolefin-based resin such as a polymer, or a resin consisting of one or more resins such as an acid-modified polyolefin-based resin obtained by modifying these resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid.
  • Films or sheets can be used. Above all, from the viewpoint of water vapor barrier property, it is preferable to use a resin film or sheet containing polypropylene as the sealant layer.
  • the above-mentioned resin film or sheet can be used in a single layer or multiple layers, and its thickness is, for example, 5 to 300 ⁇ m, preferably 10 to 150 ⁇ m.
  • the laminated film of the present invention may further contain other layers.
  • the laminated film of the present invention may contain other layers similar to the gas barrier film of the present invention, and further includes a resin layer, a light-shielding layer for imparting light-shielding properties, and absorption that absorbs or adsorbs odors. It may include a property / adsorptive layer, a light-resistant layer, a printing layer, an oxygen absorbing layer, a flame-retardant layer, a weather-resistant layer, a hard coat layer, an antibacterial / sterilizing layer, a liquid crystal layer and the like.
  • the laminated film of the present invention may have the same composition or different compositions.
  • the other layers are the surface opposite to the surface having the layer (A) and the layer (B) of the base material, between the base material and the layer (A), or between the layer (B) and the sealant layer. Can have one or more of.
  • conventionally known layers can be appropriately selected and used.
  • the resin layer is located between the layer (B) and the sealant layer, for example, has excellent mechanical, physical, chemical, etc. strength, excellent piercing resistance, etc., and also has heat resistance, moisture resistance, etc.
  • a resin film or sheet having excellent pinhole resistance, transparency, etc. can be used.
  • polyester-based resin, polyamide-based resin, polyaramid-based resin, polypropylene-based resin, polycarbonate-based resin, polyacetal-based resin, fluorine-based resin, and other tough resin films or sheets can be used.
  • any unstretched film, stretched film stretched in the uniaxial direction or biaxial direction, or the like can be used.
  • the thickness of the resin film or sheet is preferably 10 to 100 ⁇ m, particularly preferably 12 to 50 ⁇ m.
  • the laminated film of the present invention preferably has an oxygen permeability of 1.00 cc / m 2 ⁇ day ⁇ atm or less at a temperature of 23 ° C. and a relative humidity of 60% from the viewpoint of having a high gas barrier property from the initial stage of production, and is 0. .90 cc / m 2 ⁇ day ⁇ atm or less, 0.80 cc / m 2 ⁇ day ⁇ atm or less, more preferably 0.70 cc / m 2 ⁇ day ⁇ atm or less, more preferably 0.50 cc It is more preferably less than / m 2 ⁇ day ⁇ atm.
  • the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% can be specifically measured by the method described in Examples described later.
  • the laminated film of the present invention has an oxygen permeability of 1.00 cc at a temperature of 23 ° C. and a relative humidity of 60% after the boil test because the gas barrier property does not easily deteriorate even after the wet heat treatment and the gelboflex test. / M 2 ⁇ day ⁇ atm or less and After the boil test, the gelboflex test was performed under the conditions of ASTM F392-compliant temperature of 23 ° C. and relative humidity of 50%, and then the oxygen permeability at a temperature of 23 ° C. and relative humidity of 60% was 1.00 cc / m. It is preferably 2 ⁇ day ⁇ atm or less.
  • the laminated film of the present invention has an oxygen permeability of 0.95 cc / m 2 ⁇ day ⁇ atm or less at a temperature of 23 ° C. and a relative humidity of 60% after the boil test, and the gelboflex after the boil test. It is more preferable that the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% after the test is 0.95 cc / m 2 ⁇ day ⁇ atm or less, and after the boil test, the temperature is 23 ° C. and the relative humidity is 60.
  • the oxygen permeability in% is 0.90 cc / m 2 ⁇ day ⁇ atm or less, and the oxygen permeability at a temperature of 23 ° C.
  • the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% after the boil test and the gelboflex test is 0.70 cc / m 2 ⁇ day ⁇ atm or less.
  • the oxygen permeability at 60% relative humidity is not more than 0.50cc / m 2 ⁇ day ⁇ atm , and, after the boiling test, after performing the Gelbo flex test It is particularly preferable that the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% is 0.50 cc / m 2 ⁇ day ⁇ atm or less.
  • the boil test, the gelboflex test, and the measurement of oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% can be specifically carried out by the method described in Examples described later.
  • the peel strength after the boil test is determined in the T-shaped peeling test based on JIS K6854-3. 3.0N / 15mm or more and After the boil test, the peel strength measured by adhering water to the peel surface is preferably 3.0 N / 15 mm or more in the T-shaped peel test based on JIS K6854-3.
  • the peel strength after the boil test is 3.1 N / 15 mm or more in the T-shaped peel test, and the peel strength measured by adhering water to the peel surface after the boil test.
  • the peeling strength after the boil test is 3.2 N / 15 mm or more in the T-shaped peeling test and after the boil test. It is even more preferable that the peel strength measured by adhering water to the peel surface is 3.2 N / 15 mm or more in the T-shaped peel test.
  • the peel strength after the boil test and the peel strength measured by adhering water to the peel surface after the boil test can be specifically measured by the method described in Examples described later.
  • the laminated film of the present invention is produced by forming another layer on the gas barrier film of the present invention, if necessary, and laminating a heat-sealing layer via an adhesive layer, if necessary. Can be done.
  • the second laminate film of the present invention comprises a base material, a layer (A') containing a cured product of an epoxy resin, and a polycarboxylic acid-based polymer and the polycarboxylic acid adjacent to the layer (A').
  • a gas barrier film having a layer (B') containing a polyvalent metal salt of an acid polymer and having a layer thickness of 120 nm or more and 240 nm or less, and a sealant layer are provided.
  • a relative humidity of 60% is 1.00 cc / m 2 ⁇ day ⁇ atm or less
  • the gelboflex test was performed under the conditions of ASTM F392-compliant temperature of 23 ° C. and relative humidity of 50%, and then the oxygen permeability at a temperature of 23 ° C. and relative humidity of 60% was 1.00 cc / m. 2 ⁇ day ⁇ atm or less
  • the peel strength after the boil test is 3.0 N / 15 mm or more and is 3.0 N / 15 mm or more in the T-shaped peel test based on JIS K6854-3.
  • the peel strength measured by adhering water to the peel surface is 3.0 N / 15 mm or more in the T-shaped peel test based on JIS K6854-3.
  • the second laminated film of the present invention has a high gas barrier property after the wet heat treatment and further after the gelboflex test after the wet heat treatment, as specified above, by the same action as the first laminated film. It is a thing.
  • the second laminated film of the present invention has an oxygen permeability of 0.95 cc / m 2 ⁇ day ⁇ atm or less at a temperature of 23 ° C. and a relative humidity of 60% after the boil test, and after the boil test, the above.
  • the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% is more preferably 0.95 cc / m 2 ⁇ day ⁇ atm or less, and after the boil test, the temperature is 23 ° C.
  • the oxygen permeability at a relative humidity of 60% is 0.90 cc / m 2 ⁇ day ⁇ atm or less, and after the boil test and the Gelboflex test, the temperature is 23 ° C.
  • the oxygen permeability is more preferably 0.90 cc / m 2 ⁇ day ⁇ atm or less, and the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% after the boiling test is 0.70 cc / m 2 ⁇ day ⁇ atm.
  • the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 60% after the gelboflex test after the boil test is 0.70 cc / m 2 ⁇ day ⁇ atm or less. Even more preferable.
  • the peel strength after the boil test is 3.1 N / 15 mm or more in the T-shaped peel test, and after the boil test, water is adhered to the peeled surface.
  • the peel strength to be measured is more preferably 3.1 N / 15 mm or more in the T-shaped peel test, and the peel strength after the boil test is 3.1 N / 15 mm or more in the T-shaped peel test. It is more preferable that the peel strength is 3.2 N / 15 mm or more and the peel strength measured by adhering water to the peel surface after the boil test is 3.2 N / 15 mm or more in the T-shaped peel test.
  • the base material may be the same as described above.
  • the layer (A') contains a cured product of an epoxy resin. That is, the layer (A') contains a reaction product of an epoxy resin having an epoxy group and an epoxy resin curing agent.
  • the epoxy resin used for the layer (A') preferably has two or more epoxy groups in one molecule, more preferably three or more epoxy groups in one molecule. It is even more preferable to have four or more epoxy groups.
  • the epoxy resin is, for example, a saturated or unsaturated aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound or a combination thereof, which is derived from a compound having an amino group or a hydroxyl group, and is glycidyl.
  • epoxy resin a conventionally known epoxy resin can be appropriately selected and used, but it is preferable to use the same epoxy resin as that described in the layer (A). Further, the epoxy resin curing agent and other components used as necessary may be the same as those described in the layer (A).
  • the layer (B') is located adjacent to the layer (A') and contains a polycarboxylic acid-based polymer and a polyvalent metal salt of the polycarboxylic acid-based polymer.
  • the polycarboxylic acid-based polymer may be the same as the layer (B).
  • the polyvalent metal ion constituting the polyvalent metal salt include divalent or higher metal ions such as magnesium ion, calcium ion, barium ion, zinc ion, copper ion, cobalt ion, nickel ion, aluminum ion and iron ion. Among these, it is preferable to use at least one metal ion selected from the group consisting of magnesium ion, calcium ion, barium ion, zinc ion, and aluminum ion.
  • the gas barrier film used for the second laminate film of the present invention can be produced in the same manner as the gas barrier film of the present invention. It is preferable that the polyvalent metal salt of the polycarboxylic acid-based polymer is also produced in the same manner as the magnesium salt of the polycarboxylic acid-based polymer described above.
  • the sealant layer and other layers may be the same as those described in the first laminated film, and can be produced in the same manner as the first laminated film. ..
  • the packaging of the present invention is a packaging comprising the laminate film of the present invention. Since the package of the present invention includes the laminate film of the present invention, it has a high gas barrier property, and the gas barrier property is unlikely to deteriorate even after a wet heat treatment and a gelboflex test.
  • the packaging body include shapes such as a flat pouch, a standing pouch, a pouch with a nozzle, a pillow bag, a gusset bag, a bullet-shaped packaging bag, and a packaging container. , Easy-opening property, easy tearing property, shrinkage property, microwave suitability, UV blocking property, design property and the like can be imparted and used.
  • Specific shapes of other packages include bottles, trays, cups, tubes, lid materials for these containers, mouth seal materials, and the like.
  • the laminate film of the present invention is folded in half, the surfaces of the sealant layers are overlapped with each other facing each other, and the ends thereof are heat-sealed to form a tubular packaging body, and then the bottom portion is sealed. It can be manufactured by filling the contents and further sealing the top.
  • the laminated film of the present invention is bent or overlapped so that the surfaces of the inner layers thereof face each other, and the peripheral ends thereof are, for example, a side seal type, a two-way seal type, a three-way seal type, a four-way seal type, and an envelope.
  • Various types of packages are manufactured by heat-sealing with heat-sealing forms such as sticker-sticker type, gassho-sticker-seal type (pillow-seal type), fold-seal type, flat-bottom seal type, square-bottom seal type, and gusset type. be able to.
  • a self-supporting packaging bag (standing pouch) or the like is also possible.
  • the heat sealing method for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Is included in the technical scope of.
  • Example 1 to 13 correspond to the first laminated film and the second laminated film
  • Example A corresponds to the second laminated film.
  • Evaluation method ⁇ Layer thickness measurement> The thickness of each layer was measured by preparing an ultrathin section of the obtained laminated film and observing the cross section with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • ⁇ Boil test> Two sheets of the obtained laminated film were cut out to the size of A4, the two sheets were overlapped with the surfaces of the sealant layers facing each other, and the end and the bottom thereof were heat-sealed to form a packaging bag.
  • a sample containing 150 mL of pure water in a packaging bag is placed in a high-temperature and high-pressure cooking sterilizer capable of boiling and cooling under the following conditions, and is boiled in hot water at 95 ° C. for 30 minutes. , The mixture was replaced with water at 23 ° C. and cooled for 15 minutes. After that, the mixture was replaced with water at 23 ° C. and cooled for 10 minutes to complete the boiling treatment.
  • ⁇ Gelboflex test> A Gelboflex tester (manufactured by Tester Sangyo) was used to perform a Gelboflex test in accordance with ASTM F392. After the boil test, the packaging bag is cut into A4 size, set in a tubular shape with the base material side inside and having a diameter of 90 mm, and then 40 times / minute under the conditions of a temperature of 23 ° C. and a relative humidity of 50%. The process of pushing 90 mm while twisting 440 ° and further going straight 65 mm was repeated 50 times.
  • ⁇ Peeling strength> (Normal peel strength after boil test: dry) After a boil test at 95 ° C. for 30 minutes, a sample cut out in a strip shape having a width of 15 mm was prepared from a packaging bag from which water was drained. This sample was formed on the base material of the laminate film and on the base material in accordance with JIS K6854-3 using a tensile tester (manufactured by Orientec Co., Ltd. [Model name: Tencilon universal material tester]). The peel strength of the layer was measured. In the measurement, first, as shown in FIG. 3, a rectangular test piece in which the base material layer 11 and the layers (12, 13, 14) formed on the base material are peeled off by 15 mm in the long side direction.
  • the parts of the base material 11 and the layers (12, 13, 14) formed on the base material that have already been peeled off are separated from each other by the gripping tool 31 and the gripping tool 32 of the measuring instrument, respectively. I grasped it with. Further, the gripping tools 31 and 32 are opposite to each other in the direction orthogonal to the surface direction of the portion where the base material 11 and the layers (12, 13, 14) formed on the base material are still laminated, respectively. It was pulled in the direction (180 ° peeling: T-shaped peeling method) at a speed of 50 mm / min, and the average value of tensile stress in the stable region (see FIG. 5) was measured.
  • FIG. 5 is a diagram showing changes in tensile stress with respect to the interval S between the grippers 31 and 32. As shown in FIG. 5, the change in tensile stress with respect to the interval S passes through the first region and enters the second region (stable region) where the rate of change is smaller than that of the first region. The average value of the tensile stress in the stable region was measured, and the value was used as the peel strength between the base material of the laminated film and the layer formed on the base material.
  • the watering peel strength was measured by the same method as the method for measuring the normal peel strength, except for the points described below.
  • the base material of the test piece and the layer formed on the base material are peeled off by 15 mm, and then water is applied to the adhesive interface between the base material and the layer formed on the base material.
  • the peel strength in the presence of was measured.
  • the base material and the layer formed on the base material maintain the bond when viewed along the longitudinal direction of the test piece 30.
  • the measurement was carried out in a state where 100 ⁇ L of water was dropped with a dropper on the boundary portion between the portion and the portion where the base material and the layer formed on the base material were peeled off.
  • Example 1 Production of Gas Barrier Film (1-1) Formation of Layer (A) 46.1 g of methanol was weighed, and 5.2 g of ethyl acetate was added thereto to prepare a mixed solvent of methanol / ethyl acetate. 2.7 g of an epoxy resin curing agent (polyamine, manufactured by Mitsubishi Gas Chemical Company, trade name Maxive C-93T) was dissolved therein. Further, 1.0 g of an epoxy resin (N, N, N', N'-tetraglycidyl metaxylylenediamine, manufactured by Mitsubishi Gas Chemical Company, trade name TETRAD-X) having four or more epoxy groups in one molecule was added. To prepare a curable composition for forming the layer (A).
  • an epoxy resin curing agent polyamine, manufactured by Mitsubishi Gas Chemical Company, trade name Maxive C-93T
  • a curable composition for forming a layer (A) was applied onto a nylon film having a thickness of 15 ⁇ m as a base material using a wire bar, and then the coating film was dried at 140 ° C. for 2 minutes. The dried coating film was aged at 55 ° C. for 24 hours to complete the reaction and cure to obtain a film (base material 11 / layer (A) 12) having a layer (A) formed on the base material.
  • the composition for forming the layer (B) was applied directly onto the layer (A) of the film using a wire bar.
  • the coating amount was appropriately adjusted so that the layer thickness after drying would be the thickness shown in Table 1.
  • the coating film was dried at 80 ° C. for 1 minute to form a layer (A) and a layer (B) on the base material, and the gas barrier film 10 (base material 11 / layer (A) 12 / layer (B). ) 13) was obtained.
  • the column of layer (B) in Table 1 the polyvalent metal compound used for forming the salt of the polycarboxylic acid-based polymer is shown.
  • Example 1 when the gas barrier film is produced, the solid content of the composition for forming the layer (B) is such that the layer thickness after drying of the layer (B) is the thickness shown in Table 1.
  • a gas barrier film was produced and a laminated film was produced in the same manner as in Example 1 except that the concentration and the coating amount were appropriately adjusted.
  • the obtained evaluation results are shown in Table 1.
  • element distribution analysis by EDX energy dispersive X-ray analysis was performed using ultrathin sections of the laminate film used for layer thickness measurement. The result of Example 3 is shown in FIG.
  • Example 6 In Example 1, instead of using 2.3 g of magnesium chloride in the preparation of the composition for forming the layer (B) in the production of the gas barrier film, 1.4 g of magnesium hydroxide (manufactured by Kamishima Chemical Industry Co., Ltd.) ( A gas barrier film was produced and laminated in the same manner as in Example 1 except that Mg 2+ was dissolved in pure water using 0.7 chemical equivalent) and 7.2 g of hydrochloric acid with respect to the carboxy group of polyacrylic acid. Manufactured the film. The obtained evaluation results are shown in Table 1.
  • Example 7 In Example 1, when preparing the composition for forming the layer (B) in the production of the gas barrier film, instead of using 2.3 g of magnesium chloride, 1.4 g of magnesium hydroxide (manufactured by Konoshima Chemical Co., Ltd.) was used. A gas barrier film was produced and a laminated film was produced in the same manner as in Example 1 except that 6.5 g of nitric acid was used and dissolved in pure water. The obtained evaluation results are shown in Table 1.
  • Example 8 In Example 1, a curable composition for forming a layer (A) so that the layer thickness of the layer (A) after drying and curing in producing a gas barrier film is the thickness shown in Table 1. A gas barrier film was produced and a laminated film was produced in the same manner as in Example 1 except that the amount of coating was appropriately adjusted. The obtained evaluation results are shown in Table 1.
  • Example 9 In Example 1, in the composition for forming the layer (B) when producing a gas barrier film, the chemical equivalent of magnesium chloride to the carboxy group of polyacrylic acid was adjusted as shown in Table 2, and the solid content concentration was adjusted to 5 mass by mass. A composition for forming a layer (B) was prepared in the same manner as in Example 1 except that the percentage was set to%. In addition, Example 1 except that the coating amount of the composition for forming the layer (B) was appropriately adjusted so that the layer thickness of the layer (B) after drying was the thickness shown in Table 2. In the same manner as above, a gas barrier film was produced, and a laminated film was produced. The obtained evaluation results are shown in Table 2.
  • Example 11 (Second Laminated Film Example A) In Example 11, an epoxy resin (N, N, N', N'-tetra) having four or more epoxy groups in one molecule in the curable composition for forming the layer (A) when producing a gas barrier film.
  • Example 4 In Example 1, when preparing a composition for forming a layer (B) in producing a gas barrier film, instead of using 5 g of polyacrylic acid, polyvinyl alcohol (abbreviated as PVA, manufactured by Kuraray, trade name PVA-) 124) A gas barrier film was produced and a laminated film was produced in the same manner as in Example 1 except that 5 g of the film was dissolved in pure water. The obtained evaluation results are shown in Table 1.
  • PVA polyvinyl alcohol
  • Example 5 (Comparative Example 5) In Example 1, instead of using the curable composition for forming the layer (A) in producing the gas barrier film, an oxazoline resin solution (manufactured by Nippon Catalyst Co., Ltd., trade name WS-300) was used and similarly coated. After that, a gas barrier film was produced and a laminated film was produced in the same manner as in Example 1 except that the coating film was dried and cured at 60 ° C. for 3 minutes. The obtained evaluation results are shown in Table 1.
  • oxazoline resin solution manufactured by Nippon Catalyst Co., Ltd., trade name WS-300
  • Example 6 (Comparative Example 6) In Example 1, a gas barrier film was produced in the same manner as in Example 1 except that magnesium chloride was not used in the preparation of the composition for forming the layer (B) when producing the gas barrier film. , Manufactured a laminated film. The obtained evaluation results are shown in Table 1.
  • Example 7 (Comparative Example 7) In Example 1, a gas barrier film was produced and a laminated film was produced in the same manner as in Example 1 except that the layer (A) was not formed when the gas barrier film was produced. The obtained evaluation results are shown in Table 1.
  • Example 8 In Example 1, a gas barrier film was produced and a laminated film was produced in the same manner as in Example 1 except that the layer (B) was not formed when the gas barrier film was produced. The obtained evaluation results are shown in Table 1.
  • Example 8 (Comparative Example 9) In Example 8, the gas barrier film was produced and the laminated film was produced in the same manner as in Example 8 except that the layer (B) was not formed when the gas barrier film was produced. The obtained evaluation results are shown in Table 1.
  • Example 11 when producing a gas barrier film, instead of using a nylon film having a thickness of 15 ⁇ m as a base material, a polyester film (IB-PET-P manufactured by Dainippon Printing Co., Ltd.) on which aluminum oxide was vapor-deposited was used. A gas barrier film was produced and a laminated film was produced in the same manner as in Example 11 except that the layer (A) was not formed and the layer (B) was formed using an applicator. The obtained evaluation results are shown in Table 2.
  • Example 11 when producing a gas barrier film, instead of using a nylon film having a thickness of 15 ⁇ m as a base material, a polyester film (IB-PET-P manufactured by Dainippon Printing Co., Ltd.) on which aluminum oxide was vapor-deposited was used. A gas barrier film was produced and a laminated film was produced in the same manner as in Example 11 except that the layer (B) was not formed and the layer (A) was formed using an applicator. The obtained evaluation results are shown in Table 2.
  • a gas barrier laminate was obtained in the same manner as in Examples 3 to 5 of Patent Document 1 (International Publication No. 2010/001836).
  • the layer (A) containing the alkaline compound of the polyvalent metal is white and opaque, but it is made transparent together with the layer (A) by laminating the layer (B) containing polyacrylic acid on the layer (A). After laminating the layer (B), heat shrinkage occurred during the drying step, wrinkles were generated, and the appearance was deteriorated.
  • heat shrinkage is likely to occur due to the heat of neutralization due to the neutralization reaction between the carboxylic acid and the alkali after the formation of the two layers. It has been shown that the manufacturing method of Patent Document 1 (International Publication No. 2010/001836) tends to cause unevenness and heat shrinkage, and the appearance tends to deteriorate in the first place.
  • the gas barrier films and laminated films of Examples 1 to 13 having a layer (B) containing the magnesium salt of the above and having a layer thickness of 120 nm or more and 240 nm or less have a high gas barrier from the initial stage of production. It was shown that the gas barrier property is not easily deteriorated even after the wet heat treatment (boil test) and the gelboflex test after the wet heat treatment (boil test).
  • the anion (Cl ⁇ ) derived from the magnesium compound is magnesium.
  • the layer (A) contains more ions (Mg 2+ ) than the layer (B), and is on the outermost surface of the layer (B) (on the side opposite to the surface of the layer (B) having the layer (A)). It was shown that it was not included in the surface).
  • Comparative Example 1 in which the layer thickness of the layer (B) was less than 120 nm, it was shown that the gas barrier property deteriorated after the wet heat treatment. It is presumed that if the layer thickness of the layer (B) is too small, the gas barrier property due to the cross-linking of the polycarboxylic acid and the magnesium ion by the layer (B) becomes insufficient. Further, in Comparative Example 2 in which the layer thickness of the layer (B) exceeded 240 nm, it was shown that the gas barrier property of the gas barrier film alone was inferior.
  • Comparative Example 3 in which the layer thickness of the layer (B) is thicker, the gas barrier property of the gas barrier film alone is inferior, and there is a problem that the layer (B) is peeled off after the wet heat treatment. It was estimated that if the layer thickness of the layer (B) is too thick, the adhesion due to the cross-linking reaction between the layer (A) and the layer (B) will be insufficient.
  • Comparative Example 4 in which polyvinyl alcohol was used instead of polyacrylic acid as the polymer of the layer (B), the gas barrier property of the gas barrier film alone and the initial gas barrier property of the laminated film were inferior, and after the wet heat treatment. , There was a problem that the layer (B) was peeled off.
  • the gas barrier property is inferior, and if the functional group that reacts with the layer (A) is a hydroxyl group contained in the polyvinyl alcohol, the cross-linking reaction between the layer (A) and the layer (B) It was presumed that the adhesion due to the above would be insufficient.
  • Comparative Example 5 in which a cured product of the oxazoline resin was used instead of the cured product of the epoxy resin of the layer (A), it was shown that the gas barrier property of the gas barrier film alone was inferior.
  • Comparative Examples 8 and 9 in which the layer (B) was not formed the gas barrier properties of the gas barrier film alone and the laminated film were inferior even in Comparative Example 9 in which the layer (A) was thickened, and the peel strength of the test piece 30 was high. It could not be created and measured. It is presumed that the adhesion between the layer (A) and the base material is too strong.
  • Comparative Example 10 in which the layer (A) was not formed by using a polyester film on which aluminum oxide was vapor-deposited instead of using a nylon film having a thickness of 15 ⁇ m as a base material in producing the gas barrier film aluminum oxide was vapor-deposited.
  • the gas barrier property of the gas barrier film alone was improved as compared with Comparative Example 7, but the gas barrier property was inferior in the initial stage of the laminated film, after the wet heat treatment, and after the gelboflex test after the wet heat treatment.
  • the layer (B) was not formed by using a polyester film on which aluminum oxide was vapor-deposited instead of using a nylon film having a thickness of 15 ⁇ m as a base material in producing the gas barrier film, aluminum oxide was vapor-deposited.
  • the film the gas barrier property of the single gas barrier film and the gas barrier property of the laminated film at the initial stage and after the wet heat treatment were improved as compared with Comparative Example 8, but the influence of the aluminum oxide vapor deposition film after the gelboflex test after the wet heat treatment. It was shown that the gas barrier property deteriorated.

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  • Mechanical Engineering (AREA)
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Abstract

La présente invention concerne : un film barrière contre les gaz et un film stratifié ayant des propriétés de barrière contre les gaz élevées suite à la fabrication initiale, le film barrière contre les gaz et le film stratifié étant tels que leurs propriétés de barrière contre les gaz ne se détériorent pas facilement même après un traitement thermique humide et après un test Gelboflex après le traitement thermique humide ; et un emballage pourvu du film stratifié.　La présente invention concerne un film barrière contre les gaz comprenant : un substrat ; une couche (A) contenant un produit durci d'une résine époxy ayant quatre groupes époxy ou plus par molécule ; et une couche (B) adjacente à la couche (A), la couche (B) contenant un polymère à base d'acide polycarboxylique et un sel de magnésium du polymère à base d'acide polycarboxylique, l'épaisseur de couche de la couche (B) étant de 120 à 240 nm (inclus).
PCT/JP2021/003684 2020-02-05 2021-02-02 Film barrière contre les gaz, film stratifié et emballage WO2021157557A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001506550A (ja) * 1996-12-04 2001-05-22 ピーピージー インダストリーズ オハイオ，インコーポレイテッド 酸素感受性食物および飲料のための多層パッケージング材料
JP2004025616A (ja) * 2002-06-25 2004-01-29 Mitsubishi Gas Chem Co Inc ガスバリア性ポリオレフィン積層フィルム
JP2004315585A (ja) * 2003-04-11 2004-11-11 Toyo Ink Mfg Co Ltd ガスバリア性積層体の製造方法
JP2005272757A (ja) * 2004-03-26 2005-10-06 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
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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001506550A (ja) * 1996-12-04 2001-05-22 ピーピージー インダストリーズ オハイオ，インコーポレイテッド 酸素感受性食物および飲料のための多層パッケージング材料
JP2004025616A (ja) * 2002-06-25 2004-01-29 Mitsubishi Gas Chem Co Inc ガスバリア性ポリオレフィン積層フィルム
JP2004315585A (ja) * 2003-04-11 2004-11-11 Toyo Ink Mfg Co Ltd ガスバリア性積層体の製造方法
JP2005272757A (ja) * 2004-03-26 2005-10-06 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
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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