WO2015022991A1 - Matériau de barrière aux gaz, et stratifié faisant barrière aux gaz - Google Patents

Matériau de barrière aux gaz, et stratifié faisant barrière aux gaz Download PDF

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Publication number
WO2015022991A1
WO2015022991A1 PCT/JP2014/071454 JP2014071454W WO2015022991A1 WO 2015022991 A1 WO2015022991 A1 WO 2015022991A1 JP 2014071454 W JP2014071454 W JP 2014071454W WO 2015022991 A1 WO2015022991 A1 WO 2015022991A1
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Prior art keywords
gas barrier
layer
barrier laminate
laminate according
resin
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PCT/JP2014/071454
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English (en)
Japanese (ja)
Inventor
佳史子 川合
雄介 小賦
楠 張
浩介 植田
瞬也 南郷
岡部　誠司
祥人 久富
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東洋製罐株式会社
東洋製罐グループホールディングス株式会社
東罐興業株式会社
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Priority to JP2015531836A priority Critical patent/JPWO2015022991A1/ja
Publication of WO2015022991A1 publication Critical patent/WO2015022991A1/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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2439/00—Containers; Receptacles
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/02—Open containers

Definitions

  • the present invention relates to a gas barrier laminate having a gas barrier layer made of a polycarboxylic acid polymer, and more specifically, a gas barrier property in which a layer made of a thermoplastic resin by extrusion coating is formed on the gas barrier layer.
  • the present invention relates to a gas barrier laminate excellent in flexibility and productivity.
  • a laminate having a gas barrier property formed by laminating a gas barrier material such as an aluminum foil or an ethylene vinyl alcohol copolymer on a paper substrate is a packaging container.
  • a gas barrier material such as an aluminum foil or an ethylene vinyl alcohol copolymer
  • laminates made by laminating metal foil such as aluminum foil on a paper base material are excellent in gas barrier properties, but cannot be used for quality control by metal detectors, and are still sufficient in terms of separation and disposal.
  • the laminated body formed by laminating a layer made of an ethylene vinyl alcohol copolymer on a paper base material has a problem that gas barrier properties are lowered due to moisture absorption.
  • a laminate using an inorganic vapor deposition film as a gas barrier layer has also been proposed.
  • a vapor deposition surface of an inorganic vapor deposition film and a thermal adhesive resin are dry-laminated, and a non-deposition surface and paper are laminated.
  • a laminated sheet obtained by sand laminating (Patent Document 1), a film (Patent Document 2) in which an aqueous coating layer is provided on a vapor deposition layer of a metal oxide vapor deposition film, and paper is laminated via a wax hot melt layer Proposed.
  • the inorganic vapor-deposited film has a very high cost, and the vapor-deposited film is inferior in flexibility and has a problem in that it is inferior in adhesion to the substrate or other resin layer.
  • gas barrier materials formed by ion-crosslinking polycarboxylic acid polymers with polyvalent metals have been proposed as gas barrier materials that are not affected by environmental considerations or humidity conditions.
  • a gas barrier layer-forming paint (C) containing a saccharide (A) and an olefin-maleic acid copolymer (B) on a plastic substrate through an undercoat layer and after heat treatment,
  • a gas barrier laminate (Patent Document 3) obtained by heat treatment in the presence of water, or a gas barrier polycarboxylic acid resin layer formed on at least one surface of a plastic film substrate, The acid resin is cross-linked at the carboxyl group by the metal ion in the compound of a metal having a valence of 2 or more without being subjected to heat treatment. Characterized in that having both the A property, gas barrier laminate film (Patent Document 4) have been proposed.
  • the gas barrier materials described in Patent Documents 3 and 4 need to be highly cross-linked by heating at a high temperature of 150 ° C. or higher or for a long time. In addition, it is inferior in productivity and has problems in terms of consuming a great deal of energy and water, and also in terms of flexibility and retort resistance. I was not satisfied enough. In addition, when a layer made of another thermoplastic resin is laminated on the gas barrier material by extrusion coating, it is necessary to protect the gas barrier material by previously laminating another base material on the gas barrier material by dry lamination. However, it was not yet fully satisfactory in terms of productivity and economy.
  • an object of the present invention is to improve productivity by directly laminating a thermoplastic resin by extrusion coating on a gas barrier layer made of a polycarboxylic acid polymer containing a polyvalent metal element having excellent gas barrier properties and flexibility. Is to provide an excellent gas barrier laminate.
  • the gas barrier layer is 0.10 to 1.4% by weight.
  • a polycarboxylic acid system containing a monovalent metal element, 5.0 to 18.0% by weight of polyvalent metal element, and 0.01 to 3.0% by weight of nitrogen element with respect to the total weight of nitrogen and carbon A gas barrier laminate comprising a polymer and formed by extrusion coating a thermoplastic resin on the gas barrier material is provided.
  • the gas barrier material is laminated with a base material made of paper or synthetic resin through the thermoplastic resin, 2.
  • the thermoplastic resin is an ethylene- (meth) acrylic acid copolymer or ionomer resin; 3.
  • the thermoplastic resin is a polyolefin resin containing no antioxidant, or a polyolefin resin containing a reactive group capable of forming a chemical bond with a carboxyl group or a hydroxyl group, 4).
  • the polyolefin resin is a linear low density polyethylene polymerized using a single site catalyst, 5.
  • the polyolefin resin has a density of 0.950 g / cm 3 or less, 6).
  • the polyolefin resin has a melt flow rate of 7.0 g / 10 min or more, 7).
  • the gas barrier layer has a weight loss from 200 ° C. to 320 ° C. of not more than 10% in thermogravimetric analysis (TGA) measurement at a heating rate of 10 ° C. / and 200 in dynamic viscoelasticity (DMS) measurement at 20 Hz. The difference when subtracting tan ⁇ at 50 ° C from tan ⁇ at ° C is 0.010 or more, 8).
  • the monovalent metal element is sodium or potassium, 9.
  • the polyvalent metal element is at least one of calcium and magnesium; 10.
  • the nitrogen content relative to the total amount of carbon, oxygen and nitrogen in the surface layer is 1 atm% or more, 11.
  • the alkaline compound of the polyvalent metal comprises at least one of calcium, magnesium carbonate and hydroxide; 14
  • the isocyanate compound is a combination of a linear aliphatic isocyanate compound and an alicyclic isocyanate compound having an alicyclic ring structure in the skeleton; 15.
  • the aliphatic isocyanate compound has an isocyanurate structure; 16.
  • a region (a) not containing a polyvalent metal alkaline compound is formed on the gas barrier layer side of the layer (A), and the nitrogen content in the region (a) is a layer (A) other than the region (a). More than the nitrogen content of Is preferred.
  • thermoplastic resin is directly extrusion coated on a gas barrier material in which a gas barrier layer made of a polycarboxylic acid polymer is formed on a plastic substrate, and a conventional polycarboxylic acid polymer is applied.
  • the gas barrier layer of the gas barrier material used in the gas barrier laminate of the present invention has a heat decomposability that does not cause thermal decomposition in the processing temperature range in the laminate by extrusion coating, and an uncrosslinked portion exists in this processing temperature range. Therefore, it is possible to ensure a certain molecular mobility due to thermal energy and relieve the stress generated in the gas barrier layer, thereby ensuring crack resistance and directly extruding the thermoplastic resin to the gas barrier material. It becomes possible.
  • Thermal decomposition resistance in the processing temperature range can be expressed by weight loss in thermogravimetric analysis (TGA) measurement, while crack resistance in the processing temperature range is tan ⁇ in dynamic viscoelasticity (DMS) measurement.
  • the gas barrier layer made of the polycarboxylic acid polymer of the gas barrier material used in the gas barrier laminate of the present invention is subjected to thermogravimetric analysis at a heating rate of 10 ° C. /
  • the weight loss from 200 ° C. to 320 ° C. in the (TGA) measurement is 10% or less, particularly 3 to 9%
  • the dynamic viscoelasticity (DMS) measurement at 20 Hz is from tan ⁇ of 200 ° C. to 50 ° C.
  • the difference when subtracting tan ⁇ is preferably 0.010 or more, particularly in the range of 0.011 to 0.060. Extrusion coating of thermoplastic resin into the gas barrier material is improved.
  • an ethylene- (meth) acrylic copolymer, an ionomer resin, or a specific polyolefin resin, which will be described later, is used as a thermoplastic resin during the extrusion to the gas barrier layer.
  • the gas barrier layer can exhibit excellent adhesion to the gas barrier layer, prevent delamination, and crack the gas barrier layer even when the gas barrier laminate is subjected to stress such as bending or ironing. Can be suppressed, and stable gas barrier properties can be exhibited.
  • the amount of the monovalent metal element present in the gas barrier layer is in the above range, so that the transparency and gloss of the coated surface are excellent, and good appearance characteristics are expressed. It is possible and also contributes to the water resistance after bending, and it is between the gas barrier layer and the layer (A) containing a plastic base material or an isocyanate compound, or a layer made of an extrusion-coated thermoplastic resin. It is effectively prevented that peeling occurs.
  • the gas barrier layer controls the contents of monovalent metal elements, polyvalent metal elements, and nitrogen within a predetermined range, so that the gas barrier layer has excellent gas barrier properties, water resistance, retort resistance, and gloss and transparency. Appearance characteristics such as properties and water resistance after bending.
  • the gas barrier laminate of the present invention has an excellent gas barrier property and retort resistance without cross-linking the polycarboxylic acid polymer by a covalent bond using a cross-linking agent. Necessary heat treatment steps can be simplified.
  • a layer (A) containing an isocyanate compound having at least two isocyanate groups in one molecule (hereinafter sometimes referred to as “undercoat layer (A)”) is used as a gas barrier.
  • undercoat layer (A) an isocyanate compound exists near each interface of the gas barrier layer / undercoat layer (A), undercoat layer (A) / plastic substrate, and the polycarboxylic acid polymer Interfacial reaction with a functional group such as a carboxyl group or a hydroxyl group contained in the plastic substrate, or an electrical cohesive force between polar groups at the interface is generated, and the interlayer adhesion can be further improved.
  • the gas barrier material can be ionized by a polyvalent metal without being subjected to immersion treatment or spray treatment with water containing the polyvalent metal.
  • the crosslinking rate can be increased, and a gas barrier laminate having excellent gas barrier properties can be produced with high productivity.
  • the gas barrier laminate of the present invention has a sufficient gas barrier performance, and has an oxygen permeation amount (based on JIS K-7126) of 0.3 cm 3 / m 2 ⁇ day ⁇ atm (25 ° C.-80% RH). Under the environment) In addition, even when subjected to retort sterilization, it has an excellent gas barrier property and retort resistance with an oxygen permeation amount of 0.7 cm 3 / m 2 ⁇ day ⁇ atm (under an environment of 25 ° C.-80% RH) or less. ing.
  • the oxygen permeation amount when the flexibility was evaluated by the oxygen permeation amount after performing the crush treatment 200 times by the gelboflex tester after the retort treatment by the method shown in the examples, the oxygen permeation amount was 10 cm 3 / m 2 ⁇ day ⁇ atm. (Under an environment of 25 ° C. to 80% RH) The following flexibility is excellent. As a result, there is no delamination and excellent interlayer adhesion.
  • the gas barrier material used in the gas barrier laminate of the present invention is a monovalent metal element in which the gas barrier layer made of a polycarboxylic acid polymer is 0.10 to 1.4% by weight, particularly 0.30 to 1.25% by weight. And 5.0 to 18.0% by weight, especially 8.0 to 16.0% by weight of the polyvalent metal element, and 0.01 to 3.0% by weight, particularly 0, based on the total weight of nitrogen and carbon. It is an important feature to contain 0.02 to 2.8% nitrogen.
  • the monovalent metal element and the polyvalent metal element in the gas barrier layer are each a monovalent metal-containing compound used for partially neutralizing the polycarboxylic acid polymer, and between the carboxyl groups of the polycarboxylic acid polymer.
  • the nitrogen element is derived from an isocyanate compound.
  • the content of these elements is in the above range, so that the above-described effects are obtained. Expressed.
  • the content of these metal elements can be measured by using an ICP mass spectrometer after ashing the gas barrier layer, and the nitrogen element in the gas barrier layer can be measured by a combustion method,
  • the content of carbon, oxygen and nitrogen atoms in the surface layer can be measured by surface analysis using XPS (X-ray Photo-electronic Spectroscopy).
  • the gas barrier layer having such characteristics is obtained by forming a composition for forming a gas barrier layer containing a polycarboxylic acid polymer, a basic compound having a monovalent metal element necessary for partial neutralization of the polymer, and an isocyanate compound into a plastic group. It can be formed by forming a coating film on the material and ion-crosslinking carboxyl groups in these with a polyvalent metal-containing compound.
  • the undercoat layer (A) containing an isocyanate compound having at least two isocyanate groups in one molecule is formed between the plastic substrate and the gas barrier layer, the undercoat layer (A In the case where not only an isocyanate compound but also a polyvalent metal-containing composition is contained in), a solution containing a polycarboxylic acid polymer is applied on the undercoat layer (A) to form a layer. It is possible to efficiently supply polyvalent metal ions and isocyanate compounds from the undercoat layer (A) to the polycarboxylic acid-based polymer.
  • Polycarboxylic acid polymer As the polycarboxylic acid polymer constituting the gas barrier layer, a polymer partially neutralized with a monovalent metal element is preferably used, particularly 0.4 to 4.5% in terms of molar ratio to the carboxyl group. A polycarboxylic acid polymer partially neutralized in the range of 0 to 4.0% is desirable for controlling the amount of the monovalent metal element in the gas barrier material within the above range.
  • the monovalent metal sodium and potassium are particularly preferable, and it is preferable to neutralize the polycarboxylic acid polymer using these hydroxides as the monovalent metal compound.
  • polycarboxylic acid-based polymer examples include homopolymers or copolymers of monomers having a carboxyl group, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, polyitaconic acid, and acrylic acid-methacrylic acid copolymer. Polyacrylic acid and polymethacrylic acid are preferred.
  • the “weight average molecular weight” of the polycarboxylic acid polymer is not particularly limited, but is preferably in the range of 2000 to 5,000,000, particularly 10,000 to 1,000,000.
  • weight average molecular weight is measured using two separation columns, “TSK G4000PWXL” and “TSK G3000PWXL” (manufactured by Tosoh Corporation), using a 50 mmol aqueous phosphoric acid solution as an eluent and a flow rate of 1.degree. It was determined from the chromatogram and the standard polycarboxylic acid polymer calibration curve at 0 ml / min.
  • the gas barrier material preferably contains the nitrogen element in the above-described range in the gas barrier layer by blending an isocyanate compound.
  • an isocyanate compound exemplified as an isocyanate curing agent used in the undercoat layer (A) to be described later can be appropriately selected and used.
  • the isocyanate compounds a polycarboxylic acid polymer and a phase are used. It is preferable to use those having poor solubility, such as isophorone diisocyanate and derivatives thereof.
  • the isocyanate compound can be efficiently bleed out on the surface of the gas barrier material, and a chemical bond derived from the isocyanate compound can be present on the surface of the gas barrier material. It can also be granted.
  • a gas barrier material is prepared by preparing a gas barrier layer forming composition containing a polycarboxylic acid polymer, a basic compound having a monovalent metal element necessary for partial neutralization of the polymer, and an isocyanate compound. Forming a film, sheet or coating film comprising a layer-forming composition on a plastic substrate and ion-crosslinking carboxyl groups of a polycarboxylic acid polymer with a polyvalent metal alkaline compound-containing composition it can. Further, as described above, an undercoat layer (A) to be described later is formed on a plastic substrate, and a film, sheet or coating film comprising the gas barrier layer forming composition is formed on the undercoat layer (A). It can be formed by forming on top.
  • the composition for forming a gas barrier layer may be prepared by dissolving a polycarboxylic acid polymer and an isocyanate compound in a solvent containing water, or by mixing a water-containing solution of these components.
  • This is a solution in which a carboxylic acid polymer is dissociated.
  • the solvent for dissolving the polycarboxylic acid-based polymer may be water alone, but may be a mixed solvent of water such as alcohol such as methanol, ethanol and isopropanol, ketone such as 2-butanone and acetone, and aromatic solvent such as toluene.
  • a solvent having a boiling point lower than that of water can be used in combination with water.
  • the organic solvent is preferably blended in an amount of 10 to 400 parts by weight with respect to 100 parts by weight of water.
  • an inorganic dispersion can also be contained.
  • Such an inorganic dispersion has a function of blocking moisture from the outside and protecting the gas barrier material, and can further improve gas barrier properties and water resistance.
  • Such inorganic dispersions may be spherical, needle-like, layered, etc., but may have any shape, but have a wettability with respect to the polycarboxylic acid polymer, and those that disperse well in the gas barrier layer forming composition are used. Is done.
  • a silicate compound having a layered crystal structure such as water-swellable mica and clay is preferably used.
  • These inorganic dispersions preferably have an aspect ratio of 30 or more and 5000 or less in that they are dispersed in layers and block moisture.
  • the content of the inorganic dispersion is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the total of the polycarboxylic acid polymer and the isocyanate compound.
  • the amount of the polycarboxylic acid-based polymer contained in the resin composition in the gas barrier layer forming composition is at least 150 KOHmg / g or more in terms of acid value, particularly in the range of 250 to 970 KOHmg / g.
  • the acid value is obtained by determining the number of mg of potassium hydroxide necessary for neutralizing the acidic free functional group contained in 1 g of the resin by a conventional method based on alkali neutralization titration.
  • the isocyanate compound is preferably contained in an amount of 0.04 to 12 parts by weight, particularly 0.1 to 7 parts by weight, based on 100 parts by weight of the polycarboxylic acid polymer.
  • the type and content of the polycarboxylic acid polymer or isocyanate compound to be used, or the composition for forming the gas barrier layer on the plastic substrate or the composition for forming the gas barrier layer applied on the undercoat layer (A) described later Although it depends on the coating amount, it is heated at a temperature of 40 to 110 ° C. for 1 second to 1 minute (peak holding time) to form a sheet, film or coating film.
  • the undercoat layer (A) containing the polyvalent metal-containing composition is not formed, the gas barrier material is formed by ion-crosslinking the carboxyl group in the sheet, film or coating film with the polyvalent metal compound. Can be manufactured.
  • Ion cross-linking with a polyvalent metal is not limited to this, but the metal barrier can be easily treated by treating the gas barrier material with water containing an alkali compound of a polyvalent metal or an alcohol solution containing an alkali compound of a polyvalent metal. A crosslinked structure can be formed.
  • the treatment with water containing an alkali compound of a polyvalent metal includes (i) immersion treatment of a gas barrier material in water containing an alkali compound of a polyvalent metal, (ii) water containing an alkaline compound of a polyvalent metal Spray treatment to gas barrier material, (iii) atmosphere treatment in which gas barrier material is placed under high humidity after treatment of (i) to (ii), (iv) retort treatment with water containing alkaline compound of polyvalent metal (preferably , A method in which the packaging material and hot water are in direct contact), and the like.
  • the process (iii) is a process that brings about the aging effect after the processes (i) to (ii), and enables the processes (i) to (ii) to be shortened.
  • the treated water used in any of the above treatments (i) to (iii) may be cold water, but the alkali of the polyvalent metal is used so that the water containing the alkaline compound of the polyvalent metal easily acts on the gas barrier material.
  • the temperature of the water containing the compound is set to 20 ° C. or higher, particularly 40 to 100 ° C.
  • the treatment time is preferably 3 seconds or more, particularly 10 seconds to 4 days, and in the case of (iii), the treatment time (i) to (ii) is 0.
  • the treatment temperature is 101 ° C. or higher, particularly 120 to 140 ° C., and the treatment is performed for 1 second or longer, particularly 3 seconds to 120 minutes.
  • the water containing the alkali compound of the polyvalent metal is preferably neutral to alkaline.
  • the alcohol-based solution containing the polyvalent metal alkaline compound is applied onto the film, sheet, or coating film comprising the gas barrier material-forming composition described above. This can be done by coating. Since the alcohol-based solution easily penetrates into a film or the like made of the gas barrier layer forming composition, the composition for forming the gas barrier layer can be efficiently impregnated with the polyvalent metal, and the number of steps compared to the treatment with water. Or processing time can be shortened and it is excellent in productivity.
  • the solvent used in the alcohol-based solution containing the polyvalent metal alkaline compound include methanol, ethanol, isopropanol, and the like, although they vary depending on the type of the polyvalent metal alkaline compound used.
  • the polyvalent metal ion is not particularly limited as long as the carboxyl group of the polycarboxylic acid polymer can be cross-linked.
  • Alkaline earth metal magnesium Mg, calcium Ca, strontium Sr, barium Ba, etc.
  • Group 8 metal of the periodic table Examples include metal ions such as iron (Fe, ruthenium Ru, etc.), periodic table group 11 metals (copper Cu, etc.), periodic table group 12 metals (zinc Zn, etc.), periodic table group 13 metals (aluminum Al, etc.),
  • it is preferably divalent to trivalent, and divalent metal ions such as calcium, magnesium ion, and zinc can be suitably used.
  • the said metal ion can be used 1 type or in combination of 2 or more types.
  • alkaline compounds of polyvalent metals include hydroxides (eg, magnesium hydroxide, calcium hydroxide, etc.), carbonates (eg, magnesium carbonate, calcium carbonate, etc.), organic acid salts, eg, carboxylic acids of the above metals. Salts (for example, acetates such as zinc acetate and calcium acetate, or lactates such as zinc lactate and calcium lactate) can be exemplified, but there are safety viewpoints and metal ion crosslinking when used as food packaging materials. It is particularly preferable to use at least one of calcium or magnesium carbonate and hydroxide in that the by-product when formed does not remain in the gas barrier material.
  • an alkali compound of a polyvalent metal When an alkali compound of a polyvalent metal is contained in water, it is preferably 0.125 mmol / L or more, more preferably 0.5 mmol / L or more, in terms of metal atom in water, and 2.5 mmol / L. It is still more preferable that it is above.
  • the polyvalent metal used in the solution varies depending on the type of polyvalent metal alkaline compound used in the alcoholic solvent and the coating amount. In terms of metal atom, it is preferably 1 mmol / L or more, more preferably 10 mmol / L or more, and further preferably 30 mmol / L or more.
  • the carboxyl groups of the polycarboxylic acid polymer are ion-crosslinked at a ratio of 20% or more, particularly 30% or more with polyvalent metal ions. It is desirable that
  • a layer (A) containing an isocyanate compound having at least two isocyanate groups in one molecule (undercoat layer (A) between the plastic substrate and the gas barrier layer.
  • undercoat layer (A) between the plastic substrate and the gas barrier layer.
  • a polycarboxylic acid-based material is formed on the undercoat layer (A).
  • the undercoat layer (A) is an undercoat containing a main material resin and an isocyanate curing agent having at least two isocyanate groups in one molecule, preferably further containing an alkali compound of a polyvalent metal. It can be formed from the coating layer forming composition (A ′), the main material resin is a polyester polyol containing a metal element in the resin skeleton, and the isocyanate curing agent is a linear aliphatic isocyanate compound and a skeleton. A combination of alicyclic isocyanate compounds having an alicyclic ring structure therein is particularly preferred.
  • the polyester polyol containing a metal element as a main material resin in the resin skeleton can itself have an adhesive layer for the undercoat layer (A) as an undercoat agent and has a metal element. Is easily swelled with respect to a water-containing solvent, so that the gas barrier layer effectively swells by applying a paint having a polycarboxylic acid-based polymer to swell the polyvalent metal ions present in the undercoat layer (A). It becomes possible to move in.
  • the undercoat layer (A) is formed with a region (a) not containing a polyvalent metal alkaline compound, The nitrogen content in the region (a) is larger than the nitrogen content in the undercoat layer (A) other than the region (a).
  • the main material resin used for the undercoat layer (A) it is preferable to use a non-aqueous resin in which a metal element is contained in the resin skeleton, and urethane, epoxy, acrylic, polyester, etc. It is preferable to introduce a metal base into the monomer constituting these polymers, so that a metal element can be included in the formed resin skeleton.
  • the “non-aqueous resin” is a concept that excludes an emulsion or latex dispersed in a solvent containing water, or a water-soluble resin, and thereby an undercoat caused by excessive swelling that occurs upon contact with a water-containing solvent. A decrease in the mechanical strength of the layer (A) is effectively prevented.
  • the metal base suitable for introduction into the resin monomer it is desirable to have a functional group having polarity in order to improve the dispersibility of the polyvalent metal.
  • Etc examples of the metal element include lithium Li, potassium K, sodium Na, magnesium Mg, calcium Ca, copper Cu, and iron Fe.
  • a monovalent metal element is particularly preferable, and the present invention.
  • sodium sulfonate is preferably introduced.
  • an isocyanate curing agent is used to obtain excellent adhesion to a plastic substrate and to increase the dispersibility of an alkaline compound of a polyvalent metal.
  • a polyol component such as a polyester polyol, a polyether polyol, or a urethane modified product thereof, whereby a urethane bond is formed in the undercoat layer (A), and excellent adhesion to the substrate and The dispersibility of the polyvalent metal alkaline compound can be increased.
  • the isocyanate curing agent necessary for reacting the hydroxyl content in the polyol component is 1 equivalent
  • the isocyanate curing agent is preferably present so as to be at least 4 equivalents or more.
  • polyester polyol or a urethane-modified product thereof is preferable.
  • these polyester polyol components include polyester polyols obtained by reacting polyvalent carboxylic acids or their dialkyl esters or mixtures thereof with glycols or mixtures thereof.
  • the glass transition temperature of the polyester polyol is preferably ⁇ 50 ° C. to 100 ° C., more preferably ⁇ 20 ° C. to 80 ° C.
  • the number average molecular weight of these polyester polyols is preferably from 1,000 to 100,000, more preferably from 3,000 to 80,000.
  • polyvalent carboxylic acid examples include aromatic polyvalent carboxylic acids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid, and aliphatic polyvalent carboxylic acids such as adipic acid, azelaic acid, sebacic acid, and cyclohexanedicarboxylic acid.
  • glycol examples include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, and 1,6-hexanediol.
  • a non-aqueous resin having a metal element in the resin skeleton can be obtained by copolymerizing a component having a metal base introduced into the polyol component or the polyvalent carboxylic acid component.
  • the polyvalent carboxylic acid introduced with such a metal base include metals such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5 [4-sulfophenoxy] isophthalic acid. Mention may be made of salts.
  • Examples of the polyol having a metal base introduced include metal salts such as 2-sulfo-1,4-butanediol and 2,5-dimethyl-3-sulfo-2,5-hexanediol. Particularly preferred is 5-sodium sulfoisophthalic acid.
  • the component into which the metal base has been introduced is desirably copolymerized in an amount of 0.01 to 10 mol%. When the amount is less than the above range, the migration of polyvalent metal ions cannot be sufficiently promoted. On the other hand, when the amount is more than the above range, the water resistance is poor.
  • Whether or not the metal element is contained in the resin skeleton of the non-aqueous resin can be detected, for example, by analyzing the raw material resin with fluorescent X-rays.
  • isocyanate curing agent As the isocyanate curing agent used in the present invention, as described above, it is particularly preferable to use a combination of a linear aliphatic isocyanate compound and an alicyclic isocyanate compound having an alicyclic ring structure in the skeleton.
  • the linear aliphatic isocyanate compound and the alicyclic isocyanate compound are desirably blended in a weight ratio of 60:40 to 15:85, particularly 55:45 to 30:70.
  • the linear aliphatic isocyanate compound is less than the above range, sufficient adhesion cannot be obtained, and when the alicyclic isocyanate compound is less than the above range, the region (a) is formed. May be difficult to do.
  • linear aliphatic isocyanate examples include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
  • linear aliphatic isocyanate examples include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
  • those having an isocyanurate structure are preferable.
  • an isocyanurate body having 1,6-hexamethylene diisocyanate as a structural unit can be preferably used.
  • Examples of the alicyclic isocyanate compound having an alicyclic ring structure in the skeleton include 1,3-cyclohexylene diisocyanate, 4-cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4.
  • Examples include '-dicyclohexylmethane diisocyanate and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate.
  • isophorone diisocyanate and derivatives thereof can be preferably used.
  • linear aliphatic polyisocyanate compound and the alicyclic isocyanate compound examples include polyfunctional polyisocyanate compounds such as isocyanurate, burette and allophanate derived from the polyisocyanate monomer, or trimethylolpropane and glycerin.
  • a polyfunctional polyisocyanate compound containing a terminal isocyanate group obtained by a reaction with a trifunctional or higher functional polyol compound can also be used.
  • the linear aliphatic isocyanate compound easily diffuses uniformly in the undercoat layer when diffusing with the solvent volatilization, so that the glass transition temperature (Tg) is ⁇ 20 ° C. or less. It is preferable that the number average molecular weight (Mn) is 1200 or less, particularly the glass transition temperature (Tg) is ⁇ 40 ° C. or less and the number average molecular weight (Mn) is 1100 or less.
  • the alicyclic isocyanate compound remains on the barrier layer side of the undercoat layer (A) or the plastic substrate side, so that it is easy to form the region (a), so that the glass transition temperature (Tg ) Is 50 ° C. or higher, the number average molecular weight (Mn) is 400 or higher, particularly the glass transition temperature (Tg) is 60 ° C. or higher, and the number average molecular weight (Mn) is preferably 500 or higher.
  • Alkaline compound of polyvalent metal As the polyvalent metal alkaline compound to be contained in the undercoat layer (A), those mentioned above can be used, but the polyvalent metal alkaline compound that has migrated to the gas barrier layer composed of the polycarboxylic acid-based polymer dissolves quickly. Therefore, it is preferable that the surface of the particles of the alkali compound of the polyvalent metal is not subjected to chemical treatment. In addition, particles of an alkali compound of a polyvalent metal may remain in a portion other than the region (a) in the undercoat layer (A) of the gas barrier material. Depending on the remaining amount of the particles, the primary particles of the particles When the diameter exceeds 0.5 ⁇ m, the transparency of the gas barrier material may slightly decrease.
  • the primary particle diameter of the alkali metal particles of the polyvalent metal is preferably 0.5 ⁇ m or less, and particularly preferably 0.4 ⁇ m or less.
  • the primary particle diameter of the alkali compound particles of the polyvalent metal can be determined by observation with a secondary electron image of a scanning electron microscope. Further, it is preferable that the amount of the polyvalent metal alkaline compound particles remaining in the undercoat layer is small. Thereby, the adhesiveness of a plastic base material and an undercoat layer (A) improves more.
  • the residual amount (equivalent) which is the difference between the charged amount (equivalent) of the alkaline compound of the polyvalent metal and the amount (equivalent) used for ionic crosslinking is 1.1 or less, particularly 0.3 or less. Preferably there is.
  • undercoat layer forming composition (A ′) the content of the alkali compound of the polyvalent metal is based on one polyvalent metal ion.
  • the polycarboxylic acid system present in the composition forming the gas barrier layer (B) in terms of metal atoms (hereinafter referred to as “gas barrier layer forming composition (B ′)”) It is preferable to contain it so that it may become 0.3 equivalent or more with respect to the carboxyl group of a polymer, and when using it for the use attached
  • the resin content in the composition for forming an undercoat layer (A ′) is preferably adjusted to 15 to 80% by weight, particularly 20 to 60% by weight.
  • the resin content is preferably non-aqueous, and prepared with a solvent such as toluene, 2-butanone, cyclohexanone, solvesso, isophorone, xylene, ethyl acetate, or butyl acetate.
  • a low-boiling solvent in order to make it possible to form a layer at a low temperature.
  • solvents may be dissolved alone or in a mixed solution, or can be prepared by mixing solutions of respective components.
  • examples of the plastic substrate (P) for forming the gas barrier layer (B) or the undercoat layer (A) include a film or sheet made of a thermoplastic resin that can be thermoformed.
  • examples of the method for producing a film or sheet include conventionally known forming methods such as a T-die method, an inflation film forming method, and a cast film forming method.
  • the film or sheet can be used as a biaxially stretched film or sheet produced by biaxially stretching sequentially or simultaneously at a stretching temperature and heat-setting the stretched film or sheet.
  • thermoplastic resin constituting the plastic substrate are low-, medium- or high-density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene-copolymer, ionomer.
  • Resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate, polyethylene naphthalate; nylon 6, nylon 6 , 6, nylon 6,10, polyamide such as metaxylylene adipamide; polystyrene, styrene-butadiene block copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer (AB Resin) and other styrene copolymers; polyvinyl chloride and vinyl chloride copolymers such as vinyl chloride-vinyl acetate copolymer; polymethyl (meth) acrylate, polyethyl (meth) acrylate, methyl methacrylate / ethyl
  • thermoplastic resins may be used alone or exist in the form of two or more blends, and the plastic substrate may be in a single layer configuration or, for example, co-melt extrusion or other A laminated structure of two or more layers by lamination may be used.
  • the melt-moldable thermoplastic resin may contain one or more additives such as pigments, antioxidants, antistatic agents, ultraviolet absorbers, lubricants, etc. as required per 100 parts by weight of the resin. The total amount can be added in the range of 0.001 to 5.0 parts.
  • fiber reinforcing materials such as glass fibers, aromatic polyamide fibers, carbon fibers, pulp, cotton linters, powder reinforcing materials such as carbon black and white carbon, or glass flakes
  • flaky reinforcing materials such as aluminum flakes
  • one or two or more kinds of flaky reinforcing materials can be blended in an amount of 2 to 150 parts by weight as a total amount per 100 parts by weight of the thermoplastic resin. 5 to 100 parts by weight of one or more of calcium carbonate, mica, talc, kaolin, gypsum, clay, barium sulfate, alumina powder, silica powder, magnesium carbonate, etc.
  • thermoplastic resin As a total amount per 100 parts by weight of the thermoplastic resin
  • a prescription known per se in the amount of 5 to 100 parts by weight as a total amount of scaly inorganic fine powders such as water-swellable mica and clay per 100 parts by weight of the thermoplastic resin
  • an inorganic thin film layer such as silicon oxide or aluminum oxide on a plastic substrate by physical or chemical vapor deposition. Absent.
  • the gas barrier material used in the present invention is obtained by applying the gas barrier layer-forming composition described above or forming the undercoat layer (A) on at least one surface of the plastic substrate (P), and then forming the undercoat layer.
  • a gas barrier layer forming composition (B ′) is applied on (A).
  • the coating amount of the undercoat layer-forming composition (A ′) is determined by the resin content in the undercoat layer-forming composition (A ′) and the charged amount of the polyvalent metal alkaline compound, and is generally defined.
  • the gas barrier layer in which the resin content in the formed layer (A) is in the range of 0.02 to 5.0 g / m 2 , especially 0.1 to 2.5 g / m 2 and is then applied
  • the polyvalent metal ion is applied in an amount of 0.3 equivalent or more with respect to the carboxyl group of the polycarboxylic acid-based polymer in the forming composition solution (B ′). If the resin content is less than the above range, it becomes difficult to fix the undercoat layer (A) to the plastic substrate (P), while even if the resin content is more than the above range, it is only inferior in economic efficiency. There is no merit.
  • the undercoat layer-forming composition (A ′) applied on the plastic substrate (P) is 0.5 seconds to 50 ° C. at a temperature of 50 to 200 ° C., depending on the type of coating used and the coating amount. By drying for 5 minutes, particularly at a temperature of 60 to 140 ° C. for 1 second to 2 minutes, it is possible to form the undercoat layer (A) without affecting the plastic substrate, An undercoat layer (A) can be formed economically.
  • the amount of polycarboxylic acid-based polymer contained in the gas barrier layer-forming composition (B ′) applied on the plastic substrate (P) or the undercoat layer (A), that is, the amount of free carboxyl groups is at least an acid value. It is preferably 150 KOH mg / g or more, particularly in the range of 250 to 970 KOH mg / g.
  • the coating amount of the gas barrier layer-forming composition (B ′) is 0.3 to 4.5 g / m 2 in a dry state of only the resin before ionic crosslinking is formed in the gas barrier layer (B). In particular, it is preferable to apply in a range of 0.5 to 3.0 g / m 2 .
  • the applied gas barrier layer-forming composition (B ′) is subjected to heat treatment.
  • the undercoat layer (A) is formed during the heat treatment, the undercoat layer (A)
  • the polyvalent metal ions and the isocyanate compound migrate into the gas barrier layer forming composition (B ′), form a metal ion cross-linked structure between the carboxyl groups of the polycarboxylic acid polymer, and the nitrogen element derived from the isocyanate compound It exists in the interface vicinity with the surface layer and undercoat layer of a gas barrier layer.
  • the heating condition of the gas barrier layer forming composition (B ′) is preferably 40 to 110 ° C., particularly 50 to 100 ° C., preferably 1 second to 1 minute, and 2 seconds to 30 seconds. More preferably.
  • the application of the undercoat layer forming composition (A ′) and the gas barrier layer forming composition (B ′) and the drying or heat treatment described above can be performed by a conventionally known method.
  • the coating method is not limited to this, but for example, spray coating, dipping, or coating by a bar coater, roll coater, gravure coater or the like is possible.
  • the drying or heat treatment can be performed by oven drying (heating), infrared heating, high-frequency heating, or the like.
  • the undercoat layer (A) is not formed, as described above, the gas barrier layer is treated with water containing a polyvalent metal alkaline compound or an alcohol solution containing a polyvalent metal alkaline compound.
  • the carboxyl group in the gas barrier layer can be ionically crosslinked.
  • thermoplastic resin can be directly extrusion coated onto the gas barrier material. That is, as a basic layer configuration of the gas barrier laminate of the present invention, as shown in FIG. 2, for example, a gas barrier material in which a gas barrier layer (B) is formed on at least one surface of a plastic substrate (P). 1, a layer structure in which layers 2a and 2b made of a thermoplastic resin are formed by coextrusion lamination, more preferably, as shown in FIG. 3, between a plastic substrate (P) and a gas barrier layer (B).
  • Layers 2a and 2b made of a thermoplastic resin are formed on the gas barrier material 1 on which the undercoat layer (A) containing an isocyanate compound having at least two isocyanate groups in one molecule is formed by coextrusion lamination.
  • the layer structure can be mentioned.
  • the layer made of the thermoplastic resin is formed in a two-layer structure by coextrusion laminating, but of course, it may be a single layer extrusion laminating.
  • the gas barrier laminate of the present invention can perform sandwich lamination in which a base material made of paper or synthetic resin is laminated on a gas barrier material through a thermoplastic resin simultaneously with extrusion coating of a thermoplastic resin.
  • a gas barrier laminate in which a base material 3 made of paper or synthetic resin is laminated via a layer 2 made of a thermoplastic resin can be obtained (FIG. 4).
  • a base material 3 such as paper is sandwich-laminated on the gas barrier layer (B) of the gas barrier material 1 through a thermoplastic resin 2a, and then a layer made of another thermoplastic resin on the plastic base material (P) of the gas barrier material.
  • 2b can also be extrusion laminated (FIG. 5).
  • the layer 2b made of another thermoplastic resin formed by extrusion lamination in FIG. 5 can be coextruded so as to have a two-layer structure of a surface layer 2c and a lower layer 2d (FIG. 6).
  • thermoplastic resin that can be extrusion laminated on the gas barrier layer it can be used by appropriately selecting from the thermoplastic resins that can be used for the plastic substrate described above. It is preferred to have an intrinsic viscosity of 10 dL / g.
  • polyolefin resins can be particularly preferably used.
  • the polyolefin resins a substrate made of paper or a synthetic resin is interposed via a thermoplastic resin as described later. From the viewpoint of adhesion, it is particularly preferable to use an ethylene- (meth) acrylic acid copolymer or ionomer resin that forms a hydrogen bond with the gas barrier material.
  • polyolefin resins containing no antioxidants and polyolefin resins containing reactive groups such as epoxy groups capable of forming chemical bonds with polar groups such as carboxyl groups and hydroxyl groups on the surface of base materials and gas barrier materials. It can be preferably used. These are particularly suitable for applications where water resistance is required because the adhesive strength is less likely to decrease even under high humidity as compared to the ethylene- (meth) acrylic acid copolymer or ionomer resin.
  • the term “antioxidant-free” as used herein means that the antioxidant contained in the resin is 10 ppm or less, and the oxidation of the resin is promoted at the time of melt extrusion, so that polar groups increase in the resin.
  • the cohesive force with the material and the gas barrier material can be increased.
  • the polyolefin resin having the latter reactive group not only the chemical reaction is performed using the heat at the time of melt extrusion, but also by heat storage (curing) in the oven or incubator after the extrusion lamination, It is possible to increase the adhesion by promoting the reaction.
  • polystyrene resins examples include linear low density polyethylene polymerized using a single site catalyst represented by a metallocene catalyst having a low molecular weight distribution and low density.
  • a polyolefin resin is particularly advantageous in terms of an anchor effect because crystallization hardly occurs during cooling after extrusion and distortion due to crystallization is small.
  • the density (measurement conditions 23 ° C., conforming to JIS-K6922-1) 0.950g / cm 3 less preferred, from the viewpoint of the anchor effect, in particular a density 0.920 g / cm 3 or less preferred .
  • the melt flow rate (MFR: measurement conditions are 190 ° C., 2.16 kg load, conforming to JIS-K6922-1) is preferably 0.1 g / 10 min or more.
  • MFR 7.0 g / 10 min or more is preferable from the viewpoint of being easily immersed in the gas barrier material and easily obtaining excellent adhesiveness.
  • the thermoplastic resin is sufficiently bonded to the gas barrier material, and the more flexible the thermoplastic resin is, the higher the effect of relieving the stress when the laminate is subjected to stress such as bending or tension. Therefore, the occurrence of cracks in the gas barrier layer can be suppressed, which is effective in terms of oxygen barrier stability.
  • the flexural modulus of the thermoplastic resin is preferably 130 MPa or less, particularly preferably 100 MPa or less.
  • the layer made of the specific polyolefin resin described above is a lower layer located on the gas barrier material side, and a polyolefin such as low density polyethylene generally used as an inner surface side resin of a packaging container It is particularly preferred to use the resin as a surface layer in combination.
  • the base paper it can be used without any particular limitation, but examples include ivory base paper, cup base paper, Manila ball base paper, card paper, synthetic paper, etc., preferably used in the field of conventional packaging containers. It is desirable to use a paper base that is applied, and it may be either coated or non-coated. Moreover, in order to improve adhesiveness with a thermoplastic resin, surface treatments, such as a corona discharge treatment, may be given. Furthermore, a thermoplastic resin such as a polyolefin resin can be laminated on paper in advance. Moreover, as a synthetic resin used as a base material, the same thing as the plastic base material (P) of the gas barrier material mentioned above can be used.
  • the gas barrier laminate of the present invention can be molded by directly extruding a thermoplastic resin melt-kneaded by an extruder from a T die, an annular die or the like onto the aforementioned gas barrier material.
  • a base material made of paper or synthetic resin is laminated at the same time as the extrusion coating of the thermoplastic resin, the paper or synthetic resin is directly passed through the thermoplastic resin that becomes the adhesive resin by the sand lamination method.
  • the resulting substrate can be laminated to the gas barrier material. That is, as shown in FIG.
  • thermoplastic resin 2 is supplied from the extruder 11 between the gas barrier material 1 and the base material 3 made of paper or synthetic resin supplied by the laminating roll 10b, and the gas barrier material 1 / thermoplastic resin 2 / paper or synthetic resin.
  • a gas barrier laminate having the layer structure of the base material 3 is formed.
  • suitable processing conditions for extrusion lamination of a thermoplastic resin to a gas barrier material or further sand lamination of a base material made of paper or synthetic resin differ depending on the type of thermoplastic resin used, etc.
  • the polyolefin resin described above is used as the thermoplastic resin
  • the following conditions can be exemplified.
  • Resin temperature just below the die 200 ° C to 320 ° C
  • Line speed 20-600m / min
  • corona discharge treatment or plasma treatment on gas barrier material or substrate on extrusion line, ozone treatment on molten thermoplastic resin film, anchor coating on substrate Etc. may be applied.
  • co-extrusion lamination in which different types of thermoplastic resins are laminated at the same time, or multiple times of extrusion lamination by a tandem extruder may be performed on the same line.
  • the present invention will be further described in the following examples, but the present invention is not limited in any way by the following examples.
  • the gas barrier layer (B) may be simply referred to as “layer (B)”
  • the undercoat layer (A) may be simply referred to as “layer (A)”.
  • the oxygen permeation amount of the obtained plastic film and the laminate after extrusion lamination was measured using an oxygen permeation amount measuring device (manufactured by Modern Control, OX-TRAN 2/20).
  • the measurement conditions are an environmental temperature of 25 ° C. and a relative humidity of 80%. In the case of a laminate in which paper was laminated, measurement was performed after the paper was peeled off.
  • the contents of the monovalent metal element, polyvalent metal element and nitrogen element in the gas barrier layer (B) were measured.
  • a gas barrier layer made of a polycarboxylic acid polymer is immersed in an alkaline solution and dissolved, and then the solid obtained by evaporating to dryness is incinerated in an oven.
  • an ICP emission spectroscopic analyzer iCAP6000 manufactured by Thermo Fisher Scientific Co., Ltd.
  • the weight ratio of the monovalent metal element and the polyvalent metal element in the gas barrier material was analyzed.
  • a gas barrier layer made of a polycarboxylic acid-based polymer is immersed in an alkaline solution to be dissolved, and then a solid obtained by evaporating to dryness is obtained by a combustion method using an organic element analyzer (Thermoquest EA1110 manufactured by CE Instruments). The weight ratio of nitrogen to the total weight of nitrogen and oxygen was determined by analysis.
  • the ionic crosslinking rate is calculated by measuring with a Fourier transform infrared spectrophotometer using a gas barrier material after ionic crosslinking is formed.
  • the formation of ionic bridges converts the carboxylic acid to the carboxylate.
  • the characteristic absorption band of carboxylic acid is around 920 to 970 cm ⁇ 1, around 1700 to 1710 cm ⁇ 1, around 2500 to 3200 cm ⁇ 1 , and with acid anhydrides around 1770 to 1800 cm ⁇ 1. It has been known.
  • the characteristic absorption band of carboxylate is at a wavelength in the vicinity of 1480-1630 cm ⁇ 1 .
  • the calculation of the ionic crosslinking ratio, peak with a height of a peak having an apex at the wavelength region of 1600 ⁇ 1800 cm-carboxylic acids and anhydrides of -1, the vertices in the wavelength region of carboxylate 1480 ⁇ 1630 cm -1 Use height. More preferably, peak heights having apexes in the wavelength regions of 1695 to 1715 cm ⁇ 1 (i) and 1540 to 1610 cm ⁇ 1 (ii) are used. The infrared absorption spectrum of each sample is detected, and the absorbance at the wavelengths (i) and (ii) is measured to obtain the peak height.
  • the absorbance coefficients of the carboxylic acid and the carboxylate are regarded as the same, and the salt conversion rate of the carboxyl group (the ratio of conversion from the carboxylic acid to the carboxylate), that is, the ionic crosslinking rate X and the following formula (1) are calculated.
  • the alkali compound equivalent Y of the polyvalent metal used for the ion crosslinking is calculated by the following formula (2).
  • X peak height of (ii) / [peak height of (i) + peak height of (ii)] (1)
  • Y X / 100 (2)
  • the peak heights (i) and (ii) refer to the difference in absorbance between the point where the skirt portion of the peak overlaps the baseline and the peak apex.
  • the difference in oxygen permeation amount measured before and after processing that is, the oxygen permeation amount increased by the gas barrier layer being subjected to the processing load is less than 0.3 cc / m 2 ⁇ day ⁇ atm, the processing resistance is ⁇ , In the case of 0.3 to 1.0 cc / m 2 ⁇ day ⁇ atm, the work resistance was ⁇ , and in the case of exceeding 1.0 cc / m 2 ⁇ day ⁇ atm, the work resistance was x.
  • methanol / 2-propanol / MEK / water mixed solvent weight ratio 25/25/40/10
  • a biaxially stretched polyethylene terephthalate film having a thickness of 12 ⁇ m was applied to the coating solution using a bar coater ( And a film having a gas barrier precursor layer was obtained by heat treatment in a conveyor type electric oven under conditions of a set temperature of 105 ° C. and a pass time of 40 seconds.
  • “Body layer” means a gas barrier layer before introduction of ion crosslinking with a polyvalent metal. After adjusting the pH to 12.0 (value at a water temperature of 24 ° C.) by adding 360 mmol (40 g) of calcium chloride to 1 L of tap water in terms of metal, and then adding 11 g of calcium hydroxide, 40 ° C. The film having the precursor of the gas barrier layer was dipped for 3 seconds while warming and stirring well. The film was taken out from the hot water and dried to obtain a film having a gas barrier layer having a coating amount of 1.5 g / m 2 .
  • the gas barrier layer is subjected to corona treatment, and a reactive group-containing low density polyethylene resin (hereinafter referred to as “reactive group-containing LDPE”) (Nippon Polyethylene, Novatec LD LC605Y, MFR 7.3 g / 10 min, density 0.918 g).
  • reactive group-containing LDPE reactive group-containing low density polyethylene resin
  • LDPE low density polyethylene resin
  • Example 2 In Example 1, 720 mmol (80 g) of calcium chloride in terms of metal is added to 1 L of a water / ethanol mixed solvent (30/70 by weight), and then 22 g of calcium hydroxide is added, thereby applying the coating treatment liquid. Got. The film having the gas barrier layer was obtained by applying the coating treatment liquid on the gas barrier precursor layer of the film having the gas barrier precursor layer of Example 1 with a bar coater and then drying. Further, a gas barrier laminate was obtained in the same manner as in Example 1.
  • Example 3 In Example 2, except that potassium hydroxide is added instead of sodium hydroxide in the solution (B ′), and magnesium chloride and magnesium hydroxide are added instead of calcium chloride and calcium hydroxide in the coating solution.
  • a film having a gas barrier layer and a gas barrier laminate were obtained in the same manner as in Example 2.
  • Example 4 Two polyester polyols with a weight ratio of 50/50, Byron 200 (manufactured by Toyobo Co., Ltd., non-aqueous resin containing no metal element in the resin skeleton: confirmed by fluorescent X-ray) and Byron GK570 (manufactured by Toyobo Co., Ltd., resin) Calcium carbonate (CS3N, manufactured by Ube Materials Co., Ltd.) was dissolved in a solution obtained by dissolving a non-aqueous resin containing a metal element in the skeleton: confirmed by fluorescent X-rays with an ethyl acetate / MEK mixed solvent (65/35 by weight).
  • CS3N manufactured by Ube Materials Co., Ltd.
  • a coating liquid (A ′′) comprising the forming composition (A ′) was obtained.
  • the coating solution (A ′′) is applied to a 12 ⁇ m-thick biaxially stretched polyethylene terephthalate film with a bar coater, and then heat-treated with a box-type electric oven at a set temperature of 70 ° C. for a processing time of 2 minutes.
  • a polyethylene terephthalate film having a layer A corresponding to an undercoat layer (A) having an amount of 1.4 g / m 2 was obtained.
  • the gas barrier precursor layer (B0) was prepared by coating the solution (B ′) with a bar coater on the layer A of the polyethylene terephthalate film having the layer A so that the coating amount was 1.5 g / m 2 . .
  • the coating amount of the gas barrier precursor layer (B0) means that the solution (B ′) is directly applied to a biaxially stretched polyethylene terephthalate film and dried, that is, in the solution (B ′) without forming ionic crosslinks. It is the coating amount obtained by drying only polyacrylic acid.
  • a polyethylene terephthalate film having a layer (A), that is, a gas barrier laminate was obtained.
  • PET film (12 ⁇ m) / layer (A) / layer (B) / reactive group-containing LDPE (15 ⁇ m) / LDPE (35 ⁇ m)
  • a laminate having a layer structure as shown in FIG. 3 was obtained.
  • Example 5 ethylene-methacrylic acid copolymer resin (hereinafter referred to as “EMAA”) (manufactured by Mitsui DuPont Polychemicals, Nucrel AN42012C, MFR 7.0 g / 10 min, density 0.940 g / cm 3 , flexural elasticity Example 4 except that 15 ⁇ m and LDPE (Tosoh, Petrocene 204, MFR 7.0 g / 10 min, density 0.922 g / cm 3 ) 35 ⁇ m were coextruded and laminated at 320 ° C. and a line speed of 100 m / min.
  • a gas barrier laminate having a layer structure of PET film (12 ⁇ m) / undercoat layer (A) / gas barrier layer (B) / EMAA (15 ⁇ m) / LDPE (35 ⁇ m) was obtained in the same manner as above.
  • Example 6 In Example 4, an ionomer resin (Mitsui / DuPont Polychemical, High Milan 1652, MFR 5.5 g / 10 min, density 0.950 g / cm 3 , flexural modulus 160 MPa) 15 ⁇ m and LDPE (Tosoh, Petrocene 204, MFR) 7.0 g / 10 min, density 0.922 g / cm 3 ) PET film (12 ⁇ m) / undercoat layer in the same manner as in Example 4 except that 35 ⁇ m was coextruded and laminated at 320 ° C. and a line speed of 100 m / min. A gas barrier laminate having a layer structure of (A) / gas barrier layer (B) / ionomer (15 ⁇ m) / LDPE (35 ⁇ m) was obtained.
  • a gas barrier laminate having a layer structure of (A) / gas barrier layer (B) / ionomer (15 ⁇ m) / LDPE (35 ⁇ m)
  • Example 7 an antioxidant-free metallocene-based linear low-density polyethylene resin (hereinafter referred to as “anti-oxidant-free m-LLDPE”) (manufactured by Tosoh, Lumitac 08L51A, MFR 21 g / 10 min, density) 0.898 g / cm 3 , flexural modulus of 50 MPa or less) 15 ⁇ m and LDPE (Tosoh, Petrocene 204, MFR 7.0 g / 10 min, density 0.922 g / cm 3 ) 35 ⁇ m at 320 ° C., line speed 100 m / min Except for coextrusion lamination, PET film (12 ⁇ m) / undercoat layer (A) / gas barrier layer (B) / antioxidant-free m-LLDPE (15 ⁇ m) / LDPE (35 ⁇ m) in the same manner as in Example 4 Thus, a gas barrier laminate having the layer structure was obtained.
  • Example 8 metallocene linear low density polyethylene (hereinafter referred to as “m-LLDPE”) (manufactured by Nippon Polyethylene, Kernel KC577T, MFR 15 g / 10 min, density 0.910 g / cm 3 , flexural modulus 120 MPa ) 15 ⁇ m and LDPE (Tosoh, Petrocene 204, MFR 7.0 g / 10 min, density 0.922 g / cm 3 ) Same as Example 4 except that 35 ⁇ m was coextruded at 320 ° C. and a line speed of 100 m / min.
  • m-LLDPE metallocene linear low density polyethylene
  • Example 9 an antioxidant-free low density polyethylene (hereinafter referred to as “antioxidant-free LDPE”) (manufactured by Nihon Unicar, NUC-8080, MFR 7.5 g / 10 min, density 0.918 g / Other than co-extrusion laminating 15 ⁇ m cm 3 , flexural modulus 120 MPa) and LDPE (Tosoh, Petrocene 204, MFR 7.0 g / 10 min, density 0.922 g / cm 3 ) 35 ⁇ m at 320 ° C. and line speed 100 m / min.
  • antioxidant-free LDPE antioxidant-free low density polyethylene
  • Example 10 In Example 4, antioxidant-free LDPE (Nippon Polyethylene, Novatec LC520, MFR 3.6 g / 10 min, density 0.923 g / cm 3 , flexural modulus 170 MPa) and 15 ⁇ m LDPE (Tosoh, Petrocene 204, MFR) 7.0 g / 10 min, density 0.922 g / cm 3 ) PET film (12 ⁇ m) / layer (A) in the same manner as in Example 4 except that 35 ⁇ m was coextruded and laminated at 320 ° C. and a line speed of 100 m / min. ) / Layer (B) / antioxidant-free LDPE (15 ⁇ m) / LDPE (35 ⁇ m) layer structure was obtained.
  • antioxidant-free LDPE Nippon Polyethylene, Novatec LC520, MFR 3.6 g / 10 min, density 0.923 g / cm 3 , flexural modulus 170 MPa
  • Example 11 In Example 4, instead of the 12 ⁇ m thick biaxially stretched polyethylene terephthalate film, the coating liquid (A ′′) was applied to the barrier coating surface using a 12 ⁇ m thick Tech Barrier TX (manufactured by Mitsubishi Plastics, silica vapor deposition type barrier film). Except for the above, it has a layer structure of PET film (12 ⁇ m) / silica vapor deposition layer / layer (A) / layer (B) / reactive group-containing LDPE (15 ⁇ m) / LDPE (35 ⁇ m) in the same manner as in Example 4. A gas barrier laminate was obtained.
  • Example 12 In Example 4, the coating liquid (A ′′) was applied to a 15 ⁇ m-thick biaxially stretched nylon film (hereinafter referred to as ONy) instead of the 12 ⁇ m-thick biaxially stretched polyethylene terephthalate film.
  • a gas barrier material was obtained by the method described above: a reactive group-containing LDPE (manufactured by Nippon Polyethylene, Novatec LD LC605Y, MFR) subjected to corona treatment on the gas barrier layer of this barrier material and extruded at 320 ° C. and a line speed of 100 m / min.
  • Example 13 Reactive group-containing LDPE (manufactured by Nippon Polyethylene, Novatec LD LC605Y, MFR) subjected to corona treatment on the gas barrier layer of the gas barrier material obtained in the same manner as in Example 4 and extruded at 320 ° C. and a line speed of 100 m / min.
  • the base paper surface of a base paper having a basis weight of 250 g / m 2 obtained by extrusion laminating LDPE having a thickness of 15 ⁇ m was preliminarily sand-laminated through 15 ⁇ m (3 g / 10 minutes, density 0.918 g / cm 3 , flexural modulus 120 MPa).
  • reactive group-containing LDPE Nippon Polyethylene, Novatec LD LC605Y, MFR 7.3 g / 10 min, density 0.918 g / cm 3 , flexural modulus 120 MPa
  • LDPE Tosoh product
  • Petrocene 204 MFR 7.0 g / 10 min, density 0.922 g / cm 3 ) 35 ⁇ m and coextruded at 320 ° C.
  • a gas barrier laminate having a layer structure of film (12 ⁇ m) / undercoat layer (A) / gas barrier layer (B) / reactive group-containing LDPE (15 ⁇ m) / paper / LDPE (15 ⁇ m) was obtained.
  • Example 14 The gas barrier layer of the gas barrier material obtained in the same manner as in Example 4 was subjected to corona treatment, and reactive group-containing LDPE (Nippon Polyethylene, Novatec LD LC605Y, MFR 7.3 g / 10 min, density 0.918 g / cm 3 and flexural modulus 120 MPa) 15 ⁇ m and LDPE (Tosoh, Petrocene 204, MFR 7.0 g / 10 min, density 0.922 g / cm 3 ) 35 ⁇ m were co-extruded and laminated at 320 ° C. and a line speed of 100 m / min. Furthermore, through reactive group-containing LDPE extruded at 320 ° C.
  • LDPE Densoh, Petrocene 204, MFR 7.0 g / 10 min, density 0.922 g / cm 3
  • Example 15 Instead of reactive group-containing LDPE, EMAA (Mitsui / DuPont Polychemical, Nucrel AN42012C, MFR 7.0 g / 10 min, density 0.940 g / cm 3 , flexural modulus 152 MPa) is used for sand lamination with the base paper via 15 ⁇ m. Except that, LDPE (35 ⁇ m) / Reactive group-containing LDPE (15 ⁇ m) / PET film (12 ⁇ m) / Layer (A) / Layer (B) / EMAA (15 ⁇ m) / Paper / LDPE A gas barrier laminate having a layer structure of (15 ⁇ m) was obtained.
  • Example 16 M-LLDPE without antioxidant added in place of reactive group-containing LDPE (Tosoh, LumiTac 08L51A, MFR 21 g / 10 min, density 0.898 g / cm 3 , flexural modulus 50 MPa or less) Except for laminating, LDPE (35 ⁇ m) / Reactive group-containing LDPE (15 ⁇ m) / PET film (12 ⁇ m) / Layer (A) / Layer (B) / No antioxidant added in the same manner as in Example 13. A gas barrier laminate having a layer structure of LLDPE (15 ⁇ m) / paper / LDPE (15 ⁇ m) was obtained.
  • Example 17 In Example 4, a gas barrier laminate was obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in the solution (B ′) was 20/80.
  • Example 18 In Example 4, the calcium carbonate content is 100 parts by weight, the coating amount of the undercoat layer (A) is 1.0 g / m 2, and the coating amount of the solution (B ′) is 2.0 g / m 2.
  • a gas barrier laminate was obtained in the same manner as in Example 4 except that. With respect to the obtained gas barrier laminate and the gas barrier laminate obtained in Example 4, the peel strength between the undercoat layer (A) and the plastic substrate was measured in the same manner as the adhesive evaluation described above. did. In the gas barrier laminate obtained in Example 4, the residual amount (equivalent) of the polyvalent metal was 0.34 equivalent, and the peel strength between the undercoat layer (A) and the plastic substrate was 2.0 N / 15 mm.
  • the residual amount (equivalent) of the polyvalent metal was 0.02 equivalent, and the peel strength between the undercoat layer (A) and the plastic substrate was 3.0 N. / 15 mm, indicating that the adhesion was improved.
  • Example 19 the gas-barrier laminated body was obtained by the method similar to Example 4 except the neutralization degree with respect to polyacrylic acid in a solution (B ') having been 4.5%.
  • Example 20 In Example 4, a gas barrier laminate was obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in the solution (B ′) was 90/10.
  • Example 21 In Example 4, 30% by weight of a linear aliphatic polyisocyanate (Sumidor N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) was added to the polyester polyol, and the weight of the alicyclic polyisocyanate, excluding the solvent, was added to the polyester polyol.
  • the gas barrier laminate was obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in the solution (B ′) was 30/70.
  • Example 22 In Example 4, a gas barrier laminate was obtained in the same manner as in Example 4 except that the calcium carbonate in the coating liquid (A ′′) was blended to 530 parts by weight with respect to the polyester polyol.
  • Example 23 In Example 4, instead of calcium carbonate in the coating liquid (A ′′), magnesium carbonate (manufactured by Wako Pure Chemical Industries) was used, and the coating amount of the undercoat layer (A) was 1.2 g / m 2. A gas barrier laminate was obtained in the same manner as in Example 4.
  • Example 24 In Example 4, instead of Desmodur Z4470 in the coating liquid (A ′′), Takenate D110N (Mitsui Chemicals, xylylene diisocyanate-based adduct type, solid content 75%) was used, and the weight excluding the solvent was A gas barrier laminate was obtained in the same manner as in Example 4 except that the content was 20 parts by weight based on the polyester polyol.
  • Example 25 In Example 4, instead of Sumidur N3300 in the coating liquid (A ′′), Sumidur HT (manufactured by Sumika Bayer Urethane, 1,6-hexamethylene diisocyanate-based adduct type, solid content 75%) was used. A gas barrier laminate was obtained in the same manner as in Example 4 except that the weight excluding the solvent was 20 parts by weight based on the polyester polyol.
  • Example 26 In Example 4, instead of Byron GK570 in the coating liquid (A ′′), Byron 550 (manufactured by Toyobo Co., Ltd., non-aqueous resin containing no metal element in the resin skeleton: confirmed by fluorescent X-ray) is used. Except for the above, a gas barrier laminate was obtained in the same manner as in Example 5.
  • Example 1 Comparative Example 1 In Example 1, 20 parts by weight of linear aliphatic polyisocyanate (manufactured by Sumika Bayer Urethane, Sumidur N3300) was added to polyacrylic acid, and alicyclic polyisocyanate (manufactured by Sumika Bayer Urethane, Desmodur Z4470). ) was added in the same manner as in Example 1 except that the gas barrier laminate was not added.
  • linear aliphatic polyisocyanate manufactured by Sumika Bayer Urethane, Sumidur N3300
  • alicyclic polyisocyanate manufactured by Sumika Bayer Urethane, Desmodur Z4470
  • Example 4 a gas barrier laminate was obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in the solution (B ′) was 15/85.
  • Example 3 (Comparative Example 3)
  • AC-10LHP polyacrylic acid
  • a 20 wt% sodium hydroxide aqueous solution was added so that the degree of neutralization was 2% with respect to polyacrylic acid.
  • a gas barrier material was obtained in the same manner as in Example 4. Further, this gas barrier material was subjected to an immersion treatment for 3 seconds with good stirring in an immersion treatment solution which was heated to 40 ° C. by adding 40 g of calcium chloride and 11 g of calcium hydroxide to 1 L of tap water. 4 was used to obtain a gas barrier laminate.
  • Example 4 a gas barrier laminate was obtained in the same manner as in Example 4 except that the degree of neutralization with respect to polyacrylic acid in the solution (B ′) was 0.2%.
  • Example 5 (Comparative Example 5) In Example 4, a gas barrier laminate was obtained in the same manner as in Example 4 except that the degree of neutralization of the polyacrylic acid in the solution (B ′) was 5.0%.
  • Example 6 (Comparative Example 6) In Example 4, a gas barrier laminate was obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in the solution (B ′) was 100/0.
  • Example 7 (Comparative Example 7)
  • 35 parts by weight of linear aliphatic polyisocyanate was added to the polyester polyol, and alicyclic polyisocyanate was added so that the weight excluding the solvent was 35 parts by weight with respect to the polyester polyol.
  • a gas barrier laminate was obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in (B ′) was 30/70.
  • This aqueous solution was applied to a biaxially stretched polyethylene terephthalate film having a thickness of 12 ⁇ m using a bar coater, and heat-treated with a box-type electric oven at a set temperature of 200 ° C. for a treatment time of 10 minutes.
  • a gas barrier material of m 2 was obtained.
  • This barrier material was laminated in the same manner as in Example 1, and a layered structure such as PET film (12 ⁇ m) / polyacrylic acid / saccharide cross-linked layer / reactive group-containing LDPE (15 ⁇ m) / LDPE (35 ⁇ m) was laminated. Got the body.
  • Comparative Example 9 In Comparative Example 8, after the heat treatment, 40 g of calcium chloride and 11 g of calcium hydroxide were added to 1 L of tap water, and the soaking treatment liquid was warmed to 40 ° C. and soaked for 3 seconds with good stirring. A gas barrier material was obtained. This barrier material was laminated in the same manner as in Example 1 and was used as PET film (12 ⁇ m) / metal ion cross-linked polyacrylic acid / saccharide cross-linked layer / reactive group-containing LDPE (15 ⁇ m) / LDPE (35 ⁇ m). A layered laminate was obtained.
  • Table 2 shows the measurement results, the presence or absence of layer cracks in the gas barrier after extrusion lamination, and the results of evaluating the adhesion between the gas barrier layer and the thermoplastic resin.
  • the barrier properties and adhesiveness showed good results in all evaluations, but those having a small amount of polyvalent metal elements were inferior in gas barrier properties, and those having an excessive amount of polyvalent metal elements were crack resistance.
  • the appearance evaluation is inferior, and those with an excessive amount of monovalent metal elements are inferior in hot water resistance, and the nitrogen content relative to the total amount of nitrogen and carbon determined by the organic element analyzer
  • the thing with little quantity was inferior in water resistance after a bending process, and the thing with excessive nitrogen content with respect to the total amount of nitrogen and carbon calculated
  • thermoplastic resin extruded and laminated to the gas barrier layer is a reactive group-containing LDPE, the adhesiveness improved after storage over time, and the thermoplastic laminated to the gas barrier layer was extruded.
  • the adhesiveness and workability were particularly good immediately after extrusion lamination.
  • a gas barrier layer using a cross-linked polyacrylic acid / saccharide and a metal ion cross-linked polyacrylic acid / saccharide cross-linked product and a commercially available silica-deposited barrier film showed poor processing resistance. This indicates that the cracks of the gas barrier layer generated by the extrusion lamination further propagated and increased upon processing.
  • the gas barrier laminate of the present invention has excellent barrier properties and flexibility, and can be suitably used for packaging containers such as cups and trays. Moreover, since the gas barrier layer made of a polycarboxylic acid-based polymer has thermal decomposition resistance and crack resistance, a thermoplastic resin can be directly extrusion coated onto the gas barrier material, which is excellent in economy and productivity. It can be suitably used for general-purpose containers that are mass-produced.

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Abstract

L'invention concerne un stratifié faisant barrière aux gaz qui possède sur un matériau de base en plastique, un matériau de barrière au gaz constitué par formation d'une couche de barrière aux gaz à son tour constituée d'un polymère à base d'acide de polycarbonate. Plus précisément, ladite couche de barrière au gaz est constituée d'un polymère à base d'acide de polycarbonate qui contient 0,10 à 1,4% en masse d'un élément métal monovalent, 5,0 à 18,0% en masse d'un élément métal polyvalent, et 0,01 à 3,0% en masse d'un élément azote par rapport à la masse totale d'azote et carbone, ce qui permet de fournir un stratifié faisant barrière aux gaz tel qu'une résine thermoplastique peut revêtir par extrusion directe ledit matériau de barrière au gaz, qu'il possède des propriétés de barrière aux gaz et de flexibilité, et que sa productivité est excellente.
PCT/JP2014/071454 2013-08-15 2014-08-14 Matériau de barrière aux gaz, et stratifié faisant barrière aux gaz WO2015022991A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022075030A1 (fr) * 2020-10-08 2022-04-14

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2009041500A1 (fr) * 2007-09-27 2009-04-02 Toyo Seikan Kaisha, Ltd. Matériau barrière contre les gaz présentant un excellent pouvoir bloquant et son procédé de production
JP2009073007A (ja) * 2007-09-20 2009-04-09 Toppan Printing Co Ltd 紙容器用積層材料及び液体用紙容器
WO2012086589A1 (fr) * 2010-12-24 2012-06-28 東洋製罐株式会社 Stratifié constituant une barrière contre les gaz et son procédé de production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2009073007A (ja) * 2007-09-20 2009-04-09 Toppan Printing Co Ltd 紙容器用積層材料及び液体用紙容器
WO2009041500A1 (fr) * 2007-09-27 2009-04-02 Toyo Seikan Kaisha, Ltd. Matériau barrière contre les gaz présentant un excellent pouvoir bloquant et son procédé de production
WO2012086589A1 (fr) * 2010-12-24 2012-06-28 東洋製罐株式会社 Stratifié constituant une barrière contre les gaz et son procédé de production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022075030A1 (fr) * 2020-10-08 2022-04-14

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