WO2024203674A1 - 積層体および包装材 - Google Patents

積層体および包装材 Download PDF

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Publication number
WO2024203674A1
WO2024203674A1 PCT/JP2024/010897 JP2024010897W WO2024203674A1 WO 2024203674 A1 WO2024203674 A1 WO 2024203674A1 JP 2024010897 W JP2024010897 W JP 2024010897W WO 2024203674 A1 WO2024203674 A1 WO 2024203674A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas barrier
mass
resin
anionic group
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2024/010897
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
和幸 福田
徹 矢木
寿洋 吉村
征也 楠本
靖之 香川
俊彦 中川
祥子 遠藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
Original Assignee
Mitsui Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Priority to JP2025510614A priority Critical patent/JPWO2024203674A1/ja
Priority to EP24779797.0A priority patent/EP4691770A1/en
Priority to KR1020257029991A priority patent/KR20250145660A/ko
Priority to CN202480016977.4A priority patent/CN120813478A/zh
Publication of WO2024203674A1 publication Critical patent/WO2024203674A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • 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
    • B32B27/32—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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • 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
    • B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D2565/38—Packaging materials of special type or form
    • B65D2565/381—Details of packaging materials of special type or form
    • B65D2565/387—Materials used as gas barriers

Definitions

  • the present invention relates to a laminate and a packaging material, and more specifically to a laminate having a gas barrier layer and a heat seal layer.
  • laminates that include a paper base material, a gas barrier layer, and a heat seal layer are known. Such laminates are used, for example, as packaging materials.
  • the gas barrier paper-based packaging body includes a paper substrate.
  • a fixed sealing resin composition e.g., an acrylic resin aqueous emulsion
  • a gas barrier resin composition e.g., a urethane-based hybrid gas barrier resin composition
  • a heat seal agent for example, a dispersion of a polyethylene resin
  • the gas barrier layer imparts gas barrier properties to the gas barrier paper-based packaging body
  • the heat seal layer imparts heat seal properties to the gas barrier paper-based packaging body
  • gas barrier paper-based packaging materials may not have sufficient gas barrier properties (oxygen barrier properties and water vapor barrier properties). Also, gas barrier paper-based packaging materials may be required to have excellent heat seal properties.
  • the present invention is a laminate and packaging material that combines excellent gas barrier properties with excellent heat sealability.
  • the present invention [1] includes a laminate comprising a paper base material, a gas barrier layer disposed on at least one side of the paper base material, and a heat seal layer disposed on at least one side of the gas barrier layer, the amount of the heat seal layer being 1.0 g/m2 or more and 7.0 g/m2 or less .
  • the present invention [2] includes the laminate described in [1] above, in which a sealing layer is interposed between the paper base material and the gas barrier layer.
  • the present invention [3] includes the laminate described in [1] or [2] above, in which the gas barrier layer contains a gas barrier resin.
  • the present invention [4] includes the laminate described in [3] above, in which the gas barrier resin contains a gas barrier polyurethane resin.
  • the present invention [5] includes the laminate described in [4] above, in which the gas barrier polyurethane resin contains a reaction product of an isocyanate-terminated prepolymer and a chain extender, the isocyanate-terminated prepolymer contains a reaction product of a polyisocyanate component and an active hydrogen group-containing component, the polyisocyanate component contains xylylene diisocyanate and/or hydrogenated xylylene diisocyanate, and the active hydrogen group-containing component contains a short-chain diol having 2 to 6 carbon atoms and an active hydrogen compound containing an anionic group.
  • the present invention [6] includes the laminate described in any one of [1] to [5] above, in which the heat seal layer contains an anionic group-containing heat sealable resin, and the anionic group-containing heat sealable resin contains at least one resin selected from the group consisting of an anionic group-containing polyolefin resin, an anionic group-containing (meth)acrylic resin, and an anionic group-containing polyurethane resin.
  • the present invention [7] includes the laminate described in [6] above, in which the anionic group-containing heat sealable resin is neutralized with a neutralizing agent, and the neutralizing agent contains at least one selected from the group consisting of alkali metal hydroxides, ammonia, and amine compounds.
  • the present invention [8] includes the laminate described in [6] or [7] above, in which the moisture absorption expansion coefficient of the anionic group-containing heat sealable resin is 5000 ppm/RH% or more and 10000 ppm/RH% or less.
  • the present invention [9] includes a packaging material containing the laminate described in any one of [1] to [8] above.
  • the laminate of the present invention comprises a paper base material, a gas barrier layer, and a heat seal layer.
  • the amount of the heat seal layer is adjusted to a predetermined range. Therefore, in the laminate, the deterioration of the gas barrier properties due to the heat seal layer is suppressed, and excellent heat seal properties are obtained. As a result, the laminate combines excellent gas barrier properties and excellent heat seal properties.
  • the packaging material of the present invention contains the above laminate, and therefore has both excellent gas barrier properties and excellent heat sealability.
  • the laminate 1 includes a paper base material 2, a gas barrier layer 4 disposed on at least one side in the thickness direction of the paper base material 2 (the upper side of the paper surface), and a heat seal layer 5 disposed on at least one side in the thickness direction of the gas barrier layer 4 (the upper side of the paper surface).
  • the laminate 1 can further include, as an optional layer, a sealing layer 3 interposed between the paper base material 2 and the gas barrier layer 4.
  • the laminate 1 includes a sealing layer 3. That is, in FIG. 1, the laminate 1 includes a paper base material 2, a sealing layer 3, a gas barrier layer 4, and a heat seal layer 5, in that order from the other side in the thickness direction (the lower side of the paper) to one side (the upper side of the paper).
  • the paper base material 2 is a base material formed from paper.
  • Examples of the paper base material 2 include paper made from pulp. Examples of pulp include natural pulp and synthetic pulp. More specifically, examples of the paper base material 2 include glassine paper, coated paper, one-sided gloss kraft paper, roll paper, and cup base paper.
  • the paper base material 2 may be a single-layer paper or may be a multi-layer paper. The paper base material 2 is appropriately selected depending on the application of the laminate 1.
  • the shape of the paper base material 2 is not particularly limited and may be set as appropriate. Examples of the shape of the paper base material 2 include a sheet shape, a bottle shape, and a cup shape. A preferred shape of the paper base material 2 is a sheet shape.
  • the paper substrate 2 may be surface-treated as necessary.
  • surface treatments include corona discharge treatment, surface coating treatment, and vapor deposition treatment.
  • the thickness of the paper base material 2 is, for example, 3 ⁇ m or more, and preferably 5 ⁇ m or more.
  • the thickness of the paper base material 2 is, for example, 500 ⁇ m or less, and preferably 200 ⁇ m or less.
  • the paper base material 2 has a basis weight of, for example, 20 g/m 2 or more, preferably 30 g/m 2 or more.
  • the paper base material 2 has a basis weight of, for example, 400 g/m 2 or less, preferably 300 g/m 2 or less.
  • the solvent is not particularly limited, but examples include water, methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, and acetonitrile. These solvents can be used alone or in combination of two or more types.
  • the solid content concentration of the filler coating material is, for example, 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more.
  • the solid content concentration of the filler coating material is, for example, 60% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less.
  • the gas barrier layer 4 is disposed on the surface of the filling layer 3. That is, the gas barrier layer 4 is disposed on the surface of the filling layer 3 on the side of the paper base material 2 on which the filling layer 3 is disposed.
  • the gas barrier layer 4 may be disposed on both sides of the paper base material 2 together with the filling layer 3.
  • the gas barrier layer 4 is preferably disposed on only one surface of the paper base material 2 together with the filling layer 3.
  • Examples of the gas barrier layer 4 include inorganic layers and resin layers.
  • the inorganic layer contains, for example, a metal and/or a metal oxide.
  • An example of the metal is aluminum.
  • An example of the metal oxide is aluminum oxide and silicon oxide.
  • examples of the inorganic layer include a metal thin film layer and a metal vapor deposition layer.
  • the resin layer contains, for example, a gas barrier resin. More specifically, examples of the resin layer include a barrier coat layer and a barrier film layer.
  • the gas barrier layer 4 is preferably a barrier coat layer containing a gas barrier resin. More specifically, the gas barrier layer 4 is formed, for example, by applying a coating material containing a gas barrier resin (hereinafter, gas barrier coating material) to the filling layer 3 and drying it.
  • gas barrier coating material a coating material containing a gas barrier resin
  • the gas barrier resin is a resin having an oxygen permeability of a predetermined value or less. More specifically, the oxygen permeability of a 10 ⁇ m thick film made of a gas barrier resin is, for example, 1 (cc/ m2 ⁇ day ⁇ atm) or less at room temperature.
  • the oxygen permeability is measured using an oxygen permeability measuring device (MOCON, OX-TRAN2/22H) in accordance with JIS K7126 (2006) Method B. The measurement conditions are 20° C. and 80% RH (relative humidity).
  • the gas barrier resin is not particularly limited.
  • gas barrier resins include gas barrier polyurethane resins and gas barrier acrylic resins. These can be used alone or in combination of two or more types.
  • gas barrier polyurethane resins are preferably used as the gas barrier resin. That is, the gas barrier resin preferably contains a gas barrier polyurethane resin, and more preferably consists of a gas barrier polyurethane resin.
  • the gas barrier polyurethane resin is a resin that has an oxygen permeability equal to or less than the above-mentioned specified value.
  • the gas barrier polyurethane resin there are no particular limitations on the gas barrier polyurethane resin, and any known gas barrier polyurethane resin may be used.
  • the gas barrier polyurethane resin is contained in a polyurethane dispersion (PUD) that serves as a gas barrier coating material.
  • the gas barrier polyurethane resin and polyurethane dispersion are manufactured, for example, in accordance with the description in paragraphs [0026] to [0111] of JP 2015-044396 A and paragraphs [0048] to [0141] of JP 2021-115802 A.
  • the gas barrier polyurethane resin contains, for example, a reaction product of an isocyanate-terminated prepolymer and a chain extender, and preferably consists of a reaction product of an isocyanate-terminated prepolymer and a chain extender.
  • the isocyanate-terminated prepolymer contains, for example, a reaction product of a polyisocyanate component and an active hydrogen group-containing component, and preferably consists of a reaction product of a polyisocyanate component and an active hydrogen group-containing component.
  • the primary reaction product between the polyisocyanate component and the active hydrogen group-containing component is an isocyanate-terminated prepolymer.
  • the secondary reaction product between the isocyanate-terminated prepolymer and the chain extender is a gas barrier polyurethane resin.
  • the polyisocyanate component may be a known polyisocyanate component. From the viewpoint of gas barrier properties, the polyisocyanate component preferably contains xylylene diisocyanate and/or hydrogenated xylylene diisocyanate.
  • the polyisocyanate component may contain other polyisocyanates (polyisocyanates other than xylylene diisocyanate and hydrogenated xylylene diisocyanate) as necessary. Examples of other polyisocyanates include polyisocyanates that are widely used industrially.
  • polyisocyanates include, for example, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), methylene bis (cyclohexyl isocyanate) (H 12 MDI), diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), toluidine diisocyanate (TODI), naphthalene diisocyanate (NDI), and tetramethylxylylene diisocyanate (TMXDI). These may be used alone or in combination of two or more.
  • PDI pentamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • NBDI norbornene diisocyanate
  • H 12 MDI diphenylmethane diisocyanate
  • polyisocyanates preferably, methylene bis (cyclohexyl isocyanate) (H 12 MDI) may be used.
  • the polyisocyanate component may be a monomer or a derivative. Examples of the derivatives include polymers, isocyanurate modified products, allophanate modified products, polyol adducts, biuret modified products, urea modified products, oxadiazinetrione modified products, and carbodiimide modified products. These can be used alone or in combination of two or more kinds.
  • the polyisocyanate component preferably contains xylylene diisocyanate and/or hydrogenated xylylene diisocyanate and other polyisocyanates (preferably methylene bis(cyclohexyl isocyanate)).
  • xylylene diisocyanate and/or hydrogenated xylylene diisocyanate and other polyisocyanates preferably methylene bis(cyclohexyl isocyanate)
  • the active hydrogen group-containing component is an organic compound that contains an active hydrogen group.
  • the active hydrogen group include a hydroxyl group and an amino group, and preferably a hydroxyl group.
  • Examples of the active hydrogen group-containing component include known active hydrogen group-containing compounds. From the viewpoint of gas barrier properties, the active hydrogen group-containing component preferably contains a short-chain diol having 2 to 6 carbon atoms and an active hydrogen group-containing compound that contains an anionic group.
  • Short-chain diols having 2 to 6 carbon atoms are organic compounds having 2 to 6 carbon atoms and two hydroxyl groups in one molecule.
  • Examples of short-chain diols include alkanediols having 2 to 6 carbon atoms and etherdiols having 2 to 6 carbon atoms, preferably alkanediols having 2 to 6 carbon atoms.
  • alkanediols having 2 to 6 carbon atoms examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, and neopentyl glycol. These can be used alone or in combination of two or more types. From the viewpoint of gas barrier properties, ethylene glycol is preferred.
  • the active hydrogen group-containing compound containing an anionic group is preferably an organic compound having one carboxy group and two or more hydroxyl groups in one molecule, and more preferably an organic compound having one carboxy group and two hydroxyl groups in one molecule.
  • An example of an organic compound having one carboxy group and two hydroxyl groups in one molecule is a carboxy group-containing diol.
  • An example of a carboxy group-containing diol is a dihydroxyalkanoic acid.
  • dihydroxyalkanoic acid is 2,2-dimethylol acetic acid, 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid (also known as dimethylol propionic acid), 2,2-dimethylol butanoic acid, 2,2-dimethylol butyric acid, and 2,2-dimethylol valeric acid. These can be used alone or in combination of two or more kinds. From the viewpoint of water dispersibility, 2,2-dimethylol propionic acid is preferable.
  • the content of the short-chain diol having 2 to 6 carbon atoms and the content of the active hydrogen group-containing compound having an anionic group are appropriately set according to the purpose and application.
  • the active hydrogen group-containing component may further contain other polyols.
  • the other polyols include low molecular weight polyols having a valence of three or more, short-chain diols having seven or more carbon atoms, and high molecular weight polyols. These may be used alone or in combination of two or more.
  • the other polyols include low molecular weight polyols having a valence of three or more, and preferably include trihydric alcohols and tetrahydric alcohols.
  • trihydric alcohols examples include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolpropane, and 2,2-bis(hydroxymethyl)-3-butanol.
  • tetrahydric alcohols examples include tetramethylolmethane (pentaerythritol) and diglycerin. These may be used alone or in combination of two or more.
  • the low molecular weight polyols having a valence of three or more are more preferably trihydric alcohols, and even more preferably trimethylolpropane.
  • Examples of other polyols include active hydrogen group-containing compounds containing nonionic groups.
  • the active hydrogen group-containing compounds containing nonionic groups are used together with the above-mentioned active hydrogen compounds containing anionic groups.
  • the active hydrogen group-containing compounds containing nonionic groups may be used in place of the above-mentioned active hydrogen compounds containing anionic groups.
  • the content ratio of the other polyols in the active hydrogen group-containing component is appropriately set depending on the purpose and application.
  • the method for synthesizing the isocyanate-terminated prepolymer is not particularly limited.
  • the above-mentioned components are mixed in a predetermined equivalent ratio and reacted.
  • the reaction method include bulk polymerization and solution polymerization, and preferably solution polymerization.
  • a urethane catalyst can be added in an appropriate ratio as necessary.
  • the isocyanate-terminated prepolymer has an anionic group derived from an active hydrogen compound containing an anionic group
  • the isocyanate-terminated prepolymer is neutralized with a known neutralizing agent (e.g., triethylamine) to form a salt of the anionic group.
  • a known neutralizing agent e.g., triethylamine
  • the isocyanate group concentration of the isocyanate-terminated prepolymer is, for example, 4% by mass or more, preferably 5% by mass or more, and more preferably 6% by mass or more.
  • the isocyanate group concentration of the isocyanate-terminated prepolymer is, for example, 25% by mass or less, preferably 20% by mass or less, more preferably 17% by mass or less, and even more preferably 15% by mass or less.
  • the isocyanate-terminated prepolymer (primary reaction product) is reacted with a chain extender to obtain a gas-barrier polyurethane resin (secondary reaction product).
  • a chain extender for example, by reacting the isocyanate-terminated prepolymer with a chain extender in water, a gas-barrier polyurethane resin is produced and dispersed in water.
  • the chain extender is an organic compound that causes a chain extension reaction of the isocyanate-terminated prepolymer.
  • the chain extender has multiple active hydrogen groups.
  • Examples of chain extenders include polyamines, amino group-containing alkoxysilyl compounds, and amino alcohols (e.g., 2-((2-aminoethyl)amino)ethanol).
  • the method for reacting the isocyanate-terminated prepolymer with the chain extender in water is not particularly limited.
  • the isocyanate-terminated prepolymer is first dispersed in water.
  • the chain extender is added to the water in which the isocyanate-terminated prepolymer is dispersed, and the isocyanate-terminated prepolymer is chain-extended in water.
  • water can be added after the reaction is completed in order to adjust the solids concentration.
  • Primary polyurethane dispersion is an aqueous dispersion that does not contain the additives described below and contains gas-barrier polyurethane resin.
  • the gas barrier resin is not limited to the above gas barrier polyurethane resin, and is preferably prepared as an aqueous dispersion of the gas barrier resin (primary aqueous dispersion).
  • the solid content concentration of the aqueous dispersion of the gas barrier resin is, for example, 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more.
  • the solid content concentration of the aqueous dispersion of the gas barrier resin is, for example, 60% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less.
  • the above-mentioned aqueous dispersion of the gas barrier resin can be used as it is as a gas barrier coating material.
  • the gas barrier coating material can be composed of, for example, an aqueous dispersion of the above-mentioned gas barrier resin (primary aqueous dispersion).
  • the gas barrier coating material may also contain additives.
  • the gas barrier coating material contains additives.
  • an aqueous dispersion (secondary aqueous dispersion) containing the gas barrier resin and additives is used as the gas barrier coating material.
  • Additives include, for example, layered inorganic compounds, viscosity inhibitors, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, antiblocking agents, pigments, dyes, crystal nucleating agents, and hardeners. These can be used alone or in combination of two or more. From the viewpoint of gas barrier properties, layered inorganic compounds are preferably used as additives. In other words, the gas barrier layer 4 preferably contains layered inorganic compounds. The amount of additive and the timing of addition are appropriately set according to the purpose and application.
  • the solid content concentration of the gas barrier coating material is, for example, 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more.
  • the solid content concentration of the gas barrier coating material is, for example, 60% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less.
  • the method of applying the gas barrier coating material is not particularly limited. Examples of application methods include dip coating, gravure coating, reverse coating, roll coating, bar coating, spray coating, and air knife coating.
  • the drying conditions of the gas barrier coating material are not particularly limited.
  • the drying temperature is, for example, 40°C or higher, preferably 50°C or higher.
  • the drying temperature is, for example, 200°C or lower, preferably 180°C or lower.
  • the drying time is, for example, 1 second or longer, preferably 30 seconds or longer.
  • the drying time is, for example, 10 minutes or shorter, preferably 5 minutes or shorter.
  • the amount (dry mass) of the gas barrier layer 4 is, for example, 0.1 g/ m2 or more, preferably 0.2 g/ m2 or more.
  • the amount (dry mass) of the gas barrier layer 4 is, for example, 10 g/m2 or less , preferably 7 g/m2 or less .
  • the heat seal layer 5 is a resin layer having heat sealability.
  • the heat seal layer 5 is disposed on the surface of the gas barrier layer 4. That is, the heat seal layer 5 is disposed on the surface of the gas barrier layer 4 on the side of the paper base material 2 on which the gas barrier layer 4 is disposed.
  • the heat seal layer 5 may be disposed on both sides of the paper base material 2 together with the gas barrier layer 4.
  • the heat seal layer 5 is preferably disposed on only one surface of the paper base material 2 together with the gas barrier layer 4.
  • the heat seal layer 5 contains, for example, a heat sealable resin. More specifically, the heat seal layer 5 is formed, for example, by applying a coating material containing a heat sealable resin (hereinafter, a heat sealable coating material) to the gas barrier layer 4 and drying it.
  • a coating material containing a heat sealable resin hereinafter, a heat sealable coating material
  • Heat-sealable resins are resins that can be heat-sealed (thermally fused) to each other. There are no particular limitations on the heat-sealable resin, and any known heat-sealable resin can be used. More specific examples of heat-sealable resins include polyolefin resins, (meth)acrylic resins, and polyurethane resins. These can be used alone or in combination of two or more types.
  • the heat-sealable resin preferably contains an anionic group. That is, the heat-sealable resin is preferably an anionic group-containing heat-sealable resin. If the heat-sealable resin contains an anionic group, the heat-sealable resin is easily dissolved and/or dispersed in water, and the heat-sealable coating material can be efficiently obtained.
  • the anionic group include a carboxy group (carboxylic acid group) and a sulfo group (sulfonic acid group), and preferably a carboxy group.
  • the anionic group-containing heat-sealable resin examples include an anionic group-containing polyolefin resin, an anionic group-containing (meth)acrylic resin, and an anionic group-containing polyurethane resin.
  • the anionic group-containing heat-sealable resin contains at least one selected from the group consisting of an anionic group-containing polyolefin resin, an anionic group-containing (meth)acrylic resin, and an anionic group-containing polyurethane resin.
  • the anionic group-containing polyolefin resin is a resin containing an anionic group and a structural unit derived from an olefin.
  • An example of the anionic group-containing polyolefin resin is an unsaturated carboxylic acid-modified polyolefin resin.
  • the unsaturated carboxylic acid-modified polyolefin resin is obtained by copolymerization of a monomer component (hereinafter, olefin raw material monomer component) as a raw material composition.
  • the olefin raw material monomer component contains, for example, an olefin and an unsaturated carboxylic acid.
  • Examples of olefins include ⁇ -olefins.
  • Examples of ⁇ -olefins include ⁇ -olefins having 1 to 20 carbon atoms.
  • Examples of ⁇ -olefins having 1 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. These can be used alone or in combination of two or more types.
  • Examples of ⁇ -olefins include olefins having 2 to 3 carbon atoms, more preferably ethylene and/or propylene, and even more preferably ethylene.
  • the olefin content is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, based on the total amount of the olefin raw material monomer components.
  • the olefin content is, for example, 99% by mass or less, preferably 97% by mass or less, more preferably 95% by mass or less, even more preferably 93% by mass or less, and particularly preferably 90% by mass or less, based on the total amount of the olefin raw material monomer components.
  • the content of olefin in the olefin raw material monomer component is essentially the same as the content of structural units derived from olefin in the unsaturated carboxylic acid modified polyolefin resin.
  • the content of structural units derived from olefins is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, based on the total amount of the unsaturated carboxylic acid-modified polyolefin resin.
  • the content of structural units derived from olefins is, for example, 99% by mass or less, preferably 97% by mass or less, more preferably 95% by mass or less, even more preferably 93% by mass or less, and particularly preferably 90% by mass or less, based on the total amount of the unsaturated carboxylic acid-modified polyolefin resin.
  • the content of structural units derived from olefins in polyolefin resins is 50% by mass or more, and preferably 60% by mass or more, based on the total amount of polyolefin resin.
  • Polyolefin resins are distinguished from other resins that contain structural units derived from olefins by the content of structural units derived from olefins.
  • the content of structural units derived from olefins is less than 50% by mass, preferably 40% by mass or less.
  • Examples of unsaturated carboxylic acids include unsaturated monocarboxylic acids and unsaturated dicarboxylic acids.
  • Examples of unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, and isocrotonic acid.
  • Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, and norbornene dicarboxylic acid, and their acid anhydrides.
  • the unsaturated carboxylic acids can be used alone or in combination of two or more kinds.
  • Preferable examples of unsaturated carboxylic acids include unsaturated monocarboxylic acids and acid anhydrides of unsaturated dicarboxylic acids, and more preferably (meth)acrylic acid.
  • (Meth)acrylic refers to acrylic and/or methacrylic. The same applies to (meth)acrylate.
  • As the (meth)acrylic acid preferably, acrylic acid is used alone, or methacrylic acid is used alone.
  • the content of the unsaturated carboxylic acid is appropriately adjusted, for example, to balance heat sealability and hydrophilicity.
  • the content of the unsaturated carboxylic acid is, for example, 1 mass% or more, preferably 5 mass% or more, more preferably 8 mass% or more, and even more preferably 10 mass% or more, based on the total amount of the olefin raw material monomer components.
  • the content of the unsaturated carboxylic acid is, for example, less than 50 mass%, preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 25 mass% or less, based on the total amount of the olefin raw material monomer components.
  • the content of unsaturated carboxylic acid in the olefin raw material monomer component is essentially the same as the content of structural units derived from unsaturated carboxylic acid in the unsaturated carboxylic acid modified polyolefin resin.
  • the content of the structural units derived from the unsaturated carboxylic acid is, for example, 1 mass% or more, preferably 5 mass% or more, more preferably 8 mass% or more, and even more preferably 10 mass% or more, based on the total amount of the unsaturated carboxylic acid-modified polyolefin resin.
  • the content of the structural units derived from the unsaturated carboxylic acid is, for example, less than 50 mass%, preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 25 mass% or less, based on the total amount of the unsaturated carboxylic acid-modified polyolefin resin.
  • the olefin raw material monomer component may contain a copolymerizable monomer in an appropriate ratio as necessary.
  • the copolymerizable monomer is a monomer that can be copolymerized with an olefin and/or an unsaturated carboxylic acid.
  • copolymerizable monomers examples include unsaturated carboxylic acid esters, hydroxyl group-containing vinyl monomers, amino group-containing vinyl monomers, glycidyl group-containing vinyl monomers, cyano group-containing vinyl monomers, sulfonic acid group-containing vinyl monomers, acetoacetoxy group-containing vinyl monomers, phosphoric acid group-containing vinyl monomers, amide group-containing vinyl monomers, aromatic vinyl monomers, N-substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, vinylidene halide compounds, dienes, and vinyl esters. These can be used alone or in combination of two or more kinds. From the viewpoint of heat sealability, unsaturated carboxylic acid esters are preferably used as the copolymerizable monomer.
  • the unsaturated carboxylic acid ester may, for example, be an alkyl ester of the above-mentioned unsaturated carboxylic acid.
  • the unsaturated carboxylic acid ester is preferably a (meth)acrylic acid ester.
  • the (meth)acrylic acid ester may, for example, be a (meth)acrylic acid ester having an alkyl portion having 1 to 12 carbon atoms.
  • the (meth)acrylic acid ester may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. These may be used alone or in combination of two or more.
  • the (meth)acrylic acid ester is a (meth)acrylic acid ester having an alkyl portion having 1 to 4 carbon atoms. More specifically, it includes methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate.
  • the (meth)acrylic acid ester includes a (meth)acrylic acid ester having an alkyl portion having 2 to 4 carbon atoms. More specifically, the (meth)acrylic acid ester includes ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate. More preferably, the (meth)acrylic acid ester includes butyl acrylate and isobutyl acrylate, and particularly preferably, isobutyl acrylate.
  • the content of the unsaturated carboxylic acid ester is, for example, 0% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more, based on the total amount of the olefin raw material monomer components.
  • the content of the unsaturated carboxylic acid ester is, for example, 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less, based on the total amount of the olefin raw material monomer components.
  • the content of unsaturated carboxylic acid ester in the olefin raw material monomer component is essentially the same as the content of structural units derived from unsaturated carboxylic acid ester in the unsaturated carboxylic acid modified polyolefin resin.
  • the content of the structural units derived from the unsaturated carboxylic acid ester is, for example, 0 mass% or more, preferably 1 mass% or more, more preferably 5 mass% or more, even more preferably 8 mass% or more, and particularly preferably 10 mass% or more, relative to the total amount of the unsaturated carboxylic acid-modified polyolefin resin.
  • the content of the structural units derived from the unsaturated carboxylic acid ester is, for example, 30 mass% or less, preferably 25 mass% or less, and more preferably 20 mass% or less, relative to the total amount of the unsaturated carboxylic acid-modified polyolefin resin.
  • the olefin raw material monomer component is preferably a ternary monomer component consisting of ethylene, an unsaturated carboxylic acid, and an unsaturated carboxylic acid ester.
  • the olefin raw material monomer component is preferably a binary monomer component consisting of ethylene and an unsaturated carboxylic acid.
  • the unsaturated carboxylic acid modified polyolefin resin is preferably a two-component copolymer consisting of ethylene and an unsaturated carboxylic acid (hereinafter referred to as an ethylene-unsaturated carboxylic acid copolymer).
  • the unsaturated carboxylic acid modified polyolefin resin is preferably a three-component copolymer consisting of ethylene, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid (hereinafter referred to as an ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer).
  • an ethylene-unsaturated carboxylic acid copolymer in combination with an ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer as the unsaturated carboxylic acid modified polyolefin resin.
  • the ratio of the ethylene-unsaturated carboxylic acid copolymer and the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer used in combination is appropriately adjusted from the viewpoint of achieving a balance between heat sealability and hydrophilicity.
  • the content of the ethylene-unsaturated carboxylic acid copolymer relative to the total amount of the ethylene-unsaturated carboxylic acid copolymer and the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer is, for example, 20% by mass or more, preferably 40% by mass or more.
  • the content of the ethylene-unsaturated carboxylic acid copolymer relative to the total amount of the ethylene-unsaturated carboxylic acid copolymer and the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer is, for example, 80% by mass or less, preferably 60% by mass or less.
  • the content ratio of the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer relative to the total amount of the ethylene-unsaturated carboxylic acid copolymer and the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer is, for example, 20% by mass or more, preferably 40% by mass or more.
  • the content ratio of the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer relative to the total amount of the ethylene-unsaturated carboxylic acid copolymer and the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer is, for example, 80% by mass or less, preferably 60% by mass or less.
  • the method for producing the unsaturated carboxylic acid modified polyolefin resin is not particularly limited, and a known method can be used.
  • the above-mentioned olefin raw material monomer component is contacted with a known polymerization initiator (such as a peroxide) under high temperature and pressure conditions.
  • a known polymerization initiator such as a peroxide
  • the anionic group-containing (meth)acrylic resin is a resin containing an anionic group and a structural unit derived from a (meth)acrylic acid ester.
  • examples of the anionic group-containing (meth)acrylic resin include an anionic group-containing (meth)acrylic resin.
  • the anionic group-containing (meth)acrylic resin is obtained by copolymerization of a monomer component (hereinafter, acrylic raw material monomer component) as a raw material composition.
  • the acrylic raw material monomer component contains, for example, a (meth)acrylic acid ester and an unsaturated carboxylic acid.
  • (Meth)acrylic acid esters include, for example, the (meth)acrylic acid esters mentioned above in the olefin raw material monomer component. These may be used alone or in combination of two or more types.
  • the content of (meth)acrylic acid ester is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, based on the total amount of acrylic raw material monomer components.
  • the content of (meth)acrylic acid ester is, for example, 99% by mass or less, preferably 97% by mass or less, more preferably 95% by mass or less, even more preferably 93% by mass or less, and particularly preferably 90% by mass or less, based on the total amount of acrylic raw material monomer components.
  • the content of (meth)acrylic acid ester in the acrylic raw material monomer component is essentially the same as the content of structural units derived from (meth)acrylic acid ester in the anionic group-containing (meth)acrylic resin.
  • the content of the structural units derived from the (meth)acrylic acid ester is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, based on the total amount of the anionic group-containing (meth)acrylic resin.
  • the content of the structural units derived from the (meth)acrylic acid ester is, for example, 99% by mass or less, preferably 97% by mass or less, more preferably 95% by mass or less, even more preferably 93% by mass or less, and particularly preferably 90% by mass or less, based on the total amount of the anionic group-containing (meth)acrylic resin.
  • the unsaturated carboxylic acids include, for example, the unsaturated carboxylic acids mentioned above in the olefin raw material monomer component. These may be used alone or in combination of two or more types.
  • the content of the unsaturated carboxylic acid is appropriately adjusted, for example, to balance heat sealability and hydrophilicity.
  • the content of the unsaturated carboxylic acid is, for example, 1 mass% or more, preferably 5 mass% or more, more preferably 8 mass% or more, and even more preferably 10 mass% or more, based on the total amount of the acrylic raw material monomer components.
  • the content of the unsaturated carboxylic acid is, for example, less than 50 mass%, preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 25 mass% or less, based on the total amount of the acrylic raw material monomer components.
  • the content of unsaturated carboxylic acid in the acrylic raw material monomer component is essentially the same as the content of structural units derived from unsaturated carboxylic acid in the anionic group-containing (meth)acrylic resin.
  • the content of the structural units derived from the unsaturated carboxylic acid is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more, based on the total amount of the anionic group-containing (meth)acrylic resin.
  • the content of the structural units derived from the unsaturated carboxylic acid is, for example, less than 50% by mass, preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less, based on the total amount of the anionic group-containing (meth)acrylic resin.
  • the acrylic raw material monomer component can contain a copolymerizable monomer in an appropriate ratio as necessary.
  • the copolymerizable monomer is a monomer that can be copolymerized with a (meth)acrylic acid ester and/or an unsaturated carboxylic acid.
  • copolymerizable monomers examples include olefins, hydroxyl group-containing vinyl monomers, amino group-containing vinyl monomers, glycidyl group-containing vinyl monomers, cyano group-containing vinyl monomers, sulfonic acid group-containing vinyl monomers, acetoacetoxy group-containing vinyl monomers, phosphoric acid group-containing vinyl monomers, amide group-containing vinyl monomers, aromatic vinyl monomers, N-substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, vinylidene halide compounds, dienes, and vinyl esters. These can be used alone or in combination of two or more kinds. The content ratio of the copolymerizable monomers is appropriately set depending on the purpose and application.
  • the content of structural units derived from the olefin in the anionic group-containing (meth)acrylic resin is less than 50% by mass, preferably 40% by mass or less, based on the total amount of the anionic group-containing (meth)acrylic resin.
  • the anionic group-containing (meth)acrylic resin is distinguished from the above-mentioned anionic group-containing polyolefin resin by the content of structural units derived from the olefin.
  • the method for producing the unsaturated carboxylic acid modified (meth)acrylic resin is not particularly limited, and known methods can be used.
  • the above acrylic raw material monomer components are contacted with a known polymerization initiator (such as a peroxide) under high temperature and pressure conditions. This produces an anionic group-containing (meth)acrylic resin as the polymerization product of the acrylic raw material monomer components.
  • a known polymerization initiator such as a peroxide
  • the anionic group-containing polyurethane resin is a resin containing an anionic group and a urethane group.
  • examples of the anionic group-containing polyurethane resin include a reaction product of the polyisocyanate compound, the polyol compound, the active hydrogen compound containing the anionic group, and the chain extender.
  • the method for producing the anionic group-containing polyurethane resin is not particularly limited.
  • a polyisocyanate compound, a polyol compound, and an active hydrogen compound containing an anionic group are reacted with each other by the above-mentioned method to obtain an isocyanate-terminated prepolymer.
  • the isocyanate-terminated prepolymer is reacted with a chain extender by the above-mentioned method. This results in an anionic group-containing polyurethane resin.
  • the anionic group-containing heat sealable resin can be used alone or in combination of two or more types.
  • a preferred example of the anionic group-containing heat sealable resin is an anionic group-containing polyolefin resin.
  • the anionic group-containing heat-sealable resin is preferably neutralized with a neutralizing agent. That is, the anionic group-containing heat-sealable resin is preferably an anionic group-containing heat-sealable resin neutralized with a neutralizing agent. There are no particular limitations on the method for neutralizing the anionic group-containing heat-sealable resin, and the anionic group is brought into contact with the neutralizing agent at any time.
  • the neutralizing agent may be, for example, a basic compound, more specifically, an inorganic basic compound and an organic basic compound.
  • the inorganic basic compound may be, for example, an alkali metal hydroxide.
  • the alkali metal hydroxide may be, for example, sodium hydroxide and potassium hydroxide.
  • the organic basic compound may be, for example, ammonia and an amine compound.
  • the amine compound may be, for example, triethylamine (TEA), triethanolamine, dimethylethanolamine, diethanolamine, diethylamine (DEA), methylamine (MA), and N,N-dimethylethanolamine. These may be used alone or in combination of two or more.
  • the neutralizing agent may preferably be an alkali metal hydroxide, ammonia, or an amine compound.
  • the neutralizing agent preferably contains at least one selected from the group consisting of an alkali metal hydroxide, ammonia, and an amine compound.
  • the neutralizing agent is preferably a neutralizing agent that does not contain a metal, more preferably ammonia and an amine compound, even more preferably ammonia and diethylamine (DEA), and particularly preferably ammonia.
  • the amount of neutralizing agent added is, for example, 0.4 equivalents or more, and preferably 0.6 equivalents or more, per equivalent of anionic group.
  • the amount of neutralizing agent added is, for example, 1.2 equivalents or less, and preferably 1.0 equivalents or less, per equivalent of anionic group.
  • the moisture absorption expansion coefficient of the anionic group-containing heat sealable resin is, for example, 1000 ppm/RH% or more, preferably 3000 ppm/RH% or more, more preferably 5000 ppm/RH% or more, and even more preferably 6000 ppm/RH% or more.
  • the moisture absorption expansion coefficient of the anionic group-containing heat sealable resin is, for example, 20000 ppm/RH% or less, preferably 15000 ppm/RH% or less, more preferably 10000 ppm/RH% or less, and even more preferably 9000 ppm/RH% or less.
  • the moisture absorption expansion coefficient of the anionic group-containing heat sealable resin is, for example, 1000 ppm/RH% or more and 20000 ppm/RH% or less, preferably 3000 ppm/RH% or more and 15000 ppm/RH% or less, more preferably 5000 ppm/RH% or more and 10000 ppm/RH% or less, and even more preferably 6000 ppm/RH% or more and 9000 ppm/RH% or less.
  • the amount of the heat seal layer 5 is within the range described below, if the moisture absorption expansion coefficient of the anionic group-containing heat sealable resin is within the above range, particularly excellent water vapor barrier properties can be obtained.
  • the moisture absorption expansion coefficient is measured under the following conditions in accordance with the examples described below.
  • the above-mentioned anionic group-containing heat sealable resin is prepared, for example, as a solution and/or dispersion in which it is dissolved and/or dispersed in a solvent.
  • the anionic group-containing heat sealable resin is synthesized in a solvent. This results in a solution and/or dispersion of the anionic group-containing heat sealable resin.
  • the solvent is not particularly limited, but examples include water, methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, and acetonitrile. These solvents can be used alone or in combination of two or more.
  • the solids concentration of the sealing coating material is not particularly limited, and is set appropriately depending on the purpose and application.
  • heat-sealable coating materials include polyolefin dispersions containing anionic group-containing polyolefin resins, acrylic emulsions containing anionic group-containing (meth)acrylic resins, and polyurethane dispersions containing anionic group-containing polyurethane resins.
  • a preferred example of a heat-sealable coating material is a polyolefin dispersion containing anionic group-containing polyolefin resin.
  • the heat-sealable coating material may contain additives. That is, the heat-sealable coating material may contain the above-mentioned heat-sealable resin and additives.
  • additives include heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, antiblocking agents, pigments, dyes, crystal nucleating agents, and hardeners. These may be used alone or in combination of two or more types. The amount of additive and the timing of addition are appropriately set according to the purpose and application.
  • the solid content concentration of the heat-sealable coating material is, for example, 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more.
  • the solid content concentration of the heat-sealable coating material is, for example, 60% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less.
  • the method of applying the heat-sealable coating material is not particularly limited. Examples of application methods include dip coating, gravure coating, reverse coating, roll coating, bar coating, spray coating, and air knife coating.
  • the drying conditions of the gas barrier coating material are not particularly limited.
  • the drying temperature is, for example, 40°C or higher, preferably 50°C or higher.
  • the drying temperature is, for example, 200°C or lower, preferably 180°C or lower.
  • the drying time is, for example, 1 second or longer, preferably 30 seconds or longer.
  • the drying time is, for example, 10 minutes or shorter, preferably 5 minutes or shorter.
  • the amount (dry mass) of the heat seal layer 5 is set from the viewpoint of achieving both gas barrier properties and heat sealability.
  • the amount (dry mass) of the heat seal layer 5 is 1.0 g/m 2 or more, preferably more than 1.0 g/m 2 , more preferably 1.1 g/m 2 or more, even more preferably 1.5 g/m 2 or more, and particularly preferably 1.8 g/m 2 or more.
  • the amount (dry mass) of the heat seal layer 5 is 7.0 g/m 2 or less, preferably less than 5.0 g/m 2 , more preferably 4.9 g/m 2 or less, even more preferably 4.0 g/m 2 or less, and particularly preferably 3.5 g/m 2 or less.
  • the laminate 1 has a total thickness of, for example, 5 ⁇ m or more, or preferably 10 ⁇ m or more.
  • the laminate 1 has a total thickness of, for example, 1 mm or less, or preferably 0.5 mm or less.
  • the laminate 1 includes a paper base material 2, a gas barrier layer 4, and a heat seal layer 5, and the amount of the heat seal layer 5 is adjusted to the above-mentioned predetermined range. Therefore, the laminate 1 has both excellent gas barrier properties (oxygen barrier properties and water vapor barrier properties) and excellent heat seal properties.
  • the heat seal layer 5 adsorbs oxygen and water vapor. Therefore, for example, as described in Patent Document 1, when a heat seal layer 5 of 10 g/ m2 is formed on the surface of the gas barrier layer 4, the gas barrier properties of the gas barrier layer 4 may be reduced.
  • the gas barrier properties of the laminate 1 as a whole depend on the gas barrier properties of the gas barrier layer 4.
  • the gas barrier properties of the gas barrier layer 4 are reduced by the heat seal layer 5, the gas barrier properties of the laminate 1 as a whole may become insufficient.
  • the amount (dry mass) of the heat seal layer 5 is set to a particularly narrow range from the viewpoint of achieving both gas barrier properties and heat sealability. In other words, in the laminate 1, the amount of the heat seal layer 5 is adjusted to the above-mentioned predetermined range.
  • the laminate 1 has both excellent gas barrier property and excellent heat sealability.
  • the laminate 1 is suitable for use in various industrial fields that require gas barrier properties and heat sealability. More specifically, the laminate 1 is suitable for use as a packaging material. That is, the packaging material preferably contains the laminate 1, and more preferably consists of the laminate 1.
  • such a packaging material contains the laminate 1 described above, it has both excellent gas barrier properties and excellent heat sealability.
  • Such packaging materials are used in various industrial fields.
  • the packaging material is used in the food packaging field.
  • the filling layer 3 is interposed between the paper base material 2 and the gas barrier layer 4, but the filling layer 3 does not have to be interposed between the paper base material 2 and the gas barrier layer 4.
  • the filling layer 3 may be omitted depending on the type of the paper base material 2 and the type of the gas barrier layer 4, the filling layer 3 may be omitted.
  • the heat seal layer 5 may be laminated directly onto the gas barrier layer 4 as described above.
  • the heat seal layer 5 may be bonded to the gas barrier layer 4 with a known adhesive.
  • an adhesive layer (not shown) may be interposed between the gas barrier layer 4 and the heat seal layer 5.
  • Paper substrate preparation example 1 As the paper base material, one-sided glossy (bleached) kraft paper (product name: Shirogane, manufactured by Nippon Paper Industries Co., Ltd., basis weight 67 g/m 2 ) was prepared.
  • the monomer emulsion is a raw material composition containing the following components. Ion-exchanged water (solvent) 900 parts by weight Sodium dodecyl sulfate (surfactant) 5 parts by weight Acrylamide (raw monomer) 25 parts by weight Methyl methacrylate (raw monomer) 175 parts by weight 2-ethylhexyl acrylate (raw monomer) 1088 parts by weight Methacrylic acid (raw monomer) 80 parts by weight Styrene (raw monomer) 1133 parts by weight
  • the acrylic emulsion was cooled to room temperature. Ion exchange water and ammonia water (neutralizing agent) were then added to the acrylic emulsion to adjust the solids concentration to 41% by mass and the pH to 8.0.
  • an acrylic emulsion was obtained in which the (meth)acrylic resin was dispersed in water.
  • the average particle size of the acrylic emulsion was 140 nm.
  • the average particle size was measured by dynamic light scattering (measuring device FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.) (same below).
  • 1,3-xylylene diisocyanate Takenate 500, 1,3-XDI, manufactured by Mitsui Chemicals, Inc. 143.2 parts by mass Methylene bis(cyclohexyl isocyanate) (Vestanat H 12 MDI, H 12 MDI, manufactured by Evonik) 25.0 parts by weight Ethylene glycol 29.2 parts by weight Trimethylolpropane 2.7 parts by weight Dimethylolpropionic acid 14.8 parts by weight Methyl ethyl ketone (solvent) 121.6 parts by weight
  • reaction product liquid was cooled to 40°C.
  • TEA triethylamine
  • the reaction product liquid was dispersed in 838.0 parts by mass of ion-exchanged water.
  • an aqueous amine solution was added to the resulting dispersion liquid to carry out a chain extension reaction.
  • the reaction product liquid of the chain extension reaction was aged for 1 hour. This resulted in a gas barrier polyurethane resin.
  • the aqueous amine solution was a mixture of 48.4 parts by mass of ion-exchanged water and 24.2 parts by mass of 2-((2-aminoethyl)amino)ethanol.
  • the methyl ethyl ketone and ion-exchanged water were distilled off from the reaction product liquid. This adjusted the solids concentration to 30% by mass.
  • a primary polyurethane dispersion (primary PUD) was obtained in which the gas barrier polyurethane resin was dispersed in water.
  • the pH of the primary polyurethane dispersion was 8.6.
  • the average particle size of the polyurethane dispersion was 58 nm.
  • a swellable layered inorganic compound product name: ME-300-B4T, synthetic mica, manufactured by Katakura Co-op Agri Co., Ltd., solid content concentration 7.8%
  • the dispersion of the above additives (total amount 49.6 parts by mass) and 51.0 parts by mass of the primary PUD were mixed in a mixer for 5 minutes.
  • the solids concentration of the secondary PUD was 15% by mass.
  • the secondary PUD was used as a gas barrier coating material.
  • Heat-sealable coating material (1) Anionic group-containing heat-sealable resin Production example 1 (polyolefin dispersion, neutralized with potassium hydroxide) 50 parts by mass of an ethylene-acrylic acid copolymer and 50 parts by mass of an ethylene-isobutyl acrylate-methacrylic acid copolymer were melt-kneaded to obtain a resin composition (anionic group-containing polyolefin resin) as an anionic group-containing heat sealable resin.
  • a resin composition anionic group-containing polyolefin resin
  • the content of structural units derived from ethylene was 79.5% by mass, and the content of structural units derived from acrylic acid was 20.5% by mass, based on the total amount of ethylene-acrylic acid copolymer.
  • the content of structural units derived from ethylene was 80.0% by mass
  • the content of structural units derived from isobutyl acrylate was 10.0% by mass
  • the content of structural units derived from methacrylic acid was 10.0% by mass, relative to the total amount of ethylene-isobutyl acrylate-methacrylic acid copolymer.
  • the above resin composition, 4.0 parts by mass of potassium hydroxide (neutralizing agent), and 140 parts by mass of deionized water were placed in a reaction vessel and stirred.
  • the contents of the reaction vessel were heated to 150°C and kept at that temperature for 4 hours. This resulted in the resin composition being neutralized by potassium hydroxide (neutralizing agent).
  • a resin composition (anionic group-containing heat sealable resin) neutralized by the neutralizing agent was obtained.
  • the contents of the reaction vessel were then cooled to room temperature.
  • aqueous dispersion 1 of the resin composition (resin 1) was obtained.
  • the aqueous dispersion 1 was a polyolefin dispersion.
  • the solid content concentration of the aqueous dispersion 1 was 42% by mass.
  • the average particle size of the aqueous dispersion 1 was 0.5 ⁇ m.
  • the aqueous dispersion 1 was used as a heat-sealable coating material.
  • Production Example 2 Polyolefin Dispersion, Neutralized with Sodium Hydroxide
  • aqueous dispersion 2 aqueous dispersion 2 of a resin composition (resin 2) was obtained in the same manner as in Production Example 1.
  • the solid content concentration of the aqueous dispersion 2 was 42% by mass.
  • the average particle size of the aqueous dispersion 2 was 0.6 ⁇ m.
  • the aqueous dispersion 2 was used as a heat-sealable coating material.
  • Production Example 3 Polyolefin Dispersion, Ammonia Neutralized
  • 13.7 parts by mass of ammonia water (25% by mass) was used.
  • the amount of deionized water used was changed to 285 parts by mass.
  • a water dispersion (water dispersion 3) of the resin composition (resin 3) was obtained in the same manner as in Production Example 1.
  • the solid content concentration of the water dispersion 3 was 25% by mass.
  • the average particle size of the water dispersion 3 was 0.6 ⁇ m.
  • the water dispersion 3 was used as a heat-sealable coating material.
  • Production Example 4 Polyolefin Dispersion
  • Amine Neutralized Product instead of 4.0 parts by mass of potassium hydroxide, 11.7 parts by mass of diethylamine (DEA) was used.
  • the amount of deionized water used was changed to 285 parts by mass.
  • the rest was the same as in Production Example 1 to obtain an aqueous dispersion (aqueous dispersion 4) of a resin composition (resin 4).
  • the solid content concentration of aqueous dispersion 4 was 25% by mass.
  • the average particle size of aqueous dispersion 4 was 0.5 ⁇ m.
  • the aqueous dispersion 4 was used as a heat-sealable coating material.
  • Production Example 5 Polyolefin Dispersion
  • Amine Neutralized Product instead of 4.0 parts by mass of potassium hydroxide, 5.0 parts by mass of methylamine (MA) was used.
  • the amount of deionized water used was changed to 285 parts by mass.
  • the rest was the same as in Production Example 1 to obtain an aqueous dispersion (aqueous dispersion 5) of a resin composition (resin 5).
  • the solid content concentration of aqueous dispersion 5 was 25% by mass.
  • the average particle size of aqueous dispersion 5 was 0.6 ⁇ m.
  • the aqueous dispersion 5 was used as a heat-sealable coating material.
  • the heat-sealable coating materials of Production Examples 1 to 5 were poured into a polypropylene tray, dried overnight at room temperature, and then dried at 100°C for 10 minutes to obtain a film.
  • the amount of heat-sealable coating material was adjusted so that a film with a thickness of 200 ⁇ m was obtained.
  • the 200 ⁇ m thick film was cut to 20 mm x 5 mm to obtain a sample (20 mm x 5 mm x 200 ⁇ m).
  • the moisture absorption expansion coefficient of the sample was measured under the following conditions using a moisture absorption expansion measuring device (NETZSCH, HC-TMA4000SE, HC9700).
  • the moisture absorption expansion coefficient was measured in the range of 40 to 80 RH%.
  • the resin composition of Production Example 1 broke before the humidity condition reached 80 RH%. Therefore, the moisture absorption expansion coefficient of the resin composition of Production Example 1 was measured in the range of 40 to 70 RH%.
  • Laminates Examples 1 to 12 and Comparative Examples 1 to 4 (Laminates)
  • the filler coating material (Preparation Example 1) was applied to the glossy surface of a paper substrate (one-sided glossy kraft paper) using a bar coater. The amount of coating was adjusted so that the dry mass was 10 g/ m2 . The coating film of the filler coating material was then dried at 120°C for 60 seconds. This formed a filler layer.
  • the gas barrier coating material (Preparation Example 2) was applied to the surface of the filling layer using a bar coater. The amount of application was adjusted so that the dry mass was 3 g/ m2 . Next, the coating film of the gas barrier coating material was dried at 120°C for 60 seconds. As a result, a gas barrier layer was formed on the surface of the filling layer.
  • the heat-sealable coating material shown in Tables 1 and 2 was applied to the surface of the gas barrier layer using a bar coater.
  • the amount of coating was adjusted so that the dry mass would be the value (g/m 2 ) shown in Tables 1 and 2.
  • the coating film of the heat-sealable coating material was then dried at 120° C. for 60 seconds. In this way, a heat-sealable layer was formed on the surface of the gas barrier layer.
  • the layer structure of the laminate was as follows:
  • the dry mass of the filling layer was calculated by subtracting the mass of the paper substrate from the total mass of the laminate (2 layers) including the paper substrate and the filling layer.
  • the dry mass of the gas barrier layer was calculated by subtracting the total mass of the laminate (2 layers) including the paper substrate and the filler layer from the total mass of the laminate (3 layers) including the paper substrate, the filler layer, and the gas barrier layer.
  • the dry mass of the heat seal layer was calculated by subtracting the total mass of the laminate (3 layers) comprising the paper substrate, the filler layer, and the gas barrier layer from the total mass of the laminate (4 layers) comprising the paper substrate, the filler layer, the gas barrier layer, and the heat seal layer.
  • OTR Oxygen transmission rate
  • the laminate and packaging material of the present invention are suitable for use in the food packaging field.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
PCT/JP2024/010897 2023-03-28 2024-03-21 積層体および包装材 Ceased WO2024203674A1 (ja)

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EP24779797.0A EP4691770A1 (en) 2023-03-28 2024-03-21 Laminate and packaging material
KR1020257029991A KR20250145660A (ko) 2023-03-28 2024-03-21 적층체 및 포장재
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WO2015016069A1 (ja) * 2013-07-30 2015-02-05 三井化学株式会社 ポリウレタンディスパージョンおよびポリウレタン積層体
JP2015044396A (ja) 2013-07-30 2015-03-12 三井化学株式会社 ポリウレタン積層体
JP2021020398A (ja) * 2019-07-29 2021-02-18 王子ホールディングス株式会社 バリア包装材料
WO2021106891A1 (ja) * 2019-11-26 2021-06-03 王子ホールディングス株式会社 バリア性積層体
JP2021115802A (ja) 2020-01-28 2021-08-10 三井化学株式会社 積層体
JP2021138434A (ja) * 2020-03-09 2021-09-16 北越コーポレーション株式会社 包装用紙
WO2022071261A1 (ja) * 2020-10-01 2022-04-07 Ｄｉｃグラフィックス株式会社 耐水紙、及び該耐水紙を用いた包装紙又は容器
JP2022155999A (ja) 2021-03-31 2022-10-14 大日本印刷株式会社 バリア紙
JP2023027649A (ja) * 2021-08-17 2023-03-02 王子ホールディングス株式会社 バリア性積層体

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JP2001049054A (ja) * 1999-08-11 2001-02-20 Sumitomo Seika Chem Co Ltd エチレン系樹脂水性分散液、およびその水性分散液から得られるエチレン系樹脂皮膜
WO2015016069A1 (ja) * 2013-07-30 2015-02-05 三井化学株式会社 ポリウレタンディスパージョンおよびポリウレタン積層体
JP2015044396A (ja) 2013-07-30 2015-03-12 三井化学株式会社 ポリウレタン積層体
JP2021020398A (ja) * 2019-07-29 2021-02-18 王子ホールディングス株式会社 バリア包装材料
WO2021106891A1 (ja) * 2019-11-26 2021-06-03 王子ホールディングス株式会社 バリア性積層体
JP2021115802A (ja) 2020-01-28 2021-08-10 三井化学株式会社 積層体
JP2021138434A (ja) * 2020-03-09 2021-09-16 北越コーポレーション株式会社 包装用紙
WO2022071261A1 (ja) * 2020-10-01 2022-04-07 Ｄｉｃグラフィックス株式会社 耐水紙、及び該耐水紙を用いた包装紙又は容器
JP2022155999A (ja) 2021-03-31 2022-10-14 大日本印刷株式会社 バリア紙
JP2023027649A (ja) * 2021-08-17 2023-03-02 王子ホールディングス株式会社 バリア性積層体

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