WO2024203673A1 - 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
WO2024203673A1
WO2024203673A1 PCT/JP2024/010896 JP2024010896W WO2024203673A1 WO 2024203673 A1 WO2024203673 A1 WO 2024203673A1 JP 2024010896 W JP2024010896 W JP 2024010896W WO 2024203673 A1 WO2024203673 A1 WO 2024203673A1
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WO
WIPO (PCT)
Prior art keywords
resin
mass
meth
gas barrier
acrylic
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/JP2024/010896
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
徹 矢木
俊彦 中川
祥子 遠藤
和幸 福田
靖之 香川
寿洋 吉村
征也 楠本
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 KR1020257029990A priority Critical patent/KR20250148643A/ko
Priority to EP24779796.2A priority patent/EP4691769A1/en
Priority to CN202480016998.6A priority patent/CN120835833A/zh
Priority to JP2025510613A priority patent/JPWO2024203673A1/ja
Publication of WO2024203673A1 publication Critical patent/WO2024203673A1/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
    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; 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
    • 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
    • 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
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • 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
    • B32B2255/12—Coating on the layer surface on paper layer
    • 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 sealing layer and a gas barrier layer.
  • laminates that include a paper base material, a sealing layer, and a gas barrier layer are known. Such laminates are used, for example, as packaging materials.
  • the barrier paper comprises a paper base layer, a fixed filler layer, and a gas barrier layer. More specifically, either a styrene-acrylic copolymer aqueous emulsion or a polyethylene resin aqueous emulsion is applied to the paper base to form the fixed filler layer. In addition, a urethane-based hybrid gas barrier resin composition is applied to the fixed filler layer to form the gas barrier layer (see, for example, Patent Document 1 (Examples A13-15 and Comparative Examples A10-21)).
  • barrier paper is required to have both excellent handling properties and excellent bending resistance depending on the application.
  • the present invention is a laminate and packaging material that combines excellent handling properties with excellent bending resistance.
  • the present invention [1] includes a laminate comprising a paper base material, a sealing layer disposed on at least one side of the paper base material, and a gas barrier layer disposed on at least one side of the sealing layer, the sealing layer containing a polyolefin resin and a (meth)acrylic resin.
  • the present invention [2] includes the laminate described in [1] above, in which the content of the polyolefin resin is 6% by mass or more and 94% by mass or less, and the content of the (meth)acrylic resin is 6% by mass or more and 94% by mass or less, relative to the total amount of the polyolefin resin and the (meth)acrylic resin.
  • the present invention [3] includes the laminate described in [1] or [2] above, in which the glass transition temperature of the (meth)acrylic resin is -60°C or higher and 10°C or lower.
  • the present invention [4] includes a laminate according to any one of [1] to [3] above, in which the gas barrier layer contains a gas barrier resin.
  • the present invention [5] includes the laminate described in [4] above, in which the gas barrier resin contains a gas barrier polyurethane resin.
  • the present invention [6] includes the laminate described in [5] 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 [7] includes the laminate described in any one of [4] to [6] above, in which the gas barrier layer further contains a layered inorganic compound.
  • the present invention [8] further includes the laminate described in any one of [1] to [7] above, which further includes a heat seal layer disposed on at least one side of the gas barrier layer.
  • 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 substrate, a sealing layer, and a gas barrier layer.
  • the sealing layer contains a polyolefin resin and a (meth)acrylic resin. Therefore, the sealing layer has excellent blocking resistance. In other words, the laminate has excellent handleability. Furthermore, since the sealing layer contains a polyolefin resin and a (meth)acrylic resin, it has excellent flex resistance. As a result, the laminate has both excellent handleability and excellent flex resistance.
  • the packaging material of the present invention contains the above laminate, and therefore has both excellent handling properties and excellent bending resistance.
  • FIG. 1 is a schematic diagram showing one embodiment of a laminate of the present invention.
  • the laminate 1 includes a paper base material 2, a filling layer 3 arranged on at least one side in the thickness direction of the paper base material 2 (upper side of the paper surface), and a gas barrier layer 4 arranged on at least one side in the thickness direction of the filling layer 3 (upper side of the paper surface).
  • the laminate 1 may further include, as an optional layer, a heat seal layer 5 disposed on at least one side in the thickness direction of the gas barrier layer 4 (upper side of the paper).
  • the laminate 1 includes a heat seal layer 5. 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 (lower side of the paper) to one side (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 filler layer 3 is laminated on the paper base material 2 to suppress impregnation of the gas barrier coating material (described later) into the paper base material 2.
  • the filler layer 3 is also laminated on the paper base material 2 to absorb unevenness on the surface of the paper base material 2 and smooth the surface. More specifically, the filler layer 3 is disposed on at least one surface of the paper base material 2.
  • the filler layer 3 may be disposed on both sides of the paper base material 2.
  • the filler layer 3 is preferably disposed only on one surface of the paper base material 2.
  • the filling layer 3 contains a filling resin. More specifically, the filling layer 3 is formed, for example, by applying a coating material containing a filling resin (hereinafter, a filling coating material) to the surface of the paper base material 2 and drying it.
  • a coating material containing a filling resin hereinafter, a filling coating material
  • the sealing coating material examples include a solution obtained by dissolving a sealing resin in a solvent (described below) and a dispersion obtained by dispersing a sealing resin in a solvent (described below).
  • the filler resin examples include polyolefin resin and (meth)acrylic resin. More specifically, the filler resin (filler layer 3) contains polyolefin resin and (meth)acrylic resin as essential components. In other words, polyolefin resin and (meth)acrylic resin are used in combination as the filler resin.
  • a polyolefin resin is a resin containing structural units derived from an olefin, and is obtained by polymerization of monomer components (hereinafter, olefin raw material monomer components) as a raw material composition.
  • the olefin raw material monomer component contains an olefin.
  • olefins include ⁇ -olefins.
  • ⁇ -olefins include ⁇ -olefins having 1 to 20 carbon atoms.
  • ⁇ -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.
  • the ⁇ -olefin preferably, an olefin having 2 to 3 carbon atoms is used, more preferably, ethylene and/or propylene is used, and even more preferably, ethylene is used.
  • the olefin feed monomer component may contain only an olefin.
  • the olefin feed monomer component may also contain an olefin and a copolymerizable monomer.
  • the olefin feed monomer component contains an olefin and a copolymerizable monomer.
  • the copolymerizable monomer is a monomer that can be copolymerized with the olefin.
  • the copolymerizable monomer include unsaturated carboxylic acids, 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 types.
  • the copolymerizable monomer preferably, an unsaturated carboxylic acid is used. If the olefin raw material monomer component contains an unsaturated carboxylic acid, excellent water dispersibility can be obtained.
  • 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 methacrylic acid is preferable.
  • an unsaturated carboxylic acid-modified polyolefin resin is obtained as the polyolefin resin. More specifically, an example of an unsaturated carboxylic acid-modified polyolefin resin is ethylene-methacrylic acid copolymer (EMAA).
  • EEMAA ethylene-methacrylic acid copolymer
  • the content ratio of the olefin to the copolymerizable monomer is appropriately set according to the type of copolymerizable monomer.
  • the ratio of the olefin to the unsaturated carboxylic acid as the copolymerizable monomer is appropriately adjusted in order to balance the handleability (blocking resistance) and bending resistance of the sealing layer 3 with the hydrophilicity of the polyolefin resin.
  • 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.
  • 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 method for producing polyolefin resin is not particularly limited, and known methods can be used.
  • the above-mentioned olefin raw material monomer components are 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 (meth)acrylic resin is a resin containing a structural unit derived from a (meth)acrylic acid ester, and is obtained by polymerization of a monomer component (hereinafter, an acrylic raw material monomer component) as a raw material composition.
  • a monomer component hereinafter, an acrylic raw material monomer component
  • the acrylic raw material monomer component contains a (meth)acrylic acid ester.
  • the (meth)acrylic acid ester include (meth)acrylic acid esters having an alkyl portion with 1 to 12 carbon atoms. More specific examples of the (meth)acrylic acid ester include 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.
  • the (meth)acrylic acid ester preferably, a (meth)acrylic acid ester having an alkyl portion having 2 to 10 carbon atoms is used, more preferably, a (meth)acrylic acid ester having an alkyl portion having 4 to 8 carbon atoms is used, and even more preferably, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are used, and particularly preferably, 2-ethylhexyl (meth)acrylate (also known as 2-ethylhexyl (meth)acrylate) is used.
  • 2-ethylhexyl (meth)acrylate also known as 2-ethylhexyl (meth)acrylate
  • the acrylic raw material monomer component may contain only a (meth)acrylic acid ester.
  • the acrylic raw material monomer component may also contain a (meth)acrylic acid ester and a copolymerizable monomer.
  • the acrylic raw material monomer component contains a (meth)acrylic acid ester and a copolymerizable monomer.
  • the copolymerizable monomer is a monomer that can be copolymerized with the (meth)acrylic acid ester.
  • the copolymerizable monomer include olefins, unsaturated carboxylic acids, 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 types.
  • an aromatic vinyl monomer is preferably used. If the acrylic raw material monomer component contains an aromatic vinyl monomer, the blocking resistance of the sealing layer 3 is further improved.
  • Aromatic vinyl monomers include, for example, styrene, ⁇ -methylstyrene, t-butylstyrene, halogenated styrene, vinyltoluene, and vinylxylene. These can be used alone or in combination of two or more.
  • a preferred aromatic vinyl monomer is styrene.
  • an aromatic ring-containing (meth)acrylic resin is obtained as the (meth)acrylic resin. More specifically, an aromatic ring-containing (meth)acrylic resin is, for example, a styrene-(meth)acrylic acid ester copolymer.
  • the content ratio of the (meth)acrylic acid ester and the copolymerizable monomer is appropriately set according to the type of copolymerizable monomer.
  • the ratio of the (meth)acrylic acid ester and the aromatic vinyl monomer as the copolymerizable monomer is appropriately adjusted in order to balance the handleability (blocking resistance) and bending resistance of the sealing layer 3 with the glass transition temperature of the (meth)acrylic resin (described later).
  • the content of the (meth)acrylic acid ester is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more, based on the total amount of the acrylic raw material monomer components.
  • the content of the (meth)acrylic acid ester is, for example, 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 85% by mass or less, and particularly preferably 70% by mass or less, based on the total amount of the acrylic raw material monomer components.
  • the content of (meth)acrylic acid ester in the acrylic raw material monomer component is essentially synonymous with the content of structural units derived from (meth)acrylic acid ester in the (meth)acrylic resin.
  • the content of the structural units derived from the (meth)acrylic acid ester is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more, relative to the total amount of the (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 90% by mass or less, more preferably 80% by mass or less, even more preferably 85% by mass or less, and particularly preferably 70% by mass or less, relative to the total amount of the (meth)acrylic resin.
  • the content of the aromatic vinyl monomer is, from the viewpoints of handleability (blocking resistance) and glass transition temperature, for example, 1% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and particularly preferably 30% by mass or more, based on the total amount of the acrylic raw material monomer components.
  • the content of the aromatic vinyl monomer is, from the viewpoints of flex resistance and glass transition temperature, for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less, based on the total amount of the acrylic raw material monomer components.
  • the content of aromatic vinyl monomer in the acrylic raw material monomer component is essentially the same as the content of structural units derived from aromatic vinyl monomer in the (meth)acrylic resin.
  • the content of the structural units derived from aromatic vinyl monomers is, for example, 1% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and particularly preferably 30% by mass or more, relative to the total amount of (meth)acrylic resin.
  • the content of the structural units derived from aromatic vinyl monomers is, for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less, relative to the total amount of (meth)acrylic resin.
  • the content of structural units derived from the olefin in the (meth)acrylic resin is less than 50% by mass, preferably 40% by mass or less, based on the total amount of the (meth)acrylic resin.
  • the (meth)acrylic resin is distinguished from the above-mentioned polyolefin resin by the content of structural units derived from the olefin.
  • the types and ratios of (meth)acrylic acid esters and copolymerizable monomers are set in order to adjust the glass transition temperature of the (meth)acrylic resin.
  • the glass transition temperature of the (meth)acrylic resin is, for example, -90°C or higher, preferably -60°C or higher, more preferably -50°C or higher, even more preferably -40°C or higher, and particularly preferably -30°C or higher.
  • the glass transition temperature of the (meth)acrylic resin is, for example, 70°C or lower, preferably 50°C or lower, more preferably 30°C or lower, even more preferably 10°C or lower, even more preferably 0°C or lower, and particularly preferably -10°C or lower. If the glass transition temperature of the (meth)acrylic resin is in the above range, particularly excellent blocking resistance can be obtained.
  • the glass transition temperature of the (meth)acrylic resin is calculated based on the Fox formula.
  • the Fox formula is a well-known formula that shows the relationship between the glass transition temperature of a polymer and the glass transition temperature Tg of the homopolymer of the monomer that constitutes that polymer.
  • the method for producing the (meth)acrylic resin is not particularly limited, and known methods can be used.
  • the above-mentioned 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 sealing resin may contain other resins as optional components.
  • the other resins are resins other than polyolefin resins and (meth)acrylic resins.
  • examples of the other resins include polyester resins, polyamide resins, polyvinyl resins, polycarbonate resins, and cellulose resins. These may be used alone or in combination of two or more.
  • the sealing resin preferably does not contain any other resins and is made of polyolefin resin and (meth)acrylic resin.
  • the ratio of polyolefin resin to (meth)acrylic resin in the sealing resin is adjusted from the viewpoint of achieving a balance between the handleability (blocking resistance) and flex resistance of the sealing layer 3.
  • the content of polyolefin resin relative to the total amount of polyolefin resin and (meth)acrylic resin is, for example, 6% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably more than 50% by mass, even more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 75% by mass or more.
  • the content of polyolefin resin relative to the total amount of polyolefin resin and (meth)acrylic resin is, for example, 94% by mass or less, preferably 92% by mass or less, more preferably 90% by mass or less, even more preferably 88% by mass or less, and particularly preferably 85% by mass or less.
  • the content of (meth)acrylic resin relative to the total amount of polyolefin resin and (meth)acrylic resin is, for example, 6% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, even more preferably 12% by mass or more, and particularly preferably 15% by mass or more.
  • the content of (meth)acrylic resin relative to the total amount of polyolefin resin and (meth)acrylic resin is, for example, 94% by mass or less, preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably less than 50% by mass, even more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
  • the sealing layer 3 has particularly good handling properties (blocking resistance) and bending resistance.
  • the form of the filler resin is not particularly limited as long as it contains a polyolefin resin and a (meth)acrylic resin.
  • the filler resin may be a resin composition (mixed resin) containing a polyolefin resin and a (meth)acrylic resin.
  • the filler resin may also be a composite resin (polyolefin-(meth)acrylic composite resin) containing a polyolefin resin and a (meth)acrylic resin.
  • the sealing resin is a resin composition (mixed resin) containing a polyolefin resin and a (meth)acrylic resin
  • the polyolefin resin and the (meth)acrylic resin are prepared separately.
  • the polyolefin resin is prepared in a state where it is dissolved and/or dispersed in a solvent.
  • the olefin raw material monomer components are polymerized in the solvent, thereby synthesizing the polyolefin resin in the solvent. This results in a dispersion of the polyolefin resin (polyolefin dispersion).
  • 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.
  • the (meth)acrylic resin is prepared in a state of being dissolved and/or dispersed in a solvent.
  • the acrylic raw material monomer components are polymerized in the above-mentioned solvent, whereby the (meth)acrylic resin is synthesized in the solvent. This results in a dispersion of the (meth)acrylic resin (acrylic emulsion).
  • a dispersion of polyolefin resin (polyolefin dispersion) and a dispersion of (meth)acrylic resin (acrylic emulsion) are mixed.
  • the mixing ratio is adjusted, for example, so that the mass ratio of polyolefin resin to (meth)acrylic resin is within the above range.
  • the sealing resin is a composite (composite resin) containing a polyolefin resin and a (meth)acrylic resin
  • examples of the composite (composite resin) include core-shell particles.
  • the core-shell particles are manufactured by a known method. More specifically, the method for manufacturing the core-shell particles is not particularly limited, but for example, the acrylic raw material monomer component is polymerized in a dispersion liquid (polyolefin dispersion) containing the above-mentioned polyolefin resin.
  • the polymerization method is appropriately set depending on the type and amount of the acrylic raw material monomer component.
  • the (meth)acrylic resin is synthesized in the above solvent so as to coat the polyolefin resin. If necessary, the (meth)acrylic resin is neutralized with a known neutralizing agent after the reaction is completed.
  • core-shell particles that have a core containing a polyolefin resin and a shell that covers the core and contains a (meth)acrylic resin as a composite resin.
  • a solution and/or dispersion of a filling resin (composite resin) is obtained.
  • an emulsion of a polyolefin-(meth)acrylic composite resin is obtained.
  • the composite resin is not limited to the above-mentioned core-shell particles.
  • the composite resin may be a core-shell particle having a core containing a (meth)acrylic resin and a shell covering the core and containing a polyolefin resin.
  • a resin composition (mixed resin) containing the above-mentioned polyolefin resin and (meth)acrylic resin can be used in combination with a composite resin (polyolefin-(meth)acrylic composite resin) containing a polyolefin resin and a (meth)acrylic resin.
  • the sealing resin is preferably a composite resin containing a polyolefin resin and a (meth)acrylic resin (polyolefin-(meth)acrylic composite resin).
  • the sealing resin is preferably a resin composition (mixed resin) containing a polyolefin resin and a (meth)acrylic resin. That is, depending on the manufacturing method, the solid content concentration of the (meth)acrylic resin can be made relatively high. Therefore, the solid content concentration of the resin composition (mixed resin) containing a polyolefin resin and a (meth)acrylic resin can be made relatively high. And a resin composition (mixed resin) with a relatively high solid content concentration has excellent coating drying properties.
  • the solids concentration of the solution and/or dispersion of the filler resin is, for example, 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more.
  • the solids concentration of the solution and/or dispersion of the filler resin is, for example, 60% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less.
  • the filler coating material contains a solution and/or dispersion of the filler resin. That is, the filler coating material contains the filler resin and the solvent. If necessary, the filler coating material can contain an additive. That is, the filler coating material can contain the filler resin, the additive, and the solvent.
  • Additives include, for example, 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 types. The amount of additive to be added and the timing of its addition are set appropriately depending on the purpose and application.
  • 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 method of applying the filler 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 filler 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 filling layer 3 is, for example, 1 g/ m2 or more, preferably 3 g/m2 or more.
  • the amount (dry mass) of the filling layer 3 is, for example, 30 g/m2 or less , preferably 15 g/m2 or less .
  • the gas barrier layer 4 is a layer having gas barrier properties.
  • the gas barrier properties are the property of reducing the oxygen permeability. More specifically, the gas barrier layer 4 is made of a gas barrier resin having an oxygen permeability of a predetermined value or less.
  • the oxygen permeability of the gas barrier layer 4 having a thickness of 10 ⁇ m 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 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 coating 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 produced, 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 known heat-sealable resins can be used. More specifically, examples of heat-sealable resins include polyolefin resins, acrylic resins, and polyurethane resins. Examples of heat-sealable resins include resin compositions (mixed resins) containing polyolefin resins and (meth)acrylic resins. Examples of heat-sealable resins include composite resins (polyolefin-(meth)acrylic composite resins) containing polyolefin resins and (meth)acrylic resins.
  • the heat-sealable resin may be the same as the sealing resin. These can be used alone or in combination of two or more types.
  • heat-sealable resins include preferably polyolefin resins and (meth)acrylic resins, more preferably the use of polyolefin resins alone and the use of polyolefin resins and (meth)acrylic resins in combination, even more preferably the use of polyolefin resins and (meth)acrylic resins in combination, and particularly preferably the use of composite resins (polyolefin-(meth)acrylic composite resins) containing polyolefin resins and (meth)acrylic resins.
  • the heat sealable resin is preferably the same as the sealing resin.
  • the heat-sealable resin is prepared, for example, as a solution and/or dispersion dissolved and/or dispersed in a solvent.
  • the heat-sealable resin is synthesized in a solvent. This results in a solution and/or dispersion of the 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 polyolefin resins, acrylic emulsions containing acrylic resins, and polyurethane dispersions containing polyurethane resins.
  • a preferred example of a heat-sealable coating material is polyolefin dispersion.
  • 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 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, for example, 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, for example, 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 sealing layer 3, and a gas barrier layer 4.
  • the sealing layer 3 contains a polyolefin resin and a (meth)acrylic resin. Therefore, the sealing layer 3 has excellent blocking resistance. That is, the laminate 1 has excellent handleability. Furthermore, since the sealing layer 3 contains a polyolefin resin and a (meth)acrylic resin, it has excellent bending resistance. As a result, the laminate 1 has both excellent handleability and excellent bending resistance.
  • 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.
  • packaging material contains the laminate 1 described above, it has both excellent handling properties and excellent bending resistance.
  • packaging materials are used in various industrial fields.
  • the packaging material is used in the food packaging field.
  • the laminate 1 and the packaging material described above include a heat seal layer 5.
  • the heat seal layer 5 is an optional layer.
  • the laminate 1 and the packaging material may not include the heat seal layer 5 depending on the purpose and use.
  • 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.
  • any functional layer may be laminated onto the gas barrier layer 4.
  • Paper substrate preparation example 1 The following papers were prepared as paper substrates.
  • Gintake One-sided gloss (unbleached) kraft paper, product name "Gintake”, manufactured by Nippon Paper Industries Co., Ltd., basis weight 41.7 g/ m2 , 66.6 g/ m2 , 83.3 g/ m2
  • Shirogane One-sided gloss (bleached) kraft paper, product name "Shirogane”, made by Nippon Paper Industries Co., Ltd., basis weight 30 g/m 2 , 65 g/m 2
  • Kinshachi Pure white roll paper, product name "Kinshachi”, manufactured by Daio Paper Corporation, basis weight 30 g/ m2 , 65 g/ m2
  • Nagoya Sarashi Ryuo One-sided gloss (bleached) kraft paper, product name "Nagoya Sarashi Ryuo", manufactured by Daio Paper Corporation, basis weight 60 g/ m2 (5) Glassine paper; product name "Thick white
  • 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.
  • the average particle size was measured by dynamic light scattering (measuring device FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.) (same below).
  • Preparation Example 1 (Secondary Polyurethane Dispersion) A dispersion of a layered inorganic compound (product name: NTS-10NC, manufactured by Topy Industries, Ltd., solid content concentration 10.7%) (hereinafter, synthetic mica 1) was prepared. The dispersion of the layered inorganic compound and water were mixed for 5 minutes. As a result, a dispersion of an additive was obtained.
  • a layered inorganic compound product name: NTS-10NC, manufactured by Topy Industries, Ltd., solid content concentration 10.7%
  • the primary PUD from Synthesis Example 1 was mixed with the additive dispersion for 5 minutes so that the solids mass ratio of the polyurethane resin to the layered inorganic compound (polyurethane resin:layered inorganic compound) was 5:15.
  • secondary PUD a secondary polyurethane dispersion
  • the gas barrier polyurethane resin and the additive layered inorganic compound
  • the solids concentration of the secondary PUD was 15 mass%.
  • the secondary PUD was used as gas barrier coating material 1.
  • Preparation Example 2 (Secondary Polyurethane Dispersion) A dispersion of a layered inorganic compound (product name: ME300-B4T, manufactured by Katakura Co-op Agri Co., Ltd., solid content concentration 7.8%) (hereinafter, synthetic mica 2) was prepared.
  • a layered inorganic compound product name: ME300-B4T, manufactured by Katakura Co-op Agri Co., Ltd., solid content concentration 7.8%
  • a secondary polyurethane dispersion (secondary PUD) was obtained in the same manner as in Preparation Example 1, except that synthetic mica 2 was used instead of synthetic mica 1.
  • the solids concentration of the secondary PUD was 15 mass%.
  • the secondary PUD was used as gas barrier coating material 2.
  • Preparation Example 3 (Secondary Polyurethane Dispersion) A dispersion of a layered inorganic compound (product name: Kunipia RC-I, synthetic mica 3, manufactured by Kunimine Industries Co., Ltd., solid content concentration 4.0%) was prepared.
  • a secondary polyurethane dispersion (secondary PUD) was obtained in the same manner as in Preparation Example 1, except that synthetic mica 3 was used instead of synthetic mica 1.
  • the solids concentration of the secondary PUD was 15 mass%.
  • the secondary PUD was used as gas barrier coating material 3.
  • PVA Polyvinyl alcohol (product name: Kuraray Poval PVA117, manufactured by Kuraray Co., Ltd.) (hereinafter referred to as PVA) was prepared. The PVA was dispersed in water. Thus, an aqueous dispersion of PVA was obtained. The solid content concentration of the aqueous dispersion of PVA was adjusted to 30 mass%.
  • a secondary polyurethane dispersion (secondary PUD) was obtained in the same manner as in Preparation Example 2, except that an aqueous dispersion of PVA was used instead of the primary PUD.
  • the solids concentration of the secondary PUD was 15 mass%.
  • the secondary PUD was used as the gas barrier coating material 4.
  • PO polyolefin dispersion
  • EMAA polyolefin dispersion
  • the average particle size (dynamic light scattering method) of the polyolefin dispersion (PO) was 38 nm, and the solids concentration was 22% by mass.
  • 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 2-ethylhexyl acrylate (raw monomer) 1608 parts by weight Styrene (raw monomer) 893 parts by weight
  • the acrylic emulsion was cooled to room temperature. Ion-exchanged water and ammonia water (neutralizing agent) were then added to the acrylic emulsion to adjust the solids concentration to 42% by mass and the pH to 8.0.
  • an acrylic emulsion (Ac) was obtained in which the (meth)acrylic resin was dispersed in water.
  • the average particle size of the acrylic emulsion was 257 nm.
  • the theoretical glass transition temperature of the (meth)acrylic resin was calculated based on the Fox formula.
  • the theoretical glass transition temperature of the (meth)acrylic resin was -30°C.
  • Synthesis Example 4 Polyolefin-(meth)acrylic composite resin emulsion
  • PO polyolefin dispersion
  • the monomer emulsion is a raw material composition containing the following components. Ion-exchanged water (solvent) 20 parts by weight Sodium dodecyl sulfate (surfactant) 0.05 parts by weight 2-ethylhexyl acrylate (raw monomer) 16.1 parts by weight Styrene (raw monomer) 8.9 parts by weight
  • the contents of the reaction vessel were aged for 3 hours. This allowed the raw material monomers to polymerize in the polyolefin dispersion (PO), synthesizing the (meth)acrylic resin (Ac). This resulted in a polyolefin-(meth)acrylic composite resin (PO/Ac). Also, a composite resin emulsion was obtained in which the polyolefin-(meth)acrylic composite resin (PO/Ac) was dispersed in water.
  • the polyolefin-(meth)acrylic composite resin (PO/Ac) had a core-shell structure.
  • the core was polyolefin resin (PO) and the shell was (meth)acrylic resin (Ac).
  • the glass transition temperature (Fox formula) of the (meth)acrylic resin contained in the polyolefin-(meth)acrylic composite resin (PO/Ac) was -30°C.
  • the composite resin emulsion was cooled to room temperature. Ion-exchanged water was then added to the composite resin emulsion to adjust the solids concentration to 25% by mass, and the pH was adjusted to 10.0.
  • a composite resin emulsion was obtained in which polyolefin-(meth)acrylic composite resin (PO/Ac) was dispersed in water.
  • the average particle size of the composite resin emulsion was 73 nm.
  • the composite resin emulsion solid content concentration 25% by mass was used as a sealing coating material.
  • Synthesis Examples 5 to 30 Polyolefin-(meth)acrylic composite resin emulsions
  • the formulation of the monomer emulsion was changed to the formulations shown in Tables 1 to 3.
  • a composite resin emulsion in which a polyolefin-(meth)acrylic composite resin was dispersed in water was obtained in the same manner as in Synthesis Example 4.
  • the composite resin emulsion (solid content concentration: 25% by mass) was used as a sealing coating material.
  • the glass transition temperatures (Fox formula) of the (meth)acrylic resins in each formulation are shown in Tables 1 to 3.
  • Mixing preparation examples 1 to 9 (mixed resin) According to the formulation shown in Table 4, the polyolefin dispersion (EMAA dispersion) of Synthesis Example 1 and the acrylic emulsion of Synthesis Example 3 were mixed. Ion-exchanged water was added to the mixture, and the solid content was The concentration was adjusted to 25% by mass. This resulted in a mixed liquid (Po+Ac) containing a polyolefin resin and a (meth)acrylic resin. The mixed liquid (Po+Ac) containing a polyolefin resin and a (meth)acrylic resin was It was used as a sealing coating material.
  • Heat-sealable coating material Preparation example 2 (HS-POD) A dispersion of a polyolefin resin having heat sealability (HS) (product name: Chemipearl S500NW, manufactured by Mitsui Chemicals) (hereinafter, HS-POD) was prepared. The HS-POD was used as a heat sealable coating material.
  • HS polyolefin resin having heat sealability
  • Preparation example 3 A polyolefin resin film having heat sealability (HS) (product name: HC-40, thickness 40 ⁇ m, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) (hereinafter, referred to as HS-POF) was prepared.
  • the POF was used as a heat seal layer.
  • Laminates Examples 1 to 57 and Comparative Examples 1 to 3 (Laminates)
  • the filler coating material was applied to one side (smooth side or non-smooth side) of the paper substrate using a bar coater in the combinations shown in Tables 5 to 12.
  • the application amount was adjusted so that the dry mass would be the amount (g/m 2 ) shown in Tables 5 to 10.
  • the coating film of the filler coating material was then dried at 120° C. for 60 seconds. This formed a filler layer.
  • a gas barrier coating material was applied to the surface of the filling layer using a bar coater in the combinations shown in Tables 5 to 12. The application amount was adjusted so that the dry mass would be the amount (g/m 2 ) shown in Tables 5 to 12.
  • 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. As a result, a laminate was obtained.
  • the layer structure of the laminate was as follows.
  • Example 10 Example 56, and Example 57, a heat-sealable coating material was applied to the surface of the gas barrier layer using a bar coater.
  • HS-POD of Preparation Example 2 was used as the heat-sealable coating material.
  • the polyolefin-(meth)acrylic composite resin emulsion of Synthesis Example 6 was used as the heat-sealable coating material.
  • the acrylic emulsion of Synthesis Example 3 was used as the heat-sealable coating material.
  • the application amount of the heat-sealable coating material was adjusted so that the dry mass was 3 g/m 2.
  • the layer structure of the laminate was as follows.
  • Example 11 a heat sealable film was attached to the surface of the gas barrier layer using an adhesive (product name A-616/product name A-65 (manufactured by Mitsui Chemicals)). The adhesive was then cured at 40°C for two days. This resulted in a laminate.
  • the layer structure of the laminate was as follows:
  • OTR Oxygen transmission rate
  • the laminate was folded at 2 kg/ cm2 for 10 seconds at 25°C so that the coated surface (sealing layer and gas barrier layer) was on the inside.
  • the folding direction was changed by 90°C so as to form a cross crease, and the laminate was folded again at 2 kg/ cm2 for 10 seconds.
  • the laminate was folded at 2 kg/ cm2 for 10 seconds at 25°C so that the coated surface (sealing layer and gas barrier layer) was on the inside.
  • the folding direction was changed by 90°C so as to form a cross crease, and the laminate was folded again at 2 kg/ cm2 for 10 seconds.
  • Blocking resistance A laminate (two-layered body consisting of a paper substrate and a sealing layer) was prepared before forming a gas barrier layer.
  • the sealing layer of the two-layered body and the printed surface of a paper packaging material (Kit Kat Biscuit Flavor (product name), manufactured by Nestle) were pressed together with a heat sealer.
  • the pressing temperature was 30°C
  • the pressing force was 0.5 kg/ cm2
  • the pressing time was 10 seconds.
  • the blocking resistance of the sealing layer was evaluated according to the following criteria. The results are shown in Tables 5 to 12.
  • the sealant coating material was stored at 60°C for two weeks. After storage, the viscosity of the sealant coating material at 25°C was measured under the above conditions.
  • Viscosity increase rate (%) [viscosity after storage/viscosity before storage] x 100
  • the laminate and packaging material of the present invention are suitable for use in the food packaging field.

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JPH10500635A (ja) * 1994-05-25 1998-01-20 ボレアリス アクティーゼルスカブ 重合体材料および多層製品におけるその使用
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