WO2016143889A1 - 積層体、食品包装材料および積層体の製造方法 - Google Patents
積層体、食品包装材料および積層体の製造方法 Download PDFInfo
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- WO2016143889A1 WO2016143889A1 PCT/JP2016/057724 JP2016057724W WO2016143889A1 WO 2016143889 A1 WO2016143889 A1 WO 2016143889A1 JP 2016057724 W JP2016057724 W JP 2016057724W WO 2016143889 A1 WO2016143889 A1 WO 2016143889A1
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- 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
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- 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
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- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- 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
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- B05D1/00—Processes for applying liquids or other fluent materials
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Definitions
- the present invention relates to a laminate, a food packaging material, and a method for producing the laminate, and more particularly to a laminate, a food packaging material including the laminate, and a method for producing the laminate.
- a gas barrier obtained by laminating a layer containing a gas barrier polyurethane resin obtained by reacting a diisocyanate component with a diol component containing a C2-8 alkyl glycol and a base film layer.
- a gas barrier composite film obtained by forming an inorganic layer by vapor deposition or sputtering on at least one surface of a porous composite film and further a base film layer has been proposed (for example, see Patent Document 1 below).
- the gas barrier property and interlayer adhesion strength differed greatly depending on the components used for forming the coating layer and the order of the layer configuration.
- the gas barrier property and adhesive strength are not determined by the sum of the performance of each layer, but the order of each layer and the configuration of each layer are presumed to be greatly affected.
- the layer containing the gas barrier polyurethane resin described above is interposed between a hydrocarbon-based substrate such as a polyolefin sheet or a polyolefin film and an inorganic layer (metal vapor deposition layer). And the result that those interface adhesiveness was not enough was also obtained.
- an object of the present invention is to provide a laminate excellent in gas barrier properties and adhesion, and preferably excellent in heat sealability, a food packaging material provided with the laminate, and a method for producing the laminate. is there.
- a coating liquid containing a polyurethane dispersion containing a polyurethane resin obtained by a reaction between an isocyanate group-terminated prepolymer and a chain extender, and a water-dispersible polyisocyanate is obtained by coating and drying the substrate. , Including a laminate.
- the mass ratio of the resin component in the polyurethane dispersion to the resin component in the water-dispersible polyisocyanate (resin component in the polyurethane dispersion / resin component in the water-dispersible polyisocyanate)
- the laminate according to the above [1] which is in the range of 2/1 to 99/1.
- This invention [3] contains the laminated body as described in said [1] or [2] whose said base material is an unstretched polyolefin film.
- the present invention [5] includes a food packaging material comprising the laminate according to any one of [1] to [4] above.
- the present invention [6] is a laminate in which a substrate / polyurethane layer / metal vapor deposition layer are laminated in this order, the substrate is a polyolefin film, and the polyurethane layer contains the following groups in the following proportions.
- a substrate / polyurethane layer / metal vapor deposition layer is laminated in this order, the substrate is a polyolefin film, and the polyurethane layer contains the following groups in the following proportions.
- B C2-C6 alkylene group: 0.5% to 25% by mass
- C Polyalkylene oxide group : 0.5 mass% or more and 10 mass% or less (however, the entire polyurethane layer is 100 mass%)
- This invention [7] contains the laminated body as described in said [6] in which the said polyurethane layer contains the following group in the following ratio further.
- the polyurethane layer further comprises the following groups: Is included in the following ratio, including the laminate according to the above [6] or [7].
- the present invention [9] includes a food packaging material provided with the laminate according to any one of the above [6] to [8].
- the present invention is a method for producing a laminate, in which a polyurethane layer is laminated on a base material made of a heat-sealable plastic film, and a metal vapor deposition layer is laminated on the polyurethane layer to obtain a laminate.
- a polyisocyanate component containing xylylene diisocyanate and / or hydrogenated xylylene diisocyanate, a diol having 2 to 6 carbon atoms, and a polyol component containing an active hydrogen group-containing compound containing a hydrophilic group A coating solution containing a polyurethane dispersion containing a polyurethane resin obtained by reaction of an isocyanate group-terminated prepolymer obtained by the reaction with a chain extender and a water-dispersible polyisocyanate is applied to the substrate and dried.
- the manufacturing method of the laminated body is included.
- the laminate of the present invention includes a polyurethane layer between a base material made of a heat-sealable plastic film and a metal vapor-deposited layer, and the polyurethane layer contains xylylene diisocyanate and / or hydrogenated xylylene diisocyanate.
- the base material / polyurethane layer / metal vapor deposition layer are laminated in this order, the base material is a polyolefin film, and the polyurethane layer contains a specific group in a specific ratio.
- the laminate can be produced efficiently.
- FIG. 1 is a schematic configuration diagram showing an embodiment of a laminate of the present invention.
- a laminated film 1 as an embodiment of the laminated body of the present invention includes a base material 2, a polyurethane layer 3 disposed on the surface of the base material 2, and metal vapor deposition disposed on the surface of the polyurethane layer 3.
- the base material 2 is preferably a polyolefin film (including a polyolefin film having heat sealing properties and a polyolefin film not having heat sealing properties).
- polystyrene film examples include a low density polyethylene film, a linear low density polyethylene film, an unstretched polypropylene film (CPP film), a uniaxially stretched polypropylene film, a biaxially stretched polypropylene film (OPP film), and 4-methyl- Examples thereof include a 1-pentene polymer film.
- the base material 2 consists of a single layer, or the same kind or two or more kinds of laminates.
- the substrate 2 is preferably an unstretched polyolefin film.
- the thickness of the substrate 2 is, for example, 3 ⁇ m or more, preferably 5 ⁇ m or more, and for example, 500 ⁇ m or less, preferably 200 ⁇ m or less.
- the polyurethane layer 3 is a resin layer containing a polyurethane resin described later.
- the polyurethane layer 3 preferably includes the following groups (A) to (C), and more preferably further includes the following group (D) and / or the following group (E). It is out.
- (A) xylylene group and / or hydrogenated xylylene group (B) alkylene group having 2 to 6 carbon atoms (C) polyalkylene oxide group (D) alkylene group containing ionic group and / or ionic group
- the xylylene group and / or the hydrogenated xylylene group is preferably a polyurethane layer by using xylylene diisocyanate (described later) and / or hydrogenated xyly
- the (A) xylylene group and / or hydrogenated xylylene group may be formed by using, for example, a water-dispersible polyisocyanate (described later) derived from a polyisocyanate having a xylylene group and / or a hydrogenated xylylene group. Introduced into layer 3.
- the content ratio (total amount) of the xylylene group and / or hydrogenated xylylene group is, for example, 10% by mass or more, preferably 12% by mass or more, more preferably, when the entire polyurethane layer 3 is 100% by mass. 15% by mass or more, for example, 45% by mass or less, preferably 40% by mass or less, and more preferably 35% by mass or less.
- the alkylene group having 2 to 6 carbon atoms is preferably introduced into the polyurethane layer 3 by using a diol having 2 to 6 carbon atoms (described later) as a raw material of the polyurethane layer 3.
- the (C) polyalkylene oxide group is obtained, for example, by using an active hydrogen group-containing compound (described later) containing a polyalkylene oxide group (hydrophilic group (nonionic group)) as a raw material for the polyurethane layer 3. Is also introduced into the polyurethane layer 3.
- an active hydrogen group-containing compound described later
- a polyalkylene oxide group hydrophilic group (nonionic group)
- the content ratio (total amount) of the polyalkylene oxide group is, for example, 0.5% by mass or more, preferably 1% by mass or more, for example, 10% by mass when the entire polyurethane layer 3 is 100% by mass. % Or less, preferably 8% by mass or less, and more preferably 7% by mass or less.
- the (C) polyalkylene oxide group can improve the interlayer adhesive strength between the substrate 2 and the polyurethane layer 3. In other words, when the polyurethane layer 3 does not contain the (C) polyalkylene oxide group, there is a tendency to cause a decrease in interlayer adhesive strength between the substrate 2 and the polyurethane layer 3.
- the (C) polyalkylene oxide group has little influence on the gas barrier property, even if the polyurethane layer 3 contains the (C) polyalkylene oxide group, there is a tendency that the gas barrier property is not lowered. This is because the (C) polyalkylene oxide group has compatibility with the (A) xylylene group and / or hydrogenated xylylene group contributing to gas barrier properties, the (B) alkylene group having 2 to 6 carbon atoms, and the like. This is presumably because the (C) polyalkylene oxide group is relatively high and is not unevenly distributed in the polyurethane layer 3.
- a hydrogen group-containing compound described later, it is preferably introduced into the polyurethane layer 3 as necessary.
- the (D) alkylene group containing an ionic group and / or an arylene group containing an ionic group improves the solubility and dispersibility in water.
- the (D) alkylene group containing an ionic group and / or an arylene group containing an ionic group improves the interlayer adhesion strength between the polyurethane layer 3 and the metal vapor-deposited layer 4.
- At least one group selected from the group consisting of an alkylene group having an amino group skeleton, an arylene group having an amino group skeleton, an alkylene group having a thiol group skeleton, and an arylene group having a thiol group skeleton is, for example,
- a chain extender preferably an amino group-containing component (described later) described later is preferably introduced into the polyurethane layer 3 as necessary.
- (E) includes at least one group selected from the group consisting of an alkylene group having an amino group skeleton, an arylene group having an amino group skeleton, an alkylene group having a thiol group skeleton, and an arylene group having a thiol group skeleton
- the content ratio (total amount) is, for example, 1% by mass or more, preferably 1.5% by mass or more, more preferably 2% by mass or more when the entire polyurethane layer 3 is 100% by mass. For example, it is 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.
- the alkylene group having an amino group skeleton, the arylene group having an amino group skeleton, the alkylene group having a thiol group skeleton, and the arylene group having a thiol group skeleton can increase the molecular weight of the polyurethane resin.
- Such a polyurethane layer 3 is a resin layer containing a polyurethane resin, preferably a resin layer made of a polyurethane resin, and preferably a coating liquid containing a polyurethane dispersion and a water-dispersible polyisocyanate. By applying and drying on the substrate 2, it is obtained as a film formation layer.
- the polyurethane dispersion is preferably obtained by dispersing a polyurethane resin (aqueous polyurethane resin) in water.
- the polyurethane resin contained in the polyurethane dispersion includes, for example, a polyisocyanate component and a polyol component such as an active hydrogen group-containing component (for example, a diol having 2 to 6 carbon atoms described later (described later) such as an amino group-containing component ( Etc.) can be obtained as a polyadduct.
- a polyisocyanate component for example, a diol having 2 to 6 carbon atoms described later (described later) such as an amino group-containing component ( Etc.)
- Etc. an amino group-containing component
- the polyisocyanate component contains xylylene diisocyanate and / or hydrogenated xylylene diisocyanate as an essential component.
- xylylene diisocyanate As xylylene diisocyanate (XDI), 1,2-xylylene diisocyanate (o-XDI), 1,3-xylylene diisocyanate (m-XDI), and 1,4-xylylene diisocyanate (p-XDI) have the structure Listed as isomers.
- xylylene diisocyanates can be used alone or in combination of two or more.
- the xylylene diisocyanate is preferably 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and more preferably 1,3-xylylene diisocyanate.
- Hydrogenated xylylene diisocyanate also known as bis (isocyanatomethyl) cyclohexane) (H 6 XDI) includes 1,2-hydrogenated xylylene diisocyanate (1,2-bis (isocyanatomethyl) cyclohexane, o- H 6 XDI), 1,3-hydrogenated xylylene diisocyanate (1,3-bis (isocyanatomethyl) cyclohexane, m-H 6 XDI), 1,4-hydrogenated xylylene diisocyanate (1,4-bis ( Isocyanatomethyl) cyclohexane, pH 6 XDI) are listed as structural isomers.
- the hydrogenated xylylene diisocyanate is preferably 1,3-hydrogenated xylylene diisocyanate, 1,4-hydrogenated xylylene diisocyanate, and more preferably 1,3-hydrogenated xylylene diisocyanate.
- xylylene diisocyanate and / or hydrogenated xylylene diisocyanate includes derivatives thereof.
- Examples of the derivatives of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate include, for example, multimers of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate (for example, dimers, trimers (for example, isocyanurate modified products, Iminooxadiazinedione-modified products), pentamers, heptamers, etc.), allophanate-modified products (for example, xylylene diisocyanate and / or hydrogenated xylylene diisocyanate and a low molecular weight polyol described later) Modified products, etc.), polyol modified products (for example, polyol modified products (alcohol adducts) produced by the reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate with a low molecular weight polyol described later), biuret, etc.
- Modified products for example, biuret modified products produced by reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate with water or amines
- urea modified products for example, xylylene diisocyanate and / or hydrogenated xylylene diene
- Modified ureas produced by reaction of isocyanate and diamine modified oxadiazine trione (eg, oxadiazine trione produced by reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate and carbon dioxide)
- Carbodiimide modified products (carbodiimide modified products produced by decarboxylation condensation reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate), uretdione modified products, uretonimine modified products, etc. That.
- xylylene diisocyanate and hydrogenated xylylene diisocyanate can be used alone or in combination.
- the ratio of xylylene diisocyanate and hydrogenated xylylene diisocyanate is, for example, 99/1 to 1 / 99, preferably 90/10 to 10/90, more preferably 65/35 to 35/65.
- polyisocyanate component can contain other polyisocyanates as necessary.
- polyisocyanates include, for example, polyisocyanates such as aromatic polyisocyanates, araliphatic polyisocyanates (excluding xylylene diisocyanate), aliphatic polyisocyanates, and alicyclic polyisocyanates (excluding hydrogenated xylylene diisocyanate). Etc.
- aromatic polyisocyanate examples include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4, 4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof) (MDI), And aromatic diisocyanates such as 4,4′-toluidine diisocyanate (TODI) and 4,4′-diphenyl ether diisocyanate.
- TODI 4,4′-toluidine diisocyanate
- TODI 4,4′-diphenyl ether diisocyanate
- araliphatic polyisocyanate examples include, for example, tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof) (TMXDI), ⁇ , ⁇ ′- And aromatic aliphatic diisocyanates such as diisocyanate-1,4-diethylbenzene.
- TXDI tetramethylxylylene diisocyanate
- ⁇ , ⁇ ′- And aromatic aliphatic diisocyanates such as diisocyanate-1,4-diethylbenzene.
- aliphatic polyisocyanate examples include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 , 5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (also known as hexamethylene diisocyanate) (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6- Aliphatic diisocyanates such as diisocyanate methyl capate are listed.
- PDI 5-pentamethylene diisocyanate
- HDI 1,6-hexamethylene diisocyanate
- 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate 2,6- Aliphatic diisocyanates such as diisocyanate methyl capate
- Examples of alicyclic polyisocyanates include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate).
- polyisocyanates include derivatives of the same kind as described above.
- polystyrene resin can be used alone or in combination of two or more.
- Preferred are araliphatic polyisocyanates and alicyclic polyisocyanates, more preferred are alicyclic polyisocyanates, and still more preferred are methylene bis (cyclohexyl isocyanate).
- the content of xylylene diisocyanate and hydrogenated xylylene diisocyanate is 50 mass% or more with respect to the total amount of a polyisocyanate component, Preferably, it is 60 mass% or more, More preferably, it is 80 mass% or more, for example, it is 99 mass% or less.
- polyisocyanates polyisocyanates excluding xylylene diisocyanate and hydrogenated xylylene diisocyanate
- the polyisocyanate component is preferably used in combination with xylylene diisocyanate and bis (isocyanatocyclohexyl) methane. Is mentioned.
- xylylene diisocyanate and bis (isocyanatocyclohexyl) methane together, a polyurethane dispersion having excellent water dispersibility and a small average particle diameter can be obtained without impairing gas barrier properties.
- xylylene diisocyanate is, for example, 60 parts by mass or more, preferably 100 parts by mass relative to the total amount of xylylene diisocyanate and bis (isocyanatocyclohexyl) methane. 70 parts by mass or more, more preferably 80 parts by mass or more, for example, 90 parts by mass or less, preferably 93 parts by mass or less, more preferably 95 parts by mass or less.
- Bis (isocyanatocyclohexyl) methane is, for example, 10 parts by mass or more, preferably 7 parts by mass or more, more preferably 5 parts by mass or more, for example, 40 parts by mass or less, preferably 30 parts by mass. Hereinafter, it is more preferably 20 parts by mass or less.
- the polyol component contains a diol having 2 to 6 carbon atoms as an essential component.
- the diol having 2 to 6 carbon atoms is an organic compound having 2 to 6 carbon atoms having a number average molecular weight of 40 or more and less than 400, and specifically includes, for example, 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, neopentyl glycol, 3-methyl-1 , 5-pentanediol, 1,3- or 1,4-cyclohexanediol, etc., alkanediol having 2 to 6 carbon atoms (alkylene glycol having 2 to 6 carbon atoms), such as diethylene glycol, triethylene glycol, dipropylene glycol, etc. Of C2-C6 ether diols such as 1,4-dihydroxy Etc. alkene diol having 2 to 6 carbon atoms
- diols having 2 to 6 carbon atoms can be used alone or in combination of two or more.
- the diol having 2 to 6 carbon atoms is preferably an alkanediol having 2 to 6 carbon atoms, more preferably ethylene glycol.
- the mixing ratio of the diol having 2 to 6 carbon atoms is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, for example, 70 parts by mass or less, preferably 100 parts by mass of the total amount of polyol components. 65 parts by mass or less.
- the polyol component preferably contains an active hydrogen group-containing compound containing a hydrophilic group as an optional component.
- the trivalent or higher molecular weight polyol is an organic compound having a number average molecular weight of 40 or more and less than 400 and having three or more hydroxyl groups in one molecule, such as glycerin, 2-methyl-2-hydroxymethyl-1, Trihydric alcohols such as 3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolpropane, 2,2-bis (hydroxymethyl) -3-butanol (low Molecular weight triol), for example, tetramethylolmethane (pentaerythritol), tetrahydric alcohols such as diglycerin, for example, pentahydric alcohols such as xylitol, such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentol Erythritol, etc. Hexahydric
- alicyclic polyamine examples include 3-aminomethyl-3,5,5-trimethylcyclohexylamine (also known as isophoronediamine), 4,4′-dicyclohexylmethanediamine, 2,5 (2,6) -bis ( Aminomethyl) bicyclo [2.2.1] heptane, 1,4-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3- and 1,4-bis (aminomethyl) cyclohexane and mixtures thereof Etc.
- 3-aminomethyl-3,5,5-trimethylcyclohexylamine also known as isophoronediamine
- additives can be blended as necessary.
- additives include silane coupling agents, alkoxysilane compounds, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, surfactants, Examples thereof include dispersion stabilizers, colorants (pigments, dyes, etc.), fillers, colloidal silica, inorganic particles, inorganic oxide particles, and crystal nucleating agents.
- a coating liquid is obtained by mixing said polyurethane dispersion and said water dispersible polyisocyanate.
- water-soluble organic solvent examples include alcohols and ketones.
- These monools can be used alone or in combination of two or more.
- ketones can be used alone or in combination of two or more.
- addition ratio of the additive is appropriately set according to the purpose and application.
- drying conditions are such that the drying temperature is, for example, 35 ° C. or more, preferably 40 ° C. or more, for example, 180 ° C. or less, preferably 160 ° C. or less.
- the drying time is, for example, 0.1 minutes or more, preferably 0.2 minutes or more, for example, 10 minutes or less, preferably 5 minutes or less.
- the polyurethane layer 3 made of polyurethane resin can be laminated on the substrate 2.
- the polyurethane layer 3 may be cured at 20 to 60 ° C. for about 2 to 5 days, if necessary.
- the polyurethane layer 3 in which the layered inorganic compound is dispersed can be formed by applying and drying a mixture of the polyurethane dispersion and the layered inorganic compound on the substrate 2.
- the swellable layered inorganic compound include, for example, hydrous silicates (phyllosilicate minerals, etc.), such as kaolinite group clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.), anti Golite clay mineral (antigolite, chrysotile, etc.), smectite clay mineral (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), vermiculite clay mineral (vermiculite, etc.), mica or mica Group clay minerals (mica such as muscovite and phlogopite, margarite, tetrasilic mica, teniolite, etc.), synthetic mica and the like.
- hydrous silicates phyllosilicate minerals, etc.
- kaolinite group clay minerals halloysite, kaolinite, enderite, dickite, nacrite, etc.
- These swellable layered inorganic compounds may be natural clay minerals or synthetic clay minerals.
- they can be used alone or in combination of two or more, and preferably include smectite group clay minerals (such as montmorillonite), mica group clay minerals (such as water-swelling mica), and synthetic mica, more preferably synthetic mica. Is mentioned.
- the average particle diameter of the layered inorganic compound is, for example, 50 nm or more, preferably 100 nm or more, and is usually 100 ⁇ m or less, for example, 75 ⁇ m or less, preferably 50 ⁇ m or less.
- the aspect ratio of the layered inorganic compound is, for example, 10 or more, preferably 20 or more, more preferably 100 or more, and for example, 5000 or less, preferably 4000 or less, more preferably 3000 or less. .
- the above polyurethane dispersion, the above water dispersible polyisocyanate, and the above layered inorganic compound are mixed to form a mixture.
- a hybrid coating solution is prepared. And the obtained hybrid coat liquid is apply
- a layered inorganic compound may aggregate secondarily, it is preferable to disperse or mix the layered inorganic compound in a solvent, and then perform a mechanical forced dispersion treatment in which a shearing force acts.
- the dispersion is performed by using a dispersion treatment by a homomixer, a colloid mill, a jet mill, a kneader, a bead mill, a sand mill, a ball mill, a three-roll mill, an ultrasonic dispersing apparatus, or the like.
- the application method of the hybrid coating liquid is not particularly limited, and examples thereof include the above-described known coating methods.
- the drying temperature is, for example, 35 ° C. or higher, preferably 40 ° C. or higher, for example, 180 ° C. or lower, preferably 160 ° C. or lower.
- the drying time is, for example, 0.1 minutes or more, preferably 0.2 minutes or more, for example, 10 minutes or less, preferably 5 minutes or less.
- the metal vapor deposition layer 4 is laminated on the polyurethane layer 3 by vapor deposition of metal.
- Examples of the metal include, for example, magnesium, calcium, barium, group 4 titanium, zirconium, group 13 aluminum, indium, group 14 silicon, germanium, tin, and the like, which are group 2 of the periodic table.
- Examples include aluminum, aluminum oxide, magnesium oxide, titanium oxide, aluminum oxide, indium oxide, silicon oxide, silicon oxynitride, cerium oxide, calcium oxide, tin oxide, diamond-like carbon film, or a mixture thereof.
- These metals can be used alone or in combination of two or more.
- Examples of the method for forming the metal vapor deposition layer 4 include a vacuum process.
- a vacuum evaporation method sputtering method, an ion plating method, a chemical vapor deposition method (CVD method) etc.
- a vacuum evaporation apparatus is used.
- the heating method includes an electron beam heating method, a resistance heating method, an induction heating method, and the like.
- the thickness of the metal vapor-deposited layer 4 is appropriately set according to the type of metal, and is, for example, 1 to 500 nm, preferably 5 to 200 nm, more preferably 10 to 100 nm.
- the thickness of the laminated film 1 obtained in this way is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more, and for example, 1 mm or less, preferably 0.5 mm or less.
- base material 2 / polyurethane layer 3 / metal vapor deposition layer 4 is laminated in this order
- base material 2 is a polyolefin film
- polyurethane layer 3 specifies the above-mentioned specific group. Includes by percentage.
- the polyurethane layer 3 tends to have a high density of polar groups. Therefore, the laminated film 1 is excellent in adhesive strength between the base material 2, the polyurethane layer 3 and the metal vapor deposition layer 4.
- such a laminated film 1 preferably includes a polyurethane layer 3 between the base material 2 made of a heat-sealable plastic film and the metal vapor-deposited layer 4.
- the polyurethane layer 3 particularly preferably contains a polyisocyanate component containing xylylene diisocyanate and / or hydrogenated xylylene diisocyanate, a diol having 2 to 6 carbon atoms, and a hydrophilic group.
- a polyisocyanate component containing xylylene diisocyanate and / or hydrogenated xylylene diisocyanate a diol having 2 to 6 carbon atoms
- a hydrophilic group Contains an isocyanate group-terminated prepolymer obtained by reaction with a polyol component containing an active hydrogen group-containing compound, a polyurethane dispersion containing a polyurethane resin obtained by reaction with a chain extender, and a water-dispersible polyisocyanate
- the coating liquid to be applied is obtained by applying to the substrate 2 and drying.
- the above laminated film 1 can be produced efficiently.
- the oxygen permeability of the laminated film 1 is, for example, 4 cc / m 2 / day / atm or less, preferably 3 cc / m 2 / day / atm or less, more preferably 2.5 cc / m 2 / day / atm or less, More preferably, it is 2.0 cc / m 2 / day / atm or less.
- the laminated film 1 is excellent not only in gas barrier properties but also in interlayer adhesion in each layer of the base material 2, the polyurethane layer 3 and the metal vapor deposition layer 4, that is, in each layer from the base material 2 to the metal vapor deposition layer 4. It has excellent adhesion (adhesive strength) and tends to be a stable laminate.
- the laminated film 1 is suitably used in packaging materials that require gas barrier properties, specifically, packaging materials such as pharmaceuticals, food packaging materials, optical films, industrial films, etc. Are preferably used.
- Such a food packaging material includes the above laminated film, it has excellent interlaminar adhesion in each of the base material 2, the polyurethane layer 3 and the metal vapor deposition layer 4, and tends to form a stable laminate, The adhesiveness (adhesive strength) from the base material 2 to the metal vapor deposition layer 4 is excellent, and further, the gas barrier property is also excellent.
- Synthesis Example 1 (Synthesis of polyurethane dispersion 1 (PUD1)) Takenate 500 (1,3-xylylene diisocyanate, m-XDI, manufactured by Mitsui Chemicals, Inc.) 143.2g, VestanatH 12 MDI (4,4'- methylenebis (cyclohexyl isocyanate), H 12 MDI, manufactured by Evonik) 25.0 g , 29.2 g of ethylene glycol, 2.7 g of trimethylolpropane, 14.8 g of dimethylolpropionic acid, and 121.6 g of methyl ethyl ketone as a solvent, and NCO% is reduced to 6.11% or less at 65 to 70 ° C. in a nitrogen atmosphere. It was made to react until it became, and the transparent isocyanate group terminal prepolymer reaction liquid was obtained.
- PID1 polyurethane dispersion 1
- reaction solution was dispersed in 838.0 g of ion exchange water with homodisper, and an aqueous amine solution in which 24.2 g of 2-((2-aminoethyl) amino) ethanol was dissolved in 48.4 g of ion exchange water was added. And a chain extension reaction was performed.
- the obtained PUD 1 had a pH of 8.6, a viscosity of 15 mPa ⁇ s (25 ° C.), and an average particle size measured by Coulter Counter N5 (manufactured by Beckman) was 60 nm.
- the total urethane group concentration and urea group concentration by charge calculation was 39.6% by mass.
- Synthesis Example 2 (Synthesis of polyurethane dispersion 2 (PUD2)) Takenate 500 (1,3-xylylene diisocyanate, m-XDI, Mitsui Chemicals) 54.2 g, Takenate 600 (1,3-bis (isocyanatomethyl) cyclohexane, H 6 XDI, Mitsui Chemicals) 111. 9 g, ethylene glycol 28.7 g, glycerol 1.9 g, dimethylolpropionic acid 16.6 g and methyl ethyl ketone 96.7 g as a solvent are mixed, and NCO% is 6.70% or less at 65 to 70 ° C. in a nitrogen atmosphere. To obtain a transparent isocyanate group-terminated prepolymer reaction solution.
- PID2 polyurethane dispersion 2
- reaction solution was cooled to 40 ° C., and then neutralized with 12.4 g of triethylamine.
- reaction solution was dispersed in 837.5 g of ion exchange water with a homodisper, and an aqueous amine solution in which 24.4 g of 2-((2-aminoethyl) amino) ethanol was dissolved in 48.9 g of ion exchange water was added. And a chain extension reaction was performed.
- the obtained PUD 2 had a pH of 8.8, a viscosity of 15 mPa ⁇ s (25 ° C.), and an average particle size measured by Coulter Counter N5 (Beckman) was 42 nm.
- the total urethane group concentration and urea group concentration calculated by preparation was 40.0% by mass.
- Synthesis Example 3 (Synthesis of polyurethane dispersion 3 (PUD3)) Takenate 500 (1,3-xylylene diisocyanate, m-XDI, manufactured by Mitsui Chemicals) 112.1 g, Vestanat H12MDI (4,4′-methylenebis (cyclohexyl isocyanate), H 12 MDI, manufactured by Evonik) 19.5 g, ethylene 11.9 g of glycol, 2.1 g of trimethylolpropane, DIOL400 (polypropylene glycol, number average molecular weight 400, manufactured by Mitsui Chemicals) 57.4 g, 16.1 g of dimethylolpropionic acid and 113.8 g of methyl ethyl ketone as a solvent are mixed, and nitrogen is mixed. The reaction was carried out at 65 to 70 ° C. in an atmosphere until the NCO% was 4.83% or less, thereby obtaining a transparent isocyanate group-terminated prepolymer reaction liquid
- reaction solution was cooled to 40 ° C., and then neutralized with 12.0 g of triethylamine.
- reaction solution was dispersed in 848.5 g of ion exchange water with a homodisper, and an aqueous amine solution in which 18.9 g of 2-((2-aminoethyl) amino) ethanol was dissolved in 37.9 g of ion exchange water was added. And a chain extension reaction was performed.
- the obtained PUD 3 had a pH of 8.7, a viscosity of 11 mPa ⁇ s (25 ° C.), and an average particle size of 65 nm as measured by Coulter Counter N5 (manufactured by Beckman).
- the total urethane group concentration and urea group concentration by charge calculation was 31.0% by mass.
- Synthesis Example 4 (Synthesis of polyurethane dispersion 4 (PUD4)) Takenate 500 (1,3-xylylene diisocyanate, m-XDI, manufactured by Mitsui Chemicals) 143.9 g, Vestanat H12MDI (4,4′-methylenebis (cyclohexyl isocyanate), H 12 MDI, manufactured by Evonik) 25.1 g, ethylene 28.6 g of glycol, 5.5 g of trimethylolpropane, 12.4 g of dimethylolpropionic acid and 120.9 g of methyl ethyl ketone as a solvent are mixed at 65 to 70 ° C. in a nitrogen atmosphere until NCO% is 6.14% or less. Reaction was performed to obtain a transparent isocyanate group-terminated prepolymer reaction solution.
- PID4 polyurethane dispersion 4
- reaction solution was cooled to 40 ° C., and then neutralized with 9.2 g of triethylamine.
- reaction solution was dispersed in 839.7 g of ion exchange water with a homodisper, and an aqueous amine solution in which 23.3 g of 2-((2-aminoethyl) amino) ethanol was dissolved in 46.7 g of ion exchange water was added. did.
- N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to cause a chain extension reaction.
- the obtained PUD 4 had a pH of 8.6, a viscosity of 14 mPa ⁇ s (25 ° C.), and an average particle size measured by Coulter Counter N5 (manufactured by Beckman) was 55 nm.
- the total urethane group concentration and urea group concentration by charge calculation was 39.8% by mass.
- Synthesis Example 5 (Synthesis of polyurethane dispersion 5 (PUD5)) Takenate 500 (1,3-xylylene diisocyanate, m-XDI, manufactured by Mitsui Chemicals) 98.1 g, Takenate 600 (1,3-bis (isocyanatomethyl) cyclohexane, H 6 XDI, manufactured by Mitsui Chemicals) 67. 5 g, 30.8 g of ethylene glycol, 16.7 g of dimethylolpropionic acid and 121.4 g of methyl ethyl ketone as a solvent were mixed and reacted at 65 to 70 ° C. in a nitrogen atmosphere until the NCO% was 6.24% or less. An isocyanate group-terminated prepolymer reaction solution was obtained.
- reaction solution was cooled to 40 ° C., and then neutralized with 12.4 g of triethylamine.
- reaction solution was dispersed in 837.2 g of ion exchange water with a homodisper, and an aqueous amine solution in which 24.6 g of 2-((2-aminoethyl) amino) ethanol was dissolved in 49.1 g of ion exchange water was added. And a chain extension reaction was performed.
- reaction solution was cooled to 40 ° C., and then neutralized with 8.1 g of triethylamine.
- reaction solution was dispersed in 863.7 g of ion exchange water with a homodisper, and an amine aqueous solution in which 11.3 g of 2-((2-aminoethyl) amino) ethanol was dissolved in 22.6 g of ion exchange water was added. And a chain extension reaction was performed.
- the obtained PUD 6 had a pH of 7.8, a viscosity of 18 mPa ⁇ s (25 ° C.), and an average particle size measured by Coulter Counter N5 (manufactured by Beckman) was 50 nm.
- concentration by preparation calculation was 14.0 mass%.
- Comparative Example 3 Aluminum is vapor-deposited on the corona discharge-treated surface of the unstretched polypropylene film in the same manner as in Example 1, and then the coating liquid A is applied to the aluminum vapor-deposited surface using a bar coater so that the dry thickness is 0.5 g / m 2. Overcoated.
- Comparative Example 4 A laminate was obtained in the same manner as in Comparative Example 3 except that the coating liquid G was used.
- Comparative Example 7 A laminated body was obtained in the same manner as in Comparative Example 1 except that a low-density polyethylene film (LLDPE film, manufactured by Mitsui Chemicals, Inc., trade name: TUXHC, thickness: 60 ⁇ m) was used instead of the unstretched polypropylene film.
- LLDPE film low-density polyethylene film
- TUXHC thickness: 60 ⁇ m
- Comparative Example 8 A laminate was obtained in the same manner as in Example 2 except that the coating liquid I was used in place of the coating liquid A.
- Example 11 A laminate was obtained in the same manner as in Example 1 except that a biaxially stretched polypropylene film (pyrene P-2161, thickness 20 ⁇ m, manufactured by Toyobo Co., Ltd.) was used instead of the unstretched polypropylene film.
- a biaxially stretched polypropylene film pyrene P-2161, thickness 20 ⁇ m, manufactured by Toyobo Co., Ltd.
- Comparative Example 9 A laminate was obtained in the same manner as in Example 11 except that the coating liquid G was used instead of the coating liquid A.
- the oxygen permeability of the laminate was measured with an oxygen permeability measuring device (MOCON, OX-TRAN 2/20) under the conditions of 20 ° C. and relative humidity 80% (80% RH).
- the oxygen permeation amount was measured as the permeation amount per 1 m 2 , 1 day, and 1 atmosphere.
- PET film manufactured by Toyobo Co., Ltd., trade name E5102, thickness 12 ⁇ m
- the laminate strength was measured by a T-shaped peel test (15 mm width) based on JIS K 6854 (1999).
- CPP Unstretched polypropylene film, Tosero CP RXC-22, CPP film, # 60, LLDPE manufactured by Mitsui Chemicals, Inc .: Low density polyethylene film, LLDPE film, manufactured by Mitsui Chemicals, Inc., trade name: TUXHC, thickness: 60 ⁇ m
- OPP Biaxially oriented polypropylene film, pyrene P-2161, thickness 20 ⁇ m, manufactured by Toyobo Co., Ltd.
- ⁇ Discussion> According to the laminated body of each Example applicable to the structure of this invention, it is confirmed that it is excellent in gas-barrier property and laminate strength rather than the laminated body of each comparative example which does not correspond to the structure of this invention.
- each laminate is excellent in gas barrier properties and laminate strength regardless of the type of base material. Was confirmed.
- the laminate of Comparative Example 6 was inferior in laminate strength and the like because the coating liquid was different even if the type of the base material was the same as in Example 1.
- the laminate obtained in Comparative Example 4 had a low laminate strength. This is presumed to be the influence of the pinholes and cracks generated in the metal deposition layer and the coating liquid G.
- the laminated body of the present invention, the food packaging material provided with the laminated body, and the production method of the laminated body are packaging materials that require gas barrier properties such as packaging materials such as pharmaceuticals, food packaging materials, optical films, and industrial films. It is preferably used in the material field, and particularly preferably used in the food packaging material field.
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Abstract
Description
(A)キシリレン基および/または水添キシリレン基:10質量%以上45質量%以下
(B)炭素数2~6のアルキレン基:0.5質量%以上25質量%以下
(C)ポリアルキレンオキシド基:0.5質量%以上10質量%以下
(但し、ポリウレタン層全体が100質量%である。)
本発明[7]は、前記ポリウレタン層が、さらに、下記の基を下記割合で含む、上記[6]に記載の積層体を含んでいる。
(D)イオン性基を含有するアルキレン基、および/または、イオン性基を含有するアリーレン基:1質量%以上25質量%以下
本発明[8]は、前記ポリウレタン層が、さらに、下記の基を下記割合で含む、上記[6]または[7]に記載の積層体を含んでいる。
(E)アミノ基骨格を有するアルキレン基、アミノ基骨格を有するアリーレン基、チオール基骨格を有するアルキレン基、および、チオール基骨格を有するアリーレン基からなる群から選択される少なくとも1つの基:1質量%以上25質量%以下
本発明[9]は、上記[6]~[8]のいずれか一項に記載の積層体を備える、食品包装材料を含んでいる。
(A)キシリレン基および/または水添キシリレン基
(B)炭素数2~6のアルキレン基
(C)ポリアルキレンオキシド基
(D)イオン性基を含有するアルキレン基、および/または、イオン性基を含有するアリーレン基
(E)アミノ基骨格を有するアルキレン基、アミノ基骨格を有するアリーレン基、チオール基骨格を有するアルキレン基、および、チオール基骨格を有するアリーレン基からなる群から選択される少なくとも1つの基
(A)キシリレン基および/または水添キシリレン基は、好ましくは、ポリウレタン層3の原料として、キシリレンジイソシアネート(後述)および/または水添キシリレンジイソシアネート(後述)が用いられることにより、ポリウレタン層3に導入される。
タケネート500(1,3-キシリレンジイソシアネート、m-XDI、三井化学社製)143.2g、VestanatH12MDI(4,4’-メチレンビス(シクロヘキシルイソシアネート)、H12MDI、エボニック社製)25.0g、エチレングリコール29.2g、トリメチロールプロパン2.7g、ジメチロールプロピオン酸14.8gおよび溶剤としてメチルエチルケトン121.6gを混合し、窒素雰囲気下65~70℃で、NCO%が6.11%以下になるまで反応させ、透明なイソシアネート基末端プレポリマー反応液を得た。
タケネート500(1,3-キシリレンジイソシアネート、m-XDI、三井化学社製)54.2g、タケネート600(1,3-ビス(イソシアナトメチル)シクロヘキサン、H6XDI、三井化学社製)111.9g、エチレングリコール28.7g、グリセリン1.9g、ジメチロールプロピオン酸16.6gおよび溶剤としてメチルエチルケトン96.7gを混合し、窒素雰囲気下65~70℃で、NCO%が6.70%以下になるまで反応させ、透明なイソシアネート基末端プレポリマー反応液を得た。
タケネート500(1,3-キシリレンジイソシアネート、m-XDI、三井化学社製)112.1g、VestanatH12MDI(4,4’-メチレンビス(シクロヘキシルイソシアネート)、H12MDI、エボニック社製)19.5g、エチレングリコール11.9g、トリメチロールプロパン2.1g、DIOL400(ポリプロピレングリコール、数平均分子量400、三井化学社製)57.4g、ジメチロールプロピオン酸16.1gおよび溶剤としてメチルエチルケトン113.8gを混合し、窒素雰囲気下65~70℃で、NCO%が4.83%以下になるまで反応させ、透明なイソシアネート基末端プレポリマー反応液を得た。
タケネート500(1,3-キシリレンジイソシアネート、m-XDI、三井化学社製)143.9g、VestanatH12MDI(4,4’-メチレンビス(シクロヘキシルイソシアネート)、H12MDI、エボニック社製)25.1g、エチレングリコール28.6g、トリメチロールプロパン5.5g、ジメチロールプロピオン酸12.4gおよび溶剤としてメチルエチルケトン120.9gを混合し、窒素雰囲気下65~70℃で、NCO%が6.14%以下になるまで反応させ、透明なイソシアネート基末端プレポリマー反応液を得た。
タケネート500(1,3-キシリレンジイソシアネート、m-XDI、三井化学社製)98.1g、タケネート600(1,3-ビス(イソシアナトメチル)シクロヘキサン、H6XDI、三井化学社製)67.5g、エチレングリコール30.8g、ジメチロールプロピオン酸16.7gおよび溶剤としてメチルエチルケトン121.4gを混合し、窒素雰囲気下65~70℃で、NCO%が6.24%以下になるまで反応させ、透明なイソシアネート基末端プレポリマー反応液を得た。
VestanatIPDI(3-イソシアナトメチル-3,3,5-トリメチルシクロヘキシルイソシアネート、IPDI、エボニック社製)67.7g、タケラックU-5620(数平均分子量2000のポリエステルポリオール、三井化学社製)146.6g、トリエチレングリコール5.5g、ジメチロールプロピオン酸10.8gおよび溶剤としてアセトニトリル79.6gを混合し、触媒としてオクチル酸錫(スタノクト、エーピーアイコーポレーション社製)0.03g添加し、窒素雰囲気下65~70℃で、NCO%が3.10%以下になるまで反応させ、透明なイソシアネート基末端プレポリマー反応液を得た。
m-XDI:タケネート500、1,3-キシリレンジイソシアネート、m-XDI、三井化学社製
H6XDI:タケネート600、1,3-ビス(イソシアナトメチル)シクロヘキサン、1,3-H6XDI、三井化学社製
H12MDI:VestanatH12MDI、4,4’-メチレンビス(シクロヘキシルイソシアネート、エボニック社製
IPDI:VestanatIPDI、イソホロンジイソシアネート、IPDI、エボニック社製
PP440:DIOL400、ポリオキシプロピレンエーテルグリコール、数平均分子量400、三井化学社製
U-5620:タケラックU-5620、数平均分子量2000のポリエステルポリオール、三井化学社製
MEK:メチルエチルケトン
TEA:トリエチルアミン
KBM-603:商品名、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、信越化学社製
配合例1(コート液Aの調製)
56.43gのイオン交換水に、15gの2-プロパノールを添加し、マグネチックスターラーにて10分間混合後、合成例1で得られた27.43gのPUD1を徐々に添加し、10分混合した。次いで、1.14gのタケネートWD-725(水分散性ポリイソシアネート、三井化学社製)を添加し、さらに20分混合してコート液Aを調製した。このコート液(コート液)中のウレタン樹脂と水分散性ポリイソシアネートの重量比は6/1である。
表2に示す配合処方とした以外は、配合例1と同様の手順にて、コート液B~E、H、J~Mを調製した。
54.5gのイオン交換水に、15gの2-プロパノールを添加し、マグネチックスターラーにて10分間混合後、合成例1で調製した30.0gのPUD1を徐々に添加し、10分混合した。次いで、0.5gの3-グリシドキシプロピルトリメトキシシラン(KBM-403、信越化学社製)を添加し、さらに20分混合してコート液Fを調製した。
53.0gのイオン交換水に、15gの2-プロパノールを添加し、マグネチックスターラーにて10分間混合後、合成例1で調製した32.0gのPUD1を徐々に添加し、10分混合してコート液Gを調製した。
55.30のイオン交換水に、15gの2-プロパノールを添加し、マグネチックスターラーにて10分間混合後、合成例1で調製した25.8gのPUD1を徐々に添加し、10分混合した。次いで、3.90gのカルボジライトV-02(水分散性カルボジイミド、日清紡ケミカル社製)を添加し、さらに20分混合し、コート液Iを調製した。
カルボジライトV-02:水分散性カルボジイミド(カルボジイミド系硬化剤)、日清紡ケミカル社製
KBM-403:3-グリシドキシプロピルトリメトキシシラン(エポキシシラン系硬化剤)、信越化学社製
成分分析
コート液の固形分100質量%(すなわち、ポリウレタン層)中における以下の基の含有割合を、使用した原料成分の構造および仕込み比から算出した。
(A)キシリレン基および/または水添キシリレン基
(B)炭素数2~6のアルキレン基
(C)ポリアルキレンオキシド基
(D)イオン性基を含有するアルキレン基、および/または、イオン性基を含有するアリーレン基
(E)アミノ基骨格を有するアルキレン基、アミノ基骨格を有するアリーレン基、チオール基骨格を有するアルキレン基、および、チオール基骨格を有するアリーレン基からなる群から選択される少なくとも1つの基
コート液の固形分中における各基の含有割合を、表3に示す。
コート液Aを、基材(シーラント層)としての未延伸ポリプロピレンフィルム(トーセロCP RXC-22(CPPフィルム)、#60、三井化学東セロ社製)のコロナ放電処理面に、乾燥厚み0.5g/m2となるようにバーコーターを用いてコーティングし、80℃に設定した乾燥オーブンに投入して1分間乾燥した。
未延伸ポリプロピレンフィルムに代えて、低密度ポリエチレンフィルム(LLDPEフィルム、三井化学東セロ社製、商品名TUXHC、厚み60μm)を用い、さらに100gのコート液Aに対し、0.2gのBYK-348(レベリング剤、BYK社製)を添加した以外は、実施例1と同様にして、積層体を形成した。
コート液Aに代えて、実施例3はコート液B、実施例4はコート液C、実施例5はコート液D、実施例6はコート液E、実施例7はコート液J、実施例8はコート液K、実施例9はコート液L、実施例10はコート液M、比較例2はコート液G、比較例5はコート液F、比較例6はコート液Hを、それぞれ用いた以外は、実施例1と同様にして、積層体を形成した。
実施例1のコート液Aを使用しなかった(すなわし、ポリウレタン層を形成しなかった)以外は、実施例1と同様にして、積層体を形成した。
未延伸ポリプロピレンフィルムのコロナ放電処理面に、実施例1と同様にしてアルミニウムを蒸着させ、次いで、コート液Aを乾燥厚み0.5g/m2となるようにバーコーターを用いてアルミニウム蒸着面にオーバーコーティングした。
コート液Gを用いた以外は、比較例3と同様にして、積層体を得た。
未延伸ポリプロピレンフィルムに代えて、低密度ポリエチレンフィルム(LLDPEフィルム、三井化学東セロ社製、商品名TUXHC、厚み60μm)を用いた以外は、比較例1と同様にして、積層体を得た。
コート液Aに代えて、コート液Iを用いた以外は、実施例2と同様にして、積層体を得た。
未延伸ポリプロピレンフィルムに代えて、二軸延伸ポリプロピレンフィルム(パイレンP-2161、厚み20μm、東洋紡社製)を用いた以外は、実施例1同様にして、積層体を得た。
コート液Aに代えて、コート液Gを用いた以外は、実施例11と同様にして、積層体を得た。
各実施例および各比較例において得られた積層体を、以下の手順にて評価した。その結果を、表4に示す。
積層体の酸素透過度を、酸素透過度測定装置(MOCON社、OX-TRAN 2/20)にて、20℃、相対湿度80%(80%RH)の条件下で測定した。
積層体のアルミニウム蒸着面に、ドライラミネート用接着剤としてタケラックA-310(三井化学社製)とタケネートA-3(三井化学社製)との混合物(タケラックA-310/タケネートA-3=10/1(質量比))を、乾燥厚み3.0g/m2となるようにバーコーターにて塗布し、ドライヤーで乾燥させた。
積層体の基材(シーラント層)面同士を、ヒートシーラー(テスター産業株式会社、TP-701-B HEAT SEAL TESTER)に装着し、圧力1.5kg/cm2、時間1秒、幅1cmの条件で、表4に示す温度条件にてヒートシールした。
CPP:未延伸ポリプロピレンフィルム、トーセロCP RXC-22、CPPフィルム、#60、三井化学東セロ社製
LLDPE:低密度ポリエチレンフィルム、LLDPEフィルム、三井化学東セロ社製、商品名TUXHC、厚み60μm
OPP:二軸延伸ポリプロピレンフィルム、パイレンP-2161、厚み20μm、東洋紡社製
<考察>
本発明の構成に該当する各実施例の積層体によれば、本発明の構成に該当しない各比較例の積層体よりも、ガスバリア性およびラミネート強度に優れることが確認される。
2 基材
3 ポリウレタン層
4 金属蒸着層
Claims (10)
- ヒートシール性プラスチックフィルムからなる基材と、前記基材に積層されるポリウレタン層と、前記ポリウレタン層に積層される金属蒸着層とを備え、
前記ポリウレタン層は、
キシリレンジイソシアネートおよび/または水添キシリレンジイソシアネートを含むポリイソシアネート成分と、炭素数2~6のジオール、および、親水性基を含有する活性水素基含有化合物を含むポリオール成分との反応により得られるイソシアネート基末端プレポリマーと、鎖伸長剤との反応により得られるポリウレタン樹脂を含有するポリウレタンディスパージョンと、
水分散性ポリイソシアネートと
を含有するコート液を、前記基材に塗布および乾燥させて得られる
ことを特徴とする、積層体。 - 前記ポリウレタンディスパージョン中の樹脂成分と、前記水分散性ポリイソシアネート中の樹脂成分との質量比(ポリウレタンディスパージョン中の樹脂成分/水分散性ポリイソシアネート中の樹脂成分)が、2/1~99/1の範囲であることを特徴とする、請求項1に記載の積層体。
- 前記基材が、未延伸ポリオレフィンフィルムであることを特徴とする、請求項1に記載の積層体。
- 前記金属蒸着層が、アルミニウム層であることを特徴とする、請求項1に記載の積層体。
- 請求項1に記載の積層体を備えることを特徴とする、食品包装材料。
- 基材/ポリウレタン層/金属蒸着層がこの順に積層されており、
前記基材はポリオレフィンフィルムであり、
前記ポリウレタン層が、下記の基を下記割合で含むことを特徴とする、積層体。
(A)キシリレン基および/または水添キシリレン基:10質量%以上45質量%以下
(B)炭素数2~6のアルキレン基:0.5質量%以上25質量%以下
(C)ポリアルキレンオキシド基:0.5質量%以上10質量%以下
(但し、ポリウレタン層全体が100質量%である。) - 前記ポリウレタン層が、さらに、下記の基を下記割合で含むことを特徴とする、請求項6に記載の積層体。
(D)イオン性基を含有するアルキレン基、および/または、イオン性基を含有するアリーレン基:1質量%以上25質量%以下 - 前記ポリウレタン層が、さらに、下記の基を下記割合で含むことを特徴とする、請求項6に記載の積層体。
(E)アミノ基骨格を有するアルキレン基、アミノ基骨格を有するアリーレン基、チオール基骨格を有するアルキレン基、および、チオール基骨格を有するアリーレン基からなる群から選択される少なくとも1つの基:1質量%以上25質量%以下 - 請求項6に記載の積層体を備えることを特徴とする、食品包装材料。
- ヒートシール性プラスチックフィルムからなる基材に、ポリウレタン層を積層し、前記ポリウレタン層に金属蒸着層を積層し、積層体を得る積層体の製造方法であって、
前記ポリウレタン層の積層において、
キシリレンジイソシアネートおよび/または水添キシリレンジイソシアネートを含むポリイソシアネート成分と、炭素数2~6のジオール、および、親水性基を含有する活性水素基含有化合物を含むポリオール成分との反応により得られるイソシアネート基末端プレポリマーと、鎖伸長剤との反応により得られるポリウレタン樹脂を含有するポリウレタンディスパージョンと、
水分散性ポリイソシアネートと
を含有するコート液を、前記基材に塗布および乾燥する
ことを特徴とする、積層体の製造方法。
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