WO2024157983A1 - 積層体 - Google Patents

積層体 Download PDF

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Publication number
WO2024157983A1
WO2024157983A1 PCT/JP2024/001891 JP2024001891W WO2024157983A1 WO 2024157983 A1 WO2024157983 A1 WO 2024157983A1 JP 2024001891 W JP2024001891 W JP 2024001891W WO 2024157983 A1 WO2024157983 A1 WO 2024157983A1
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WO
WIPO (PCT)
Prior art keywords
polyurethane
mass
polyurethane resin
layer
less
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/JP2024/001891
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
知紀 杉原
千佳子 甲田
俊彦 中川
和幸 福田
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 KR1020257023450A priority Critical patent/KR20250125390A/ko
Priority to CN202480007542.3A priority patent/CN120548252A/zh
Priority to JP2024573199A priority patent/JPWO2024157983A1/ja
Priority to EP24747310.1A priority patent/EP4656382A1/en
Publication of WO2024157983A1 publication Critical patent/WO2024157983A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C09D7/63—Additives non-macromolecular organic
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
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    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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    • C08K5/544—Silicon-containing compounds containing nitrogen

Definitions

  • the present invention relates to a laminate.
  • Laminates composite films with gas barrier properties have been known in the past.
  • the laminates include, for example, a substrate, an anchor coat layer disposed on one side of the substrate, and an inorganic vapor deposition layer disposed on one side of the anchor coat layer.
  • a polyurethane layer is known as an anchor coat layer for a laminate.
  • the polyurethane layer is formed, for example, by applying a polyurethane dispersion to a substrate and drying it.
  • the polyurethane dispersion is, for example, the following polyurethane dispersion.
  • This polyurethane dispersion is an aqueous dispersion of polyurethane resin.
  • the polyurethane resin is a reaction product of an isocyanate-terminated prepolymer and a chain extender.
  • the isocyanate-terminated prepolymer contains a reaction product of a polyisocyanate component containing xylylene diisocyanate, a short-chain diol having 2 to 6 carbon atoms, and an active hydrogen group-containing component containing an active hydrogen group-containing compound containing a hydrophilic group.
  • the chain extender contains ethylenediamine.
  • the ratio of ethylenediamine to the total amount of the chain extender is 25 mol% or more.
  • the polyurethane dispersion is applied to a substrate and dried to form a gas barrier coating material. Furthermore, aluminum is vapor-deposited on the gas barrier coating material to form an inorganic vapor deposition layer. This produces a laminate (see, for example, Patent Document 1 (Example 15)).
  • the substrate contains a polyolefin resin.
  • the adhesion between the substrate and the gas barrier coating material may not be sufficient.
  • the laminate is required to have excellent adhesion.
  • the laminate is required to maintain excellent adhesion even after a moist heat (retort) test.
  • the substrate when the substrate contains a polyolefin resin, the substrate may thermally expand in a moist and hot (retort) environment.
  • the gas barrier coating material and the inorganic vapor deposition layer may follow the expansion of the substrate, causing damage to the inorganic vapor deposition layer.
  • the laminate described above is required to have improved moist and heat resistance (retort resistance).
  • the present invention is a laminate with excellent adhesion and moisture and heat resistance.
  • the present invention [1] includes a laminate comprising a polyolefin substrate, a polyurethane layer disposed on the polyolefin substrate, and an inorganic vapor deposition layer disposed on the polyurethane layer, wherein the polyurethane layer has a thermal expansion coefficient of 150 ⁇ 10 ⁇ 5 K ⁇ 1 or less, measured in a temperature range of 90° C. to 120° C.
  • the present invention [2] includes the laminate described in [1] above, in which the polyurethane layer includes a dried polyurethane dispersion, and the polyurethane dispersion includes a polyurethane resin.
  • the present invention [3] includes the laminate described in [2] above, in which the polyurethane resin contains ester groups and the molar amount (mmol) of the ester groups is 0.5 mmol/g or more and 6.0 mmol/g or less relative to the mass (g) of the polyurethane resin.
  • the present invention [4] includes the laminate described in [3] above, in which the polyurethane resin contains an aromatic ring, and the content of the aromatic ring is 0.01% by mass or more and 30% by mass or less relative to the total amount of the polyurethane resin.
  • the present invention [5] includes the laminate described in any one of [2] to [4] above, in which the polyurethane resin includes a reaction product of an isocyanate-terminated prepolymer and a chain extender, and the isocyanate-terminated prepolymer includes a reaction product of a polyisocyanate component, a high molecular weight polyol including a polyester polyol, a low molecular weight polyol, and a carboxy group-containing polyol.
  • the present invention [6] includes the laminate described in any one of the above [2] to [5], in which the polyurethane dispersion includes a crosslinking agent, and the crosslinking agent includes at least one selected from the group consisting of an epoxy crosslinking agent, a carbodiimide crosslinking agent, and an isocyanate crosslinking agent.
  • the present invention [7] includes the laminate described in any one of the above [2] to [6], in which the raw material for the polyurethane resin contains a silane coupling agent, and the content of the silane coupling agent is 0.01% by mass or more and 20% by mass or less relative to the total amount of the raw material for the polyurethane resin.
  • the present invention [8] includes the laminate described in [5] above, in which the chain extender includes a silane coupling agent containing an amino group, and/or the polyurethane dispersion includes a crosslinking agent, the crosslinking agent includes an epoxy crosslinking agent, and the epoxy crosslinking agent includes a silane coupling agent containing an epoxy group.
  • a polyurethane layer is disposed on a polyolefin substrate.
  • an inorganic vapor deposition layer is disposed on the polyurethane layer.
  • the polyurethane layer contains a dried polyurethane dispersion.
  • the polyurethane dispersion contains a polyurethane resin.
  • the polyurethane resin contains a reaction product of an isocyanate-terminated prepolymer and a chain extender.
  • the polyurethane layer has a coefficient of thermal expansion measured in a temperature range of 90°C to 120°C that is equal to or less than a predetermined value. Therefore, the polyurethane layer has excellent adhesion and resistance to moist heat.
  • the polyurethane layer if the polyurethane layer is disposed on a polyolefin substrate, the polyurethane layer suppresses the thermal expansion of the polyolefin substrate. Therefore, damage to the inorganic vapor deposition layer is suppressed.
  • the laminate has excellent adhesion and resistance to moisture and heat.
  • FIG. 1 is a schematic diagram showing an embodiment of the laminate of the present invention.
  • FIG. 2 is a schematic diagram of a laminate film including the laminate of FIG.
  • laminate 1 is a composite film having a plurality of layers.
  • Laminate 1 includes a polyolefin substrate 2 (substrate layer), a polyurethane layer 3 disposed on polyolefin substrate 2, and an inorganic vapor deposition layer 4 disposed on polyurethane layer 3.
  • polyolefin substrate 2, polyurethane layer 3, and inorganic vapor deposition layer 4 are laminated in this order along the thickness direction of laminate 1.
  • the polyolefin substrate 2 is a substrate containing a polyolefin resin.
  • the polyolefin substrate 2 is a substrate made of a polyolefin resin.
  • a substrate made of a polyolefin resin can achieve mono-materialization (single material) of the laminate film 10 (see FIG. 2) described later, and can improve recyclability.
  • polyolefin resins examples include polyethylene, polypropylene, and ethylene-propylene copolymers (random/block). These can be used alone or in combination of two or more.
  • a preferred example of the polyolefin resin is polypropylene.
  • a preferred example of the polyolefin substrate 2 is a polypropylene substrate. More specifically, a preferred example of the polyolefin substrate 2 is a polyolefin film, more preferably a polypropylene film.
  • substrates include films, sheets, bottles, and cups, and preferably films. Examples of substrates include non-stretched substrates, uniaxially stretched substrates, and biaxially stretched substrates, and preferably biaxially stretched substrates.
  • the polyolefin substrate 2 may be a single layer or multiple layers.
  • the polyolefin substrate 2 may be surface-treated. Examples of surface treatments include corona discharge treatment.
  • the shape of the polyolefin substrate 2 may be, for example, a sheet, a bottle, or a cup.
  • the thickness of the polyolefin substrate 2 is, for example, 3 ⁇ m or more, preferably 5 ⁇ m or more.
  • the thickness of the polyolefin substrate 2 is, for example, 500 ⁇ m or less, preferably 200 ⁇ m or less.
  • the polyurethane layer 3 is a resin layer containing a polyurethane resin.
  • the polyurethane layer 3 is disposed between the polyolefin substrate 2 and the inorganic vapor deposition layer 4 so as to be in contact with the polyolefin substrate 2. That is, in Fig. 1, the polyurethane layer 3 is an anchor coat layer.
  • the polyurethane layer 3 contains a dried polyurethane dispersion. More specifically, the polyurethane layer 3 is obtained by applying an anchor coating agent (described below) containing a polyurethane dispersion to one side of the polyolefin substrate 2 and drying it.
  • an anchor coating agent described below
  • the polyurethane dispersion contains a polyurethane resin. More specifically, the polyurethane dispersion is an aqueous dispersion of a polyurethane resin.
  • An example of the polyurethane resin is a polyurethane resin that has gas barrier properties. Gas barrier properties are the property of reducing oxygen permeability.
  • the polyurethane resin contains a reaction product of an isocyanate-terminated prepolymer and a chain extender.
  • the isocyanate-terminated prepolymer is obtained by reacting a polyisocyanate component with an active hydrogen group-containing component.
  • the isocyanate-terminated prepolymer is the primary reaction product between the polyisocyanate component and the active hydrogen group-containing component
  • the polyurethane resin is the secondary reaction product between the isocyanate-terminated prepolymer and the chain extender.
  • Polyurethane resin and polyurethane dispersion can be obtained, for example, by the following method.
  • an isocyanate-terminated prepolymer is synthesized.
  • the isocyanate-terminated prepolymer is a polyurethane prepolymer that has two or more free isocyanate groups at the molecular end.
  • the isocyanate-terminated prepolymer is obtained by reacting a polyisocyanate component with an active hydrogen group-containing component.
  • polyisocyanate component examples include aromatic polyisocyanates, araliphatic polyisocyanates, and aliphatic polyisocyanates.
  • Aromatic polyisocyanates include, for example, aromatic polyisocyanate monomers and aromatic polyisocyanate derivatives.
  • Aromatic polyisocyanate monomers include, for example, aromatic diisocyanates.
  • Aromatic diisocyanates include, for example, tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), and diphenylmethane diisocyanate (MDI).
  • Aromatic polyisocyanate derivatives include modified products obtained by modifying aromatic polyisocyanate monomers by known methods.
  • modified products include, for example, polymers, allophanate modified products, polyol modified products, 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 types.
  • Examples of the araliphatic polyisocyanate include araliphatic polyisocyanate monomers and araliphatic polyisocyanate derivatives.
  • Examples of the araliphatic polyisocyanate monomers include araliphatic diisocyanates.
  • Examples of the araliphatic diisocyanates include xylylene diisocyanate (XDI) and tetramethyl xylylene diisocyanate (TMXDI).
  • Examples of the araliphatic polyisocyanate derivatives include the above-mentioned modified products of the araliphatic polyisocyanate monomers. These can be used alone or in combination of two or more types.
  • aliphatic polyisocyanates examples include linear aliphatic polyisocyanates and alicyclic polyisocyanates.
  • Examples of the chain aliphatic polyisocyanate include chain aliphatic polyisocyanate monomers and chain aliphatic polyisocyanate derivatives.
  • Examples of the chain aliphatic polyisocyanate monomers include chain aliphatic diisocyanates.
  • Examples of the chain aliphatic diisocyanates include ethylene diisocyanate, butylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), and 1,6-hexamethylene diisocyanate (HDI).
  • Examples of the chain aliphatic polyisocyanate derivatives include the above-mentioned modified chain aliphatic polyisocyanate monomers. These can be used alone or in combination of two or more types.
  • Examples of the alicyclic polyisocyanate include alicyclic polyisocyanate monomers and alicyclic polyisocyanate derivatives.
  • Examples of the alicyclic polyisocyanate monomer include alicyclic diisocyanates.
  • Examples of the alicyclic diisocyanates include bis(isocyanatomethyl)cyclohexane (H 6 XDI), methylene bis(cyclohexyl isocyanate) (H 12 MDI), isophorodiisocyanate (IPDI) and norbornane diisocyanate (NBDI).
  • Examples of the alicyclic polyisocyanate derivative include the above-mentioned modified products of the alicyclic polyisocyanate monomers. These can be used alone or in combination of two or more types.
  • the polyisocyanate component is preferably an aromatic polyisocyanate and an alicyclic polyisocyanate. That is, the polyisocyanate component preferably contains an aromatic polyisocyanate and/or an alicyclic polyisocyanate. From the viewpoint of gas barrier properties, the polyisocyanate component is more preferably an alicyclic polyisocyanate, even more preferably an alicyclic diisocyanate, and particularly preferably methylene bis(cyclohexyl isocyanate).
  • the active hydrogen group-containing component contains multiple active hydrogen groups in one molecule.
  • active hydrogen groups include hydroxyl groups and amino groups. More specifically, examples of active hydrogen group-containing components include polyols and polyamines, and preferably polyols.
  • polyols examples include high molecular weight polyols, low molecular weight polyols, and ionic group-containing polyols.
  • High molecular weight polyols are organic compounds that have two or more hydroxyl groups in the molecule, do not have ionic groups (described below), and have a relatively high molecular weight.
  • a relatively high molecular weight indicates that the number average molecular weight (Mn) is 650 or more, preferably 700 or more.
  • the high molecular weight polyol contains, for example, a polyester polyol.
  • the polyester polyol include condensation polyester polyols and ring-opening polyester polyols.
  • the polyester polyol is preferably a condensation polyester polyol.
  • Condensation polyester polyols are obtained by the condensation reaction (esterification reaction) of polycarboxylic acids and polyhydric alcohols.
  • polycarboxylic acids examples include polycarboxylic acids containing aromatic rings (hereinafter, aromatic ring-containing polycarboxylic acids) and polycarboxylic acids not containing aromatic rings (hereinafter, aromatic ring-free polycarboxylic acids).
  • polycarboxylic acids containing aromatic rings include phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, their acid anhydrides, their dialkyl esters, and their acid halides.
  • polycarboxylic acids not containing aromatic rings examples include adipic acid, sebacic acid, azelaic acid, their acid anhydrides, their dialkyl esters, and their acid halides. These may be used alone or in combination of two or more.
  • polyhydric alcohols examples include polyhydric alcohols containing an aromatic ring (hereinafter, aromatic ring-containing polyhydric alcohols) and polyhydric alcohols not containing an aromatic ring (hereinafter, aromatic ring-free polyhydric alcohols).
  • aromatic ring-containing polyhydric alcohols include dihydroxydiphenyl, dihydroxytriphenyl, dihydroxybenzophenone, and hydroquinone.
  • non-aromatic ring-containing polyhydric alcohols include alkanediols having 2 to 6 carbon atoms, which will be described later, etherdiols having 2 to 6 carbon atoms, which will be described later, and alkenediols having 2 to 6 carbon atoms, which will be described later. These may be used alone or in combination of two or more types.
  • the polycarboxylic acid and the polyhydric alcohol are dehydrated and condensed by a known method to produce a condensed polyester polyol.
  • the mixing ratio of the polycarboxylic acid and the polyhydric alcohol and the reaction conditions are not particularly limited and are set appropriately.
  • the condensed polyester polyol is preferably a condensed polyester polyol containing an aromatic ring (hereinafter, aromatic ring-containing polyester polyol).
  • aromatic ring-containing polyester polyol can be obtained by the above condensation reaction, for example, when the polycarboxylic acid contains an aromatic ring-containing carboxylic acid and/or the polyhydric alcohol contains an aromatic ring-containing polyhydric alcohol.
  • the polyurethane resin and polyurethane layer 3 contain aromatic rings, as described below. This results in excellent adhesion and resistance to moist heat.
  • the high molecular weight polyol may include other high molecular weight polyols.
  • the other high molecular weight polyols are high molecular weight polyols other than polyester polyols.
  • high molecular weight polyols include, for example, polyether polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer modified polyols.
  • Other high molecular weight polyols preferably include polyether polyols and polycarbonate polyols.
  • polyether polyols include, for example, polyoxyalkylene polyols.
  • polyoxyalkylene polyols include, for example, polyoxyalkylene (C2-3) polyols and polytetramethylene ether polyols.
  • polycarbonate polyols include, for example, ring-opening polymers of ethylene carbonate using a low molecular weight polyol (described later) as an initiator. These can be used alone or in combination of two or more types.
  • the high molecular weight polyol preferably does not contain other high molecular weight polyols and is composed of a polyester polyol, more preferably a condensed polyester polyol, and even more preferably an aromatic ring-containing polyester polyol.
  • the average number of hydroxyl groups (average number of functional groups) of the high molecular weight polyol is, for example, 2 or more.
  • the average number of hydroxyl groups (average number of functional groups) of the high molecular weight polyol is, for example, 6 or less, preferably 4 or less, more preferably 3 or less, and even more preferably 2.5 or less.
  • the average number of hydroxyl groups (average number of functional groups) of the high molecular weight polyol is most preferably 2.
  • the average number of hydroxyl groups (average number of functional groups) can be calculated from the amount of raw material for the high molecular weight polyol.
  • the number average molecular weight of the high molecular weight polyol is 650 or more, preferably 700 or more, more preferably 800 or more, even more preferably 1000 or more, and particularly preferably 1500 or more.
  • the number average molecular weight of the high molecular weight polyol is, for example, 5000 or less, preferably 4000 or less, more preferably 3000 or less, and even more preferably 2500 or less.
  • the content of the high molecular weight polyol in the active hydrogen group-containing component is adjusted so that the thermal expansion coefficient of the polyurethane layer 3 falls within the range described below.
  • the content of the high molecular weight polyol in the active hydrogen group-containing component is adjusted so that the content ratio of the ester group in the polyurethane resin falls within the range described below.
  • the content of the high molecular weight polyol in the active hydrogen group-containing component is adjusted so that the content ratio of the aromatic ring in the polyurethane resin falls within the range described below.
  • the content of the high molecular weight polyol in the active hydrogen group-containing component is adjusted so that the content ratio of the silane coupling agent relative to the raw material (described below) of the polyurethane resin falls within the range described below.
  • the content of the high molecular weight polyol is, for example, 30 parts by mass or more, preferably 50 parts by mass or more, and more preferably 70 parts by mass or more, per 100 parts by mass of the total amount of the active hydrogen group-containing components.
  • the content of the high molecular weight polyol is, for example, 95 parts by mass or less, preferably 90 parts by mass or less, and more preferably 88 parts by mass or less, per 100 parts by mass of the total amount of the active hydrogen group-containing components.
  • Low molecular weight polyols are organic compounds that have two or more hydroxyl groups in the molecule, do not have ionic groups (described below), and have a relatively high molecular weight.
  • a relatively low molecular weight means that the number average molecular weight (Mn) is less than 650, preferably 600 or less, more preferably 500 or less, and even more preferably 400 or less.
  • the molecular weight of the low molecular weight polyol is less than 650, preferably 600 or less, more preferably 500 or less, and even more preferably 400 or less.
  • the molecular weight of the low molecular weight polyol is, for example, 50 or more. Note that, when the low molecular weight polyol has a molecular weight distribution, the molecular weight indicates the number average molecular weight in terms of polystyrene measured by GPC.
  • Low molecular weight polyols include, for example, short-chain diols having 2 to 6 carbon atoms and other low molecular weight polyols.
  • Short-chain diols with 2 to 6 carbon atoms have two hydroxyl groups and are organic compounds with 2 to 6 carbon atoms.
  • Examples of short-chain diols with 2 to 6 carbon atoms include alkane diols with 2 to 6 carbon atoms, ether diols with 2 to 6 carbon atoms, and alkene diols with 2 to 6 carbon atoms.
  • alkane diols having 2 to 6 carbon atoms include ethylene glycol, propylene glycol, 1,3-propane diol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentane diol, 1,6-hexane diol, neopentyl glycol, 3-methyl-1,5-pentane diol, 1,3-cyclohexane diol, and 1,4-cyclohexane diol.
  • ether diols having 2 to 6 carbon atoms include diethylene glycol, triethylene glycol, and dipropylene glycol.
  • alkene diols having 2 to 6 carbon atoms include 1,4-dihydroxy-2-butene.
  • the short-chain diol having 2 to 6 carbon atoms can be used alone or in combination of two or more kinds.
  • the short-chain diol having 2 to 6 carbon atoms is preferably an ether diol having 2 to 6 carbon atoms, more preferably triethylene glycol.
  • the content of the short-chain diol having 2 to 6 carbon atoms in the active hydrogen group-containing component is adjusted so that the thermal expansion coefficient of the polyurethane layer 3 falls within the range described below. Also, preferably, the content of the ester group in the polyurethane resin falls within the range described below. Also, preferably, the content of the short-chain diol having 2 to 6 carbon atoms in the active hydrogen group-containing component is adjusted so that the content of the aromatic ring in the polyurethane resin falls within the range described below.
  • the content of the short-chain diol having 2 to 6 carbon atoms in the active hydrogen group-containing component is adjusted so that the content of the silane coupling agent relative to the raw material (described below) of the polyurethane resin falls within the range described below.
  • the content of the short-chain diol having 2 to 6 carbon atoms is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1.0 parts by mass or more, per 100 parts by mass of the total amount of the active hydrogen group-containing components.
  • the content of the short-chain diol having 2 to 6 carbon atoms is, for example, 60 parts by mass or less, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the total amount of the active hydrogen group-containing components.
  • low molecular weight polyols are low molecular weight polyols excluding short chain diols having 2 to 6 carbon atoms.
  • Examples of other low molecular weight polyols include diols having 7 or more carbon atoms and low molecular weight polyols having a valence of 3 or more.
  • diols with 7 or more carbon atoms examples include alkane (7 to 20 carbon atoms)-1,2-diol, 2,6-dimethyl-1-octene-3,8-diol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and bisphenol A. These can be used alone or in combination of two or more types.
  • Examples of low molecular weight polyols having a hydricity of three or more include trihydric alcohols and tetrahydric alcohols.
  • Examples of trihydric alcohols 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.
  • Examples of tetrahydric alcohols include pentaerythritol and diglycerin. These can be used alone or in combination of two or more types.
  • the other low molecular weight polyols can be used alone or in combination of two or more kinds.
  • the other low molecular weight polyols are preferably trihydric or higher low molecular weight polyols, more preferably trihydric alcohols, and particularly preferably trimethylolpropane.
  • the content of the other low molecular weight polyol in the active hydrogen group-containing component is adjusted so that the thermal expansion coefficient of the polyurethane layer 3 is within the range described below.
  • the content of the other low molecular weight polyol in the active hydrogen group-containing component is adjusted so that the content ratio of the ester group in the polyurethane resin is within the range described below.
  • the content of the other low molecular weight polyol in the active hydrogen group-containing component is adjusted so that the content ratio of the aromatic ring in the polyurethane resin is within the range described below.
  • the content of the other low molecular weight polyol in the active hydrogen group-containing component is adjusted so that the content ratio of the silane coupling agent to the raw material (described below) of the polyurethane resin is within the range described below.
  • the content of the other low molecular weight polyols is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 0 parts by mass, per 100 parts by mass of the total amount of the active hydrogen group-containing components.
  • the low molecular weight polyol preferably contains only short-chain diols having 2 to 6 carbon atoms, and does not contain other low molecular weight polyols.
  • the content (total amount) of low molecular weight polyol in the active hydrogen group-containing component is adjusted so that the thermal expansion coefficient of the polyurethane layer 3 is within the range described below.
  • the content (total amount) of low molecular weight polyol in the active hydrogen group-containing component is adjusted so that the content ratio of ester groups in the polyurethane resin is within the range described below.
  • the content (total amount) of low molecular weight polyol in the active hydrogen group-containing component is adjusted so that the content ratio of aromatic rings in the polyurethane resin is within the range described below.
  • the content (total amount) of low molecular weight polyol in the active hydrogen group-containing component is adjusted so that the content ratio of silane coupling agent to the raw material of the polyurethane resin (described below) is within the range described below.
  • the content (total amount) of the low molecular weight polyol is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1.0 parts by mass or more, per 100 parts by mass of the total amount of the active hydrogen group-containing components.
  • the content (total amount) of the low molecular weight polyol is, for example, 60 parts by mass or less, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the total amount of the active hydrogen group-containing components.
  • An ionic group-containing polyol is an organic compound having two or more hydroxyl groups and one or more ionic groups in the molecule.
  • ionic groups include anionic groups and cationic groups, and preferably anionic groups. That is, examples of ionic group-containing polyols include anionic group-containing polyols and cationic group-containing polyols, and preferably anionic group-containing polyols.
  • examples of the anionic group include a carboxy group (a carboxylic acid group) and a sulfo group (a sulfonic acid group). From the viewpoint of gas barrier properties and water resistance, the anionic group is preferably a carboxy group. In other words, the anionic group-containing polyol is preferably a carboxy group-containing polyol.
  • Carboxy group-containing polyols include, for example, polyhydroxyalkanoic acids.
  • Polyhydroxyalkanoic acids include, for example, 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid (also known as dimethylolpropionic acid), 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid. These can be used alone or in combination of two or more kinds.
  • Carboxy group-containing polyols are preferably, for example, polyhydroxyalkanoic acids, and more preferably, 2,2-dimethylolpropionic acid.
  • the content of the ionic group-containing polyol in the active hydrogen group-containing component is adjusted so that the thermal expansion coefficient of the polyurethane layer 3 falls within the range described below.
  • the content of the ionic group-containing polyol in the active hydrogen group-containing component is adjusted so that the content ratio of the ester group in the polyurethane resin falls within the range described below.
  • the content of the ionic group-containing polyol in the active hydrogen group-containing component is adjusted so that the content ratio of the aromatic ring in the polyurethane resin falls within the range described below.
  • the content of the ionic group-containing polyol in the active hydrogen group-containing component is adjusted so that the content ratio of the silane coupling agent relative to the raw material (described below) of the polyurethane resin falls within the range described below.
  • the content of the ionic group-containing polyol is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of the total amount of the active hydrogen group-containing components.
  • the content of the ionic group-containing polyol is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 15 parts by mass or less, per 100 parts by mass of the total amount of the active hydrogen group-containing components.
  • the active hydrogen group-containing component preferably includes a high molecular weight polyol including polyester polyol, a low molecular weight polyol, and an ionic group-containing polyol.
  • the active hydrogen group-containing component more preferably includes a polyester polyol, a short-chain diol having 2 to 6 carbon atoms, and a carboxy group-containing polyol.
  • the isocyanate-terminated prepolymer preferably contains a reaction product of a polyisocyanate component, a high molecular weight polyol including a polyester polyol, a low molecular weight polyol, and a carboxy group-containing polyol.
  • the isocyanate-terminated prepolymer preferably contains a reaction product of an alicyclic polyisocyanate, a polyester polyol, a short-chain diol having 2 to 6 carbon atoms, and a carboxy group-containing polyol.
  • the isocyanate-terminated prepolymer is obtained by reacting the above components at a predetermined equivalent ratio.
  • the equivalent ratio is the equivalent ratio of isocyanate groups to active hydrogen groups (hydroxyl groups) (isocyanate groups/active hydrogen groups).
  • the equivalent ratio (isocyanate groups/active hydrogen groups) is, for example, greater than 1, and preferably 1.1 or greater.
  • the equivalent ratio (isocyanate groups/active hydrogen groups) is, for example, 20 or less, and preferably 10 or less.
  • polymerization methods are used in the synthesis of the isocyanate-terminated prepolymer.
  • the polymerization method include bulk polymerization and solution polymerization. From the viewpoint of adjusting the reactivity, solution polymerization is preferably used as the polymerization method.
  • bulk polymerization for example, the above components are mixed and reacted in a nitrogen atmosphere.
  • the reaction temperature is, for example, 75 to 85°C.
  • the reaction time is, for example, 1 to 20 hours.
  • solution polymerization for example, the above components are mixed and reacted in an organic solvent in a nitrogen atmosphere.
  • the reaction temperature is, for example, 20 to 80°C.
  • the reaction time is, for example, 1 to 20 hours.
  • the organic solvent may be a solvent inactive to the isocyanate group.
  • a catalyst can be added as necessary.
  • catalysts include amine catalysts and organometallic catalysts. These catalysts can be used alone or in combination of two or more types. The amount of catalyst added is appropriately set depending on the purpose and application.
  • the polymerization is terminated, for example, when the isocyanate group concentration in the reaction product reaches the range described below.
  • the unreacted polyisocyanate component can be removed by a known removal method. Examples of the removal method include distillation and extraction. This results in an isocyanate-terminated prepolymer.
  • the isocyanate group concentration of the isocyanate-terminated prepolymer is, for example, 1% by mass or more, preferably 2% by mass or more, and more preferably 4% 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 average number of functional groups of the isocyanate groups is, for example, 1.5 or more, preferably 1.9 or more, and more preferably 2.0 or more.
  • the average number of functional groups of the isocyanate groups is, for example, 3.0 or less, and preferably 2.5 or less.
  • a neutralizing agent is added to the isocyanate-terminated prepolymer to neutralize it and form a salt of the anionic groups.
  • the neutralizing agent include conventional bases.
  • Specific examples of the base include organic bases and inorganic bases.
  • Examples of organic bases include tertiary amines and secondary amines.
  • Examples of tertiary amines include trialkylamines and alkanolamines.
  • Examples of trialkylamines include trialkylamines having 1 to 4 carbon atoms. Examples of such trialkylamines include trimethylamine and triethylamine.
  • Examples of alkanolamines include dimethylethanolamine, methyldiethanolamine, triethanolamine, and triisopropanolamine.
  • Examples of secondary amines include heterocyclic amines. Examples of heterocyclic amines include morpholine.
  • Examples of inorganic bases include ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, and alkali metal carbonates.
  • Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, and lithium hydroxide.
  • Examples of alkaline earth metal hydroxides include magnesium hydroxide and calcium hydroxide.
  • Examples of alkali metal carbonates include sodium carbonate and potassium carbonate.
  • neutralizing agents can be used alone or in combination of two or more.
  • an organic base is preferably used, a tertiary amine is more preferably used, a trialkylamine is even more preferably used, and triethylamine is particularly preferably used.
  • the amount of neutralizing agent added is, for example, 0.4 equivalents or more, and preferably 0.6 equivalents or more, per equivalent of anionic group.
  • the amount of neutralizing agent added is, for example, 1.2 equivalents or less, and preferably 1.0 equivalents or less, per equivalent of anionic group.
  • the isocyanate-terminated prepolymer (primary reaction product) is then reacted with a chain extender to obtain a polyurethane resin (secondary reaction product).
  • a polyurethane dispersion can be obtained by reacting an isocyanate-terminated prepolymer with a chain extender in water.
  • the chain extender is an organic compound that has multiple active hydrogen groups and causes a chain extension reaction of the isocyanate-terminated prepolymer.
  • chain extenders include polyamines, amino alcohols, and amino silanes.
  • polyamines examples include aromatic polyamines, araliphatic polyamines, alicyclic polyamines, and aliphatic polyamines.
  • aromatic polyamines examples include 4,4'-diphenylmethanediamine and tolylenediamine.
  • araliphatic polyamines examples include 1,3-xylylenediamine and 1,4-xylylenediamine.
  • alicyclic polyamines examples include ethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (also known as isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 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-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane.
  • aliphatic polyamines examples include propylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, hydrazine, hydrazine hydrate, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminoethane, 1,2-diaminopropane, and 1,3-diaminopentane.
  • amino alcohols examples include 2-((2-aminoethyl)amino)ethanol (also known as N-(2-aminoethyl)ethanolamine) and 2-((2-aminoethyl)amino)-1-methylpropanol (also known as N-(2-aminoethyl)isopropanolamine).
  • Aminosilanes include, for example, silane coupling agents containing an amino group. More specifically, silane coupling agents containing an amino group include, for example, alkoxysilyl compounds having a primary amino group, and alkoxysilyl compounds having a primary amino group and a secondary amino group.
  • alkoxysilyl compounds having a primary amino group examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, and N-phenyl- ⁇ -aminopropyltrimethoxysilane.
  • alkoxysilyl compounds having a primary amino group and a secondary amino group examples include N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane (also known as N-2-(aminoethyl)-3-aminopropyltrimethoxysilane), N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane (also known as N-2-(aminoethyl)-3-aminopropyltriethoxysilane), N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane (also known as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane), and N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldiethoxysilane (also known as N-2-(aminoethyl)-3-aminopropylmethyldie
  • the chain extender can be used alone or in combination of two or more kinds.
  • the chain extender is preferably a polyamine or an aminosilane, more preferably an alicyclic polyamine or a silane coupling agent containing an amino group, and even more preferably ethylenediamine or N-2-(aminoethyl)-3-aminopropyltrimethoxysilane.
  • the type and amount of the chain extender are adjusted so that the thermal expansion coefficient of the polyurethane layer 3 falls within the range described below.
  • the type and amount of the chain extender are adjusted so that the content of ester groups in the polyurethane resin falls within the range described below.
  • the type and amount of the chain extender are adjusted so that the content of aromatic rings in the polyurethane resin falls within the range described below.
  • the type and amount of the chain extender are adjusted so that the content of silane coupling agent relative to the raw material for the polyurethane resin (described below) falls within the range described below.
  • the chain extender more preferably contains polyamine and aminosilane.
  • the content ratio of polyamine and the content ratio of aminosilane are appropriately set according to the purpose and application.
  • the content ratio of polyamine relative to the total amount of polyamine and aminosilane is, for example, 1 mass% or more, preferably 10 mass% or more, more preferably 20 mass% or more.
  • the content ratio of polyamine relative to the total amount of polyamine and aminosilane is, for example, 80 mass% or less, preferably 60 mass% or less, more preferably 40 mass% or less.
  • the content ratio of aminosilane relative to the total amount of polyamine and aminosilane is, for example, 20 mass% or more, preferably 40 mass% or more, more preferably 60 mass% or more. Furthermore, the content ratio of aminosilane relative to the total amount of polyamine and aminosilane is, for example, 99 mass% or less, preferably 90 mass% or less, more preferably 80 mass% or less.
  • the isocyanate-terminated prepolymer is reacted with a chain extender in water. More specifically, for example, the isocyanate-terminated prepolymer is first dispersed in water. Next, the chain extender is added to the aqueous dispersion of the isocyanate-terminated prepolymer, and the isocyanate-terminated prepolymer is chain-extended by the chain extender.
  • the method for dispersing the isocyanate-terminated prepolymer in water For example, the isocyanate-terminated prepolymer is added to water while stirring the water. In this case, the amount of water is 100 to 1,000 parts by mass per 100 parts by mass of the isocyanate-terminated prepolymer.
  • the chain extender is dropped into the water.
  • the equivalent ratio of the active hydrogen groups of the chain extender to the isocyanate groups of the isocyanate-terminated prepolymer is, for example, 0.6 to 1.2.
  • the chain extension reaction is completed, for example, at room temperature. The time until the reaction is completed is, for example, 0.1 to 10 hours.
  • the organic solvent and/or water can be removed after the reaction is completed in order to adjust the solids concentration.
  • water can be added after the reaction is completed in order to adjust the solids concentration.
  • a solvent can be added in order to adjust the solids concentration. Examples of the solvent include water, methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, and acetonitrile. These solvents can be used alone or in combination of two or more types.
  • the pH of the polyurethane dispersion is, for example, 5 or more, and preferably 6 or more.
  • the pH of the polyurethane dispersion is, for example, 11 or less, and preferably 10 or less.
  • the average particle diameter of the polyurethane dispersion is, for example, 10 nm or more, preferably 20 nm or more, and more preferably 50 nm or more.
  • the average particle diameter of the polyurethane dispersion is, for example, 500 nm or less, preferably 300 nm or less, and more preferably 200 nm or less.
  • the solid content concentration of the polyurethane dispersion 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 polyurethane dispersion is, for example, 60% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less.
  • the solid content concentration is appropriately adjusted by a known method.
  • the polyurethane dispersion may contain additives.
  • additives include fillers, alkoxysilane compounds, thickeners, antioxidants, heat stabilizers, UV absorbers, plasticizers, antistatic agents, lubricants, antiblocking agents, surfactants, dispersion stabilizers, colorants, pigments, dyes, colloidal silica, inorganic particles, inorganic oxide particles, layered inorganic compounds, leveling agents, crystal nucleating agents, and crosslinking agents.
  • additives may be used alone or in combination of two or more types.
  • a polyurethane dispersion that contains a polyurethane resin but no additives may be referred to as a primary polyurethane dispersion (primary PUD).
  • a polyurethane dispersion that contains a polyurethane resin and additives may be referred to as a secondary polyurethane dispersion (secondary PUD).
  • the secondary polyurethane dispersion preferably contains a crosslinking agent as an additive.
  • crosslinking agents include epoxy crosslinking agents, melamine crosslinking agents, carbodiimide crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, isocyanate crosslinking agents, and reactive crosslinking agents. These may be used alone or in combination of two or more types.
  • the type and amount of crosslinking agent are adjusted so that the thermal expansion coefficient of the polyurethane layer 3 falls within the range described below.
  • the type and amount of crosslinking agent are adjusted so that the content of ester groups in the polyurethane resin falls within the range described below.
  • the type and amount of crosslinking agent are adjusted so that the content of aromatic rings in the polyurethane resin falls within the range described below.
  • the type and amount of crosslinking agent are adjusted so that the content of silane coupling agent relative to the raw materials for the polyurethane resin (described below) falls within the range described below.
  • a polyurethane resin that is not crosslinked by a crosslinking agent contains a carboxy group as a hydrophilic group
  • preferred examples of the crosslinking agent include an epoxy crosslinking agent, a carbodiimide crosslinking agent, and an isocyanate crosslinking agent. That is, the crosslinking agent preferably includes at least one selected from the group consisting of an epoxy crosslinking agent, a carbodiimide crosslinking agent, and an isocyanate crosslinking agent.
  • An epoxy crosslinking agent is a compound that has an epoxy group. If the secondary polyurethane dispersion contains an epoxy crosslinking agent, a polyurethane layer 3 with excellent resistance to moist heat can be obtained.
  • Epoxy crosslinking agents include, for example, silane coupling agents containing epoxy groups.
  • Epoxy crosslinking agents include, for example, epoxy silanes.
  • Epoxy silanes include, for example, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane. These can be used alone or in combination of two or more types.
  • As epoxy silanes trialkoxysilanes are preferred, and 3-glycidoxypropyl trimethoxysilane is more preferred.
  • Epoxy crosslinkers (silane coupling agents containing epoxy groups) are available, for example, as commercially available products.
  • Commercially available epoxy crosslinkers include, for example, KBM-403 (glycidoxypropyltrimethoxysilane), KBE-403 (3-glycidoxypropyltriethoxysilane), KBM-402 (3-glycidoxypropylmethyldimethoxysilane), KBE-402 (3-glycidoxypropylmethyldiethoxysilane), and KBM-303 (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) (all manufactured by Shin-Etsu Chemical Co., Ltd.). These can be used alone or in combination of two or more types.
  • the amount of epoxy crosslinking agent added is appropriately set according to the purpose and application.
  • the epoxy group in the epoxy crosslinking agent is, for example, 0.1 mol or more, preferably 0.3 mol or more, more preferably 0.5 mol or more, and even more preferably 0.8 mol or more per 1.0 mol of carboxy group in the polyurethane resin.
  • the epoxy group in the epoxy crosslinking agent is, for example, 5.0 mol or less, preferably 3.0 mol or less, more preferably 2.1 mol or less, even more preferably 1.5 mol or less, and especially preferably 1.2 mol or less per 1.0 mol of carboxy group in the polyurethane resin.
  • the carbodiimide crosslinking agent is a compound having a carbodiimide group (carbodiimide compound). If the secondary polyurethane dispersion contains a carbodiimide crosslinking agent, a polyurethane layer 3 having excellent resistance to moist heat can be obtained.
  • Carbodiimide crosslinking agents are available, for example, as commercially available products.
  • Commercially available carbodiimide crosslinking agents include, for example, Carbodilite V-02, Carbodilite V-02-L2, Carbodilite SV-02, Carbodilite V-04, Carbodilite V-10, Carbodilite SW-12G, Carbodilite E-02, Carbodilite E-03A, and Carbodilite E-05 (all manufactured by Nisshinbo Chemical Co., Ltd.), and Carbodilite V-02-L2.
  • Examples include Planet MM-103, XTB-3003 (all manufactured by BASF), Stabucksol P (manufactured by Sumitomo Bayer Urethanes), PICASSIAN XL-701, XL-702, XL-721, XL-725, XL-732, XL-752, XL-755, and XL-782 (all manufactured by STAHL POLYMERS).
  • the amount of the carbodiimide crosslinking agent added is appropriately set according to the purpose and application.
  • the amount of the carbodiimide group in the carbodiimide crosslinking agent is, for example, 0.05 mol or more, preferably 0.1 mol or more, more preferably 0.3 mol or more, even more preferably 0.5 mol or more, even more preferably 0.7 mol or more, and particularly preferably 0.9 mol or more per 1.0 mol of the carboxy group in the polyurethane resin.
  • the amount of the carbodiimide group in the carbodiimide crosslinking agent is, for example, 3.0 mol or less, preferably 2.0 mol or less, more preferably 1.5 mol or less, even more preferably 1.2 mol or less, and particularly preferably 1.0 mol or less per 1.0 mol of the carboxy group in the polyurethane resin.
  • the isocyanate crosslinking agent may be a known isocyanate crosslinking agent, preferably a water-dispersible polyisocyanate. If the secondary polyurethane dispersion contains an isocyanate crosslinking agent, a polyurethane layer 3 having excellent resistance to moist heat can be obtained.
  • Isocyanate crosslinkers are available, for example, as commercially available products.
  • Commercially available isocyanate crosslinking agents include, for example, Takenate WD-720, Takenate WD-725, Takenate WD-220, Takenate XWD-HS7, Takenate XWD-HS30 (all manufactured by Mitsui Chemicals), Aquanate 100, Aquanate 110, Aquanate 200, Aquanate 210, etc.
  • Water-dispersible polyisocyanates are polyisocyanates that can be dispersed in water.
  • Examples of water-dispersible polyisocyanates include polyisocyanates that have alkylene oxide groups with 2 to 3 carbon atoms as repeating units. These can be used alone or in combination of two or more types.
  • Water-dispersible polyisocyanates can be obtained, for example, by dispersing polyisocyanates containing polyethylene oxide groups in water using a known dispersant (e.g., an ionic dispersant, a nonionic dispersant, etc.). Water-dispersible polyisocyanates can be used alone or in combination of two or more types.
  • a known dispersant e.g., an ionic dispersant, a nonionic dispersant, etc.
  • Water-dispersible polyisocyanates can be used alone or in combination of two or more types.
  • the amount of the isocyanate crosslinking agent added is appropriately set according to the purpose and application.
  • the amount of the isocyanate group in the isocyanate crosslinking agent is, for example, 0.1 mol or more, preferably 0.5 mol or more, more preferably 0.8 mol or more, and even more preferably 1.0 mol or more, per 1.0 mol of the carboxy group in the polyurethane resin.
  • the isocyanate groups in the isocyanate crosslinking agent are, for example, 5.0 mol or less, preferably 4.0 mol or less, more preferably 3.0 mol or less, even more preferably 2.1 mol or less, and particularly preferably 1.8 mol or less.
  • the crosslinking agent is preferably an epoxy crosslinking agent or an isocyanate crosslinking agent, and more preferably an epoxy crosslinking agent.
  • the solids concentration of the secondary polyurethane dispersion 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 secondary polyurethane dispersion is, for example, 60% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less. The solids concentration is adjusted as appropriate by a known method.
  • the above polyurethane dispersion (primary polyurethane dispersion and/or secondary polyurethane dispersion) is used as an anchor coating agent. If necessary, the solids concentration of the anchor coating agent is appropriately adjusted.
  • the solid content concentration of the anchor coating agent 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 anchor coating agent is, for example, 60% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less.
  • the anchor coating agent is applied to, for example, the polyolefin substrate 2 and dried by heating.
  • application methods include dip coating, gravure coating, reverse coating, roll coating, bar coating, spray coating, air knife coating, and in-line coating.
  • drying conditions There are no particular limitations on the drying conditions.
  • 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, 0.1 minutes or more, preferably 0.2 minutes or more.
  • the drying time is, for example, 10 minutes or less, preferably 5 minutes or less.
  • a dried product of the anchor coating agent (including polyurethane dispersion) is formed on the polyolefin substrate 2.
  • the dried product is a polyurethane layer 3 (anchor coating layer) that contains polyurethane resin.
  • the polyurethane resin may be a polyurethane resin crosslinked by a crosslinking agent (a crosslinked polyurethane resin), or it may be an uncrosslinked polyurethane resin.
  • the anchor coating agent including the polyurethane dispersion
  • the polyurethane resin may be heated under appropriate conditions to crosslink the polyurethane resin, if necessary.
  • a polyurethane layer 3 anchor coating layer containing crosslinked polyurethane resin is formed.
  • the polyurethane resin (uncrosslinked polyurethane resin and/or crosslinked polyurethane resin; the same applies below) preferably contains an ester group.
  • the active hydrogen group-containing component may contain a high molecular weight polyol.
  • the high molecular weight polyol may contain a polyester polyol.
  • the polyester polyol may contain an ester group. Therefore, the polyurethane resin may contain an ester group.
  • the content of ester groups in the polyurethane resin is adjusted from the viewpoint of adhesion and resistance to moist heat. More specifically, the molar amount (mmol) of ester groups relative to the mass (g) of the polyurethane resin is adjusted.
  • the molar amount (mmol) of the ester group is, for example, 0.5 mmol/g or more, preferably 1.0 mmol/g or more, more preferably 2.0 mmol/g or more, even more preferably 3.0 mmol/g or more, even more preferably 4.0 mmol/g or more, and particularly preferably 4.5 mmol/g or more, relative to the mass (g) of the polyurethane resin.
  • the molar amount (mmol) of the ester group is, for example, 6.0 mmol/g or less, preferably 5.5 mmol/g or less, more preferably 5.0 mmol/g or less, relative to the mass (g) of the polyurethane resin.
  • the content ratio of the ester group is the content of the ester group (-COO-) relative to the total solid content of the polyurethane resin, and is calculated based on the formulation of the polyurethane resin.
  • the polyurethane resin preferably contains an aromatic ring.
  • the polyisocyanate component may contain a polyisocyanate containing an aromatic ring (aromatic polyisocyanate and/or aromatic aliphatic polyisocyanate).
  • the active hydrogen group-containing compound may contain a high molecular weight polyol containing an aromatic ring (aromatic ring-containing polyester polyol). In such a case, the polyurethane resin contains an aromatic ring.
  • the content of aromatic rings in the polyurethane resin is adjusted from the viewpoint of moist heat resistance. More specifically, the mass ratio (mass%) of aromatic rings to the total amount (total mass) of the polyurethane resin is adjusted.
  • the content of aromatic rings is, for example, 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 1.0 mass% or more, even more preferably 3.0 mass% or more, even more preferably 5.0 mass% or more, and particularly preferably 6.0 mass% or more, relative to the total amount of polyurethane resin.
  • the content of aromatic rings is, for example, 30 mass% or less, preferably 20 mass% or less, more preferably 10 mass% or less, and even more preferably 8.0 mass% or less, relative to the total amount of polyurethane resin.
  • the content of aromatic rings is the content of aromatic rings relative to the total amount of solids in the polyurethane resin, and is calculated based on the formulation of the polyurethane resin.
  • the raw material for the polyurethane resin preferably contains a silane coupling agent.
  • polyurethane resin is obtained by reacting a polyisocyanate component, an active hydrogen group-containing component, a chain extender, and a crosslinking agent used as needed.
  • the raw materials for polyurethane resin include a polyisocyanate component, an active hydrogen group-containing component, a chain extender, and a crosslinking agent used as needed.
  • the chain extender may contain a silane coupling agent containing an amino group.
  • the crosslinker as described above, may contain a silane coupling agent containing an epoxy group.
  • the raw materials for the polyurethane resin chain extender and/or crosslinker
  • may contain a silane coupling agent a silane coupling agent containing an amino group and/or a silane coupling agent containing an epoxy group.
  • the content (total amount) of the silane coupling agent in the raw materials for the polyurethane resin is adjusted from the viewpoint of adhesion. More specifically, the mass ratio (mass%) of the silane coupling agent to the total amount (total mass) of the raw materials for the polyurethane resin is adjusted.
  • the content of the silane coupling agent is, for example, 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 1.0 mass% or more, even more preferably 1.5 mass% or more, and particularly preferably 2.0 mass% or more, based on the total amount of the raw materials of the polyurethane resin.
  • the content of the silane coupling agent is, for example, 20 mass% or less, preferably 15 mass% or less, more preferably 10 mass% or less, even more preferably 5.0 mass% or less, and particularly preferably 2.5 mass% or less, based on the total amount of the raw materials of the polyurethane resin.
  • the content of the silane coupling agent is the content of the silane coupling agent relative to the total amount of solids in the raw materials of the polyurethane resin, and is calculated based on the formulation of the polyurethane resin.
  • the polyurethane layer 3 has a dry mass of, for example, 0.1 g/ m2 or more, preferably 0.3 g/ m2 or more, more preferably 0.5 g/ m2 or more.
  • the polyurethane layer 3 has a dry mass of, for example, 10 g/ m2 or less, preferably 5 g/ m2 or less, more preferably 3 g/ m2 or less, and even more preferably 1.5 g/ m2 or less.
  • the dry thickness of the polyurethane layer 3 is, for example, 0.1 ⁇ m or more, preferably 0.3 ⁇ m or more.
  • the dry thickness of the polyurethane layer 3 is, for example, 10 ⁇ m or less, preferably 5 ⁇ m or less.
  • Such a polyurethane layer 3 has excellent adhesion and resistance to moisture and heat.
  • the resistance to moisture and heat of the polyurethane layer 3 is evaluated based on the coefficient of thermal expansion.
  • the thermal expansion coefficient of the polyurethane layer 3, measured in a temperature range of 90°C to 120°C, is 150.0 ⁇ 10 -5 K -1 or less, preferably 120.0 ⁇ 10 -5 K -1 or less, more preferably 100.0 ⁇ 10 -5 K -1 or less, even more preferably 50.0 ⁇ 10 -5 K -1 or less, and particularly preferably 10.0 ⁇ 10 -5 K -1 or less.
  • the thermal expansion coefficient of the polyurethane layer 3 is usually 1.0 ⁇ 10 -5 K -1 or more.
  • the thermal expansion coefficient of the polyurethane layer 3 is measured using a single film of the polyurethane layer 3 in accordance with the examples described later.
  • the inorganic vapor deposition layer 4 is disposed on one surface of the polyurethane layer 3 so as to be in contact with the polyurethane layer 3. More specifically, the inorganic vapor deposition layer 4 is formed on one surface of the polyurethane layer 3 by vapor deposition of an inorganic material.
  • Inorganic materials include, for example, metals and metal oxides.
  • Metals include, for example, magnesium, calcium, barium, titanium, zirconium, aluminum, indium, silicon, germanium and tin, and preferably include aluminum.
  • Metal oxides include, for example, aluminum oxide, magnesium oxide, titanium oxide, indium oxide, silicon oxide, silicon oxide nitride, cerium oxide, calcium oxide and tin oxide, and preferably include aluminum oxide and silicon oxide.
  • the inorganic material may further include a diamond-like carbon film. These may be used alone or in combination of two or more.
  • a metal is used, and more preferably, aluminum is used.
  • the method for forming the inorganic vapor deposition layer 4 may be, for example, a vacuum process.
  • the vacuum process is not particularly limited, but may be, for example, a vacuum deposition method, a sputtering method, an ion plating method, or a chemical vapor deposition method (CVD method).
  • a preferred example of the vacuum process is a vacuum deposition method.
  • Examples of the heating method used in the vacuum deposition method include an electron beam heating method, a resistance heating method, and an induction heating method.
  • a laminate 1 is obtained which comprises, in order, the polyolefin substrate 2, the polyurethane layer 3, and the inorganic vapor deposition layer 4.
  • the thickness of the inorganic vapor deposition layer 4 is set appropriately depending on the type of inorganic material.
  • the thickness of the inorganic vapor deposition layer 4 is, for example, 1 nm or more, preferably 5 nm or more.
  • the thickness of the inorganic vapor deposition layer 4 is, for example, 500 nm or less, preferably 200 nm or less.
  • the total thickness of the laminate 1 is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more.
  • the total thickness of the laminate 1 is, for example, 1 mm or less, preferably 0.5 mm or less.
  • the laminate 1 may include an overcoat layer (not shown) as necessary.
  • the laminate 1 preferably includes an overcoat layer (not shown).
  • the overcoat layer (not shown) is disposed, for example, on one side of the inorganic vapor deposition layer 4 so as to be in contact with the inorganic vapor deposition layer 4. More specifically, the overcoat layer (not shown) is formed by applying and drying an overcoat agent on one side of the inorganic vapor deposition layer 4.
  • the overcoat agent is not particularly limited.
  • Examples of the overcoat agent include known overcoat agents, more specifically known polyurethane dispersions.
  • the polyurethane dispersion can contain the above-mentioned crosslinking agent as necessary.
  • the polyurethane dispersion preferably contains the above-mentioned crosslinking agent.
  • the content ratio of the crosslinking agent is appropriately set depending on the purpose and application.
  • the solids concentration of the overcoat agent is adjusted as appropriate depending on the purpose and application.
  • the overcoat agent is applied, for example, to the inorganic vapor deposition layer 4 and then heated and dried.
  • the amount applied and drying conditions are set as appropriate depending on the purpose and application.
  • a dried product of the overcoat agent is formed on the inorganic vapor deposition layer 4.
  • the dried product is an overcoat layer (not shown).
  • the overcoat layer (not shown) can improve the gas barrier properties of the laminate 1.
  • the polyurethane layer 3 is disposed on the polyolefin substrate 2.
  • the inorganic vapor deposition layer 4 is disposed on the polyurethane layer 3.
  • the polyurethane layer 3 contains a dried polyurethane dispersion.
  • the polyurethane dispersion contains a polyurethane resin.
  • the polyurethane resin contains a reaction product of an isocyanate-terminated prepolymer and a chain extender.
  • the polyurethane layer 3 has a thermal expansion coefficient measured in a temperature range of 90°C to 120°C that is equal to or less than a predetermined value. Therefore, the polyurethane layer 3 has excellent adhesion and moist heat resistance. Furthermore, if the polyurethane layer 3 is disposed on the polyolefin substrate 2, the thermal expansion of the polyolefin substrate 2 is suppressed by the polyurethane layer 3.
  • the laminate 1 can prevent damage to the inorganic vapor deposition layer 4 and has excellent adhesion and resistance to moisture and heat.
  • the laminate film 10 includes the laminate 1 as the first film 11, an adhesive layer 5, and a second film 12, which are arranged in this order along the thickness direction of the laminate 1.
  • the laminate 1 (first film 11), the adhesive layer 5, and the second film 12 are arranged in this order along the thickness direction of the laminate film 10.
  • the second film 12 includes a polyolefin resin layer 6, and is preferably made of a polyolefin resin layer 6.
  • the laminate film 10 (see FIG. 2 ) can be made into a mono-material together with the polyolefin substrate 2 of the laminate 1, and recyclability can be improved.
  • the second film 12 may be, for example, a base film or a sealant film.
  • the base film may be, for example, a base material containing the polyolefin resin described above.
  • the base film may preferably be a polypropylene film.
  • the sealant film may, for example, be a polyethylene film or an unstretched polypropylene film.
  • the sealant film may preferably be an unstretched polypropylene film.
  • the polyolefin resin layer 6 may be a single layer or multiple layers.
  • the polyolefin resin layer 6 may also be surface-treated. Examples of surface treatments include corona discharge treatment and anchor coat treatment.
  • the shape of the polyolefin resin layer 6 may be, for example, a sheet shape, a bottle shape, or a cup shape.
  • the thickness of the second film 12 (polyolefin resin layer 6) is, for example, 3 ⁇ m or more, preferably 5 ⁇ m or more.
  • the thickness of the second film 12 (polyolefin resin layer 6) is, for example, 500 ⁇ m or less, preferably 200 ⁇ m or less.
  • the adhesive layer 5 is, for example, a cured coating of a polyurethane adhesive.
  • polyurethane adhesives include one-component curing polyurethane adhesives and two-component curing polyurethane adhesives.
  • polyurethane adhesives include two-component curing polyurethane adhesives.
  • the two-component curing polyurethane adhesive includes, for example, a base agent and a curing agent. The base agent and the curing agent are mixed at the time of use. More specifically, the adhesive layer 5 is formed by interposing a mixture of the base agent and the curing agent between the laminate 1 (first film 11) and the second film 12 and curing the mixture. The thickness of the adhesive layer 5 is appropriately set according to the purpose and use.
  • the laminate film 10 can be obtained, for example, by bonding the above-mentioned laminate 1 (first film 11) and the second film 12 with a two-component curing polyurethane adhesive. More specifically, in this method, the curing agent and the base agent of the two-component curing polyurethane adhesive are first mixed. Then, the mixture of the base agent and the curing agent is applied to the surface of either the inorganic deposition layer 4 (or an overcoat layer (not shown) that is provided as needed) of the laminate 1 (first film 11) or the surface of the second film 12 (polyolefin resin layer 6). This results in a coating layer of the two-component curing polyurethane adhesive.
  • the other of the laminate 1 (first film 11) and the second film 12 (the other of the one mentioned above) is bonded to the applied layer of the two-component curing polyurethane adhesive by a known method.
  • a known laminating device is used.
  • laminating devices include a forward transfer type coating device and a reverse transfer type coating device (reverse coater).
  • the coating layer of the two-component curing polyurethane adhesive is heated as necessary, and cured as necessary. This causes the coating layer of the two-component curing polyurethane adhesive to harden, forming the adhesive layer 5.
  • the adhesive layer 5 is interposed between the inorganic vapor deposition layer 4 (or an overcoat layer (not shown) that is provided as necessary) and the polyolefin resin layer 6.
  • the heating conditions and curing conditions are not particularly limited, and are set appropriately depending on the purpose and application.
  • a laminate film 10 which comprises, in order, a polyolefin substrate 2, a polyurethane layer 3, an inorganic vapor deposition layer 4 (and an optional overcoat layer (not shown)), an adhesive layer 5, and a polyolefin resin layer 6.
  • the total thickness of the laminate film 10 is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more.
  • the total thickness of the laminate film 10 is, for example, 1 mm or less, preferably 0.5 mm or less.
  • the laminate film 10 includes the laminate 1 as the first film 11. Therefore, the laminate film 10 has excellent adhesion and moist heat resistance.
  • the laminate 1 and laminate film 10 described above are suitable for use as packaging materials in various industrial fields.
  • packaging materials include food packaging films, pharmaceutical packaging films, food packaging containers, optical films, and industrial films.
  • the laminate 1 has excellent heat resistance and is therefore suitable for use as food packaging films that are subjected to high-temperature sterilization treatment and food packaging films that are subjected to cooking.
  • Polyester polyol Preparation Example 1 (polyester polyol not containing an aromatic ring) 635.7 g of adipic acid (aromatic ring-free polycarboxylic acid), 440.1 g of 1,6-hexanediol (aromatic ring-free polyhydric alcohol), and 130.0 g of neopentyl glycol (aromatic ring-free polyhydric alcohol) were subjected to an esterification reaction under a nitrogen gas flow at 180 to 220° C. As a result, an aromatic ring-free polyester polyol having a number average molecular weight of about 2000 was obtained.
  • PUD1 to PUD18 A polyurethane dispersion (PUD) was prepared according to the recipe shown in Tables 1 and 2. That is, a polyisocyanate component, an active hydrogen group-containing component, a solvent, and a catalyst, if necessary, were mixed and reacted at 65 to 70°C under a nitrogen atmosphere. When the isocyanate group concentration of the reaction solution reached the value of the isocyanate group concentration of the prepolymer shown in Tables 1 and 2, the reaction solution was cooled. As a result, a reaction solution containing an isocyanate group-terminated prepolymer was obtained.
  • Anchor Coating Agents Production Examples 1 to 24 and Production Comparative Examples 1 to 3
  • the PUD of each synthesis example was mixed with water and a solvent according to the formulations shown in Tables 3 to 6.
  • the PUD of each synthesis example was mixed with a crosslinking agent, water, and a solvent as necessary. In this way, an anchor coating agent was obtained.
  • Laminates Examples 1 to 25 and Comparative Examples 1 to 3 Laminates were obtained according to the formulations shown in Tables 3 to 6. More specifically, first, a biaxially oriented polypropylene film (substrate, BOPP, product name Pylen Film OT P2171, thickness 30 ⁇ m, manufactured by Toyobo Co., Ltd.) was prepared as a polyolefin substrate.
  • a biaxially oriented polypropylene film substrate, BOPP, product name Pylen Film OT P2171, thickness 30 ⁇ m, manufactured by Toyobo Co., Ltd.
  • anchor coating agent was applied to the polyolefin substrate using a bar coater.
  • the anchor coating agent was then dried at 80°C for 1 minute. This resulted in a polyurethane layer (anchor coating layer) being formed on the surface of the polyolefin substrate.
  • the amount of the anchor coating agent applied was adjusted so that the dry mass (g/ m2 ) was the value shown in Tables 3 to 6.
  • the polyolefin substrate and the polyurethane layer (anchor coat layer) were set in a vacuum deposition apparatus (manufactured by ULVAC). Then, aluminum, aluminum oxide or silicon oxide was deposited (vacuum condition of 1 ⁇ 10 ⁇ 4 Pa, RH method) on the surface of the polyurethane layer (anchor coat layer) according to the descriptions in Tables 3 to 6 to form an inorganic deposition layer.
  • the thickness of the inorganic deposition layer made of aluminum was 50 nm.
  • the thickness of the inorganic deposition layer made of aluminum oxide was 20 nm.
  • the thickness of the inorganic deposition layer made of silicon oxide was 30 nm.
  • a laminate was obtained that included a polyolefin substrate, a polyurethane layer (anchor coat layer) disposed on the polyolefin substrate, and an inorganic vapor deposition layer disposed on the polyurethane layer (anchor coat layer).
  • Examples 26 to 31 A laminate was obtained according to the formulation shown in Table 7. More specifically, in each of Examples 26 to 31, a polyolefin substrate, an anchor coat layer, and an inorganic vapor deposition layer were laminated together in the same manner as in Examples 5, 16, 18, 19, 20, and 24.
  • an overcoat agent was applied to the inorganic vapor deposition layer using a bar coater according to the formulation shown in Table 7.
  • the overcoat agent was then dried at 80° C. for 1 minute. As a result, an overcoat layer was formed on the surface of the inorganic vapor deposition layer.
  • the amount of the overcoat agent applied was adjusted so that the dry mass (g/m 2 ) was the value shown in Table 7.
  • a laminate was obtained that included a polyolefin substrate, a polyurethane layer (anchor coat layer) disposed on the polyolefin substrate, an inorganic vapor deposition layer disposed on the polyurethane layer (anchor coat layer), and an overcoat layer disposed on the inorganic vapor deposition layer.
  • Aromatic Ring The content (mass%) of aromatic rings in the polyurethane resin was calculated based on the formulation.
  • Silane coupling agent The content (mass%) of the silane coupling agent in the raw material of the polyurethane resin was calculated based on the preparation recipe.
  • the amount of the silane coupling agent was the sum of the amount of the silane coupling agent (chain extender) containing an amino group and the amount of the silane coupling agent (epoxy crosslinker) containing an epoxy group.
  • the thermal expansion coefficient (K -1 ) of the polyurethane layer measured in the temperature range of 90 to 120° C. was calculated by the following method. That is, the anchor coating agent was placed in a plastic tray and dried for one day under conditions of 25° C. and relative humidity of 55%, and then heated for five days at 60° C. This resulted in an anchor coated film (thickness 100 ⁇ m).
  • the anchor coat film was cut to a length of 15 mm and a width of 5 mm. This resulted in a sample being obtained.
  • a thermomechanical analyzer (Shimadzu Corporation, TMA-50) was used to measure the thermal expansion coefficient of the sample in the temperature range of 90 to 120°C. The measurement conditions were set to a nitrogen atmosphere (gas flow rate of 40 mL/min), load setting of 0 g, and heating rate of 10°C/min. The measurement was also in accordance with JIS K7197 (1991).
  • Laminate film A polyurethane adhesive was applied to the inorganic vapor deposition layer of the laminate to a dry thickness of 3.0 g/ m2 and dried.
  • the polyurethane adhesive was a mixture of the following base agent, curing agent, and ethyl acetate. More specifically, ethyl acetate was added to the mixture of the base agent and curing agent to adjust the solid content concentration of the mixture to 25 mass%.
  • Base agent Takelac A-626, manufactured by Mitsui Chemicals, Inc., 8.0 parts by mass
  • Curing agent Takenate A-50, manufactured by Mitsui Chemicals, Inc., 1.0 part by mass
  • an unstretched polypropylene film (CPP, Tocello CP RXC-22, #60, manufactured by Mitsui Chemicals Tocello Co., Ltd.) was laminated onto the surface coated with the polyurethane adhesive and aged at 40°C for three days. This resulted in a laminated film.
  • the oxygen permeability (cc/ m2 ⁇ day ⁇ atm) of the laminate film was measured in accordance with JIS K7126-2 (2006) under the following conditions.
  • Device Oxygen permeation measuring device, product name OX-TRAN2/20, manufactured by MOCON Temperature: 20°C Humidity: 80% RH
  • the laminate film was then immersed in hot water at 121°C for 30 minutes for hot water treatment.
  • the oxygen permeability of the hot water treated laminate film was then measured under the above conditions.
  • the rate of increase in oxygen permeability was calculated using the following formula. Note that a higher rate of increase in oxygen permeability indicates a lower rating for hot water resistance.
  • the oxygen transmission rate of the laminate also depends on the hot water resistance of the overcoat layer, and may differ significantly before and after the hot water treatment. Therefore, in Examples 26 to 31, in order to evaluate the hot water resistance derived from the polyurethane layer, the oxygen transmission rate (cc/ m2 day atm) after the hot water treatment was confirmed, instead of the increase rate (%) of the oxygen transmission rate.
  • Increase in oxygen permeability (%) [(oxygen permeation amount after hot water treatment - oxygen permeation amount before hot water treatment) / oxygen permeation amount before hot water treatment]
  • the lamination strength of the laminate film was measured using a T-peel test (15 mm width) in accordance with JIS K 6854 (1999).
  • the biaxially oriented polypropylene film (bottom layer, BOPP) and the unoriented polypropylene film (top layer, CPP) were grasped and pulled in opposite directions to expose the interface between the biaxially oriented polypropylene film (substrate) and the polyurethane layer (anchor coat layer).
  • a T-peel test was performed to measure the peel strength (lamination strength) of the interface between the biaxially oriented polypropylene film (substrate) and the polyurethane layer (anchor coat layer).
  • the laminate film was then immersed in hot water at 121°C for 30 minutes for hot water treatment.
  • the peel strength (lamination strength) of the hot water treated laminate film was then measured under the same conditions as above.
  • m-XDI m-xylylene diisocyanate H 12 MDI; methylene bis(cyclohexyl isocyanate) MEK; methyl ethyl ketone AN; acetonitrile TEA; triethylamine TEG; triethylene glycol EG; ethylene glycol TMP; trimethylolpropane DMPA; dimethylolpropionic acid Stannoct; stannous octoate, urethane catalyst Aminosilane; N-2-(aminoethyl)-3-aminopropyltrimethoxysilane AEA; 2-((2-aminoethyl)amino)ethanol EDA; ethylenediamine BOPP; biaxially oriented polypropylene film AL; aluminum AlOx; aluminum oxide SiOx; silicon oxide KBM-403: trade name KBM-403, epoxy crosslinking agent, 3-glycidoxypropyl
  • Laminate 2 Polyolefin substrate 3
  • adhesive layer 6 polyolefin resin layer
  • the laminate of the present invention is suitably used in food packaging films, pharmaceutical packaging films, food packaging containers, optical films and industrial films.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
PCT/JP2024/001891 2023-01-27 2024-01-23 積層体 Ceased WO2024157983A1 (ja)

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Publication number Priority date Publication date Assignee Title
JP2020105243A (ja) * 2018-12-26 2020-07-09 三井化学株式会社 アンカーコート剤および多層フィルム
US20210098752A1 (en) * 2019-09-27 2021-04-01 Benq Materials Corporation Composite packaging material for lithium battery
WO2022158445A1 (ja) 2021-01-22 2022-07-28 三井化学株式会社 ポリウレタンディスパージョン、ガスバリア性コート材および積層体
WO2022220200A1 (ja) * 2021-04-13 2022-10-20 凸版印刷株式会社 ガスバリアフィルム、包装材及び包装袋
WO2022259968A1 (ja) * 2021-06-11 2022-12-15 三井化学株式会社 接着剤および積層体

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KR102485842B1 (ko) 2021-05-24 2023-01-05 노정기 구이기 겸용 화목난로

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Publication number Priority date Publication date Assignee Title
JP2020105243A (ja) * 2018-12-26 2020-07-09 三井化学株式会社 アンカーコート剤および多層フィルム
US20210098752A1 (en) * 2019-09-27 2021-04-01 Benq Materials Corporation Composite packaging material for lithium battery
WO2022158445A1 (ja) 2021-01-22 2022-07-28 三井化学株式会社 ポリウレタンディスパージョン、ガスバリア性コート材および積層体
WO2022220200A1 (ja) * 2021-04-13 2022-10-20 凸版印刷株式会社 ガスバリアフィルム、包装材及び包装袋
WO2022259968A1 (ja) * 2021-06-11 2022-12-15 三井化学株式会社 接着剤および積層体

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Title
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