WO2022009829A1 - コーティング組成物および積層体 - Google Patents

コーティング組成物および積層体 Download PDF

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Publication number
WO2022009829A1
WO2022009829A1 PCT/JP2021/025283 JP2021025283W WO2022009829A1 WO 2022009829 A1 WO2022009829 A1 WO 2022009829A1 JP 2021025283 W JP2021025283 W JP 2021025283W WO 2022009829 A1 WO2022009829 A1 WO 2022009829A1
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Prior art keywords
monomer
coating composition
mass
examples
polyol
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Ceased
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PCT/JP2021/025283
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English (en)
French (fr)
Japanese (ja)
Inventor
朋治 宮永
司 村上
和幸 福田
隆 内田
寿洋 吉村
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Application filed by Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Priority to JP2022535313A priority Critical patent/JP7604492B2/ja
Priority to EP21837060.9A priority patent/EP4177051A4/en
Priority to CN202180042243.XA priority patent/CN115698202A/zh
Priority to US18/011,248 priority patent/US20230295459A1/en
Publication of WO2022009829A1 publication Critical patent/WO2022009829A1/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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/6715—Unsaturated monofunctional alcohols or amines
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8029—Masked aromatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Definitions

  • the present invention relates to a coating composition and a laminate.
  • a packaging material for example, a laminate in which a plurality of films having various functions are laminated is used.
  • a laminate for example, a laminate having a base material, a resin coating film obtained from a primer, an ink layer, an adhesive layer, and a sealant layer has been proposed.
  • the primer for forming the resin coating include methyl methacrylate (MMA), acrylonitrile (AN), ⁇ -hydroxyethyl methacrylate ( ⁇ -HEMA), styrene (St), butyl acrylate (BA) and methacrylic acid (
  • a primer has been proposed in which MAA) is copolymerized to prepare a main agent solution, and the obtained main agent solution is mixed with a trimethyllylene propaneadductate (XDI-TMP) of xylylene diisocyanate as a curing agent (for example,). See Patent Document 1 (Comparative Example Primer 4)).
  • the laminate obtained by using such a primer is required to further improve the gas barrier property and the retort resistance (heat resistant water).
  • the present invention is obtained by using a coating composition which is excellent in handleability and workability, and which can efficiently obtain a laminate excellent in gas barrier property and retort resistance (heat-resistant water-based), and the coating composition thereof. It is a laminated body.
  • the present invention contains a polyisocyanate component and a polyol component, the polyisocyanate component contains an aromatic ring-containing isocyanate, the polyol component contains an acrylic polyol, and the acrylic polyol is a hydroxyl group-containing polymerizable monomer and It contains a coating composition which is a polymer of a monomer composition containing a carboxyl group-containing polymerizable monomer and not containing (meth) acrylonitrile.
  • the present invention [2] contains the coating composition according to the above [1], wherein the aromatic ring-containing isocyanate contains a xylylene diisocyanate and / or a derivative thereof.
  • the present invention [3] includes the coating composition according to the above [1] or [2], wherein the monomer composition contains an aromatic vinyl monomer.
  • the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the polyol component is 1.2 or more and 6.0 or less, the above [1] to [3]. Contains the coating composition according to any one of the above.
  • the mass ratio of the content of the carboxy group-containing monomer to the content of the hydroxyl group-containing monomer is 0.03 or more and 0.
  • the content ratio of the carboxy group-containing monomer is 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the total amount of the monomer composition.
  • the coating composition according to any one of [5] is contained.
  • the present invention [7] includes the coating composition according to any one of the above [1] to [6], wherein the acrylic polyol has a glass transition temperature of ⁇ 25 ° C. or higher and 80 ° C. or lower.
  • the present invention [7] includes the coating composition according to any one of the above [1] to [6], wherein the acrylic polyol has a number average molecular weight of 6000 or more.
  • the resin film, the inorganic thin film layer arranged on one side in the thickness direction of the resin film, the polyurethane layer arranged on one side in the thickness direction of the inorganic thin film layer, and the thickness of the polyurethane layer are provided, and the polyurethane layer is in any one of the above [1] to [7].
  • the present invention includes the laminate according to the above [8], wherein the inorganic thin film layer contains aluminum oxide and / or silicon oxide.
  • the present invention [10] includes the laminate according to the above [8] or [9], wherein the resin film contains a polyester resin and / or a polyolefin resin.
  • the monomer composition which is a raw material of the acrylic polyol does not contain (meth) acrylonitrile. Therefore, the coating composition of the present invention is excellent in solubility in an alkyl ester, and as a result, is excellent in handleability and workability.
  • the coating composition of the present invention contains an aromatic ring-containing isocyanate as a polyisocyanate component.
  • the acrylic polyol contains a polymer of a monomer composition containing a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer.
  • the coating composition of the present invention can obtain a laminate having excellent gas barrier properties and retort resistance (heat resistant water).
  • the laminate of the present invention is obtained by using the above coating composition, it is well obtained in workability, and is also excellent in gas barrier property and retort resistance.
  • FIG. 1 is a schematic configuration diagram showing an embodiment of the laminated body of the present invention.
  • the coating composition of the present invention contains a polyisocyanate component and a polyol component.
  • the polyisocyanate component contains an isocyanate compound as an active ingredient.
  • the isocyanate compound contains an aromatic ring-containing isocyanate as an essential component.
  • Aromatic ring-containing isocyanate is a polyisocyanate containing an aromatic ring in its molecular skeleton.
  • aromatic ring-containing isocyanate examples include an aromatic ring-containing isocyanate monomer and a derivative of the aromatic ring-containing isocyanate monomer (hereinafter, referred to as an aromatic ring-containing isocyanate derivative).
  • aromatic ring-containing isocyanate monomer examples include aromatic polyisocyanates and aromatic aliphatic polyisocyanates.
  • aromatic polyisocyanate examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TODI), paraphenylenedi isocyanate, naphthalene diisocyanate (NDI) and the like, and tolylene diisocyanate (TDI) is preferable.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • TODI toluene diisocyanate
  • NDI naphthalene diisocyanate
  • MDI diphenylmethane diisocyanate
  • examples of the tolylene diisocyanate examples include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
  • diphenylmethane diisocyanate examples include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate and the like.
  • Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI).
  • Examples of the xylylene diisocyanate include 1,3-xylylene diisocyanate and 1,4-xylylene diisocyanate.
  • Examples of the tetramethylxylylene diisocyanate include 1,3-tetramethylxylylene diisocyanate and 1,4-tetramethylxylylene diisocyanate.
  • aromatic ring-containing isocyanate monomers can be used alone or in combination of two or more.
  • aromatic ring-containing isocyanate monomer examples include aromatic polyisocyanate and aromatic aliphatic polyisocyanate, more preferably tolylene diisocyanate and xylylene diisocyanate, and further preferably xylylene diisocyanate. Will be.
  • aromatic ring-containing isocyanate derivative examples include a modified product obtained by modifying the above-mentioned aromatic ring-containing isocyanate monomer by a known method.
  • aromatic ring-containing isocyanate derivative examples include multimers, allophanate-modified products, polyol-modified products, biuret-modified products, urea-modified products, oxadiazine-trione-modified products, and carbodiimide-modified products.
  • Examples of the multimer include a dimer, a trimer, a pentamer, a hepatic, and the like.
  • Examples of the trimer include isocyanurate-modified products and iminooxadiazinedione-modified products.
  • the allophanate modified product examples include an allophanate modified product produced by the reaction of the above-mentioned aromatic ring-containing isocyanate monomer with a monohydric alcohol or a divalent alcohol.
  • modified polyol examples include an alcohol adduct produced by the reaction of the above-mentioned aromatic ring-containing isocyanate monomer with a trihydric or higher alcohol.
  • biuret modified product examples include a biuret modified product produced by reacting the above-mentioned aromatic ring-containing isocyanate monomer with water and / or amines.
  • urea modified product examples include the urea modified product produced by the reaction between the above-mentioned aromatic ring-containing isocyanate monomer and diamine.
  • Examples of the oxadiazine trion modified product include the oxadiazine trion modified product produced by the reaction between the above-mentioned aromatic ring-containing isocyanate monomer and carbon dioxide gas.
  • carbodiimide modified product examples include a carbodiimide modified product produced by the decarboxylation condensation reaction of the above-mentioned aromatic ring-containing isocyanate monomer.
  • aromatic ring-containing isocyanate derivative examples include uretdione modified product, uretonimine modified product, polymethylene polyphenylene polyisocyanate (crude MDI, polypeptide MDI) and the like.
  • aromatic ring-containing isocyanate derivatives can be used alone or in combination of two or more.
  • aromatic ring-containing isocyanate derivative examples are preferably a derivative of tolylene diisocyanate and a derivative of xylylene diisocyanate, more preferably a derivative of xylylene diisocyanate, and further preferably 1,3-xylylene diisocyanate. Derivatives can be mentioned.
  • the derivative preferably includes an isocyanurate modified product and a polyol modified product (alcohol adduct), more preferably a polyol modified product (alcohol adduct), and particularly preferably a trimethylolpropane adduct. Can be mentioned.
  • aromatic ring-containing isocyanates can be used alone or in combination of two or more.
  • aromatic ring-containing isocyanate examples include xylylene diisocyanate and / or a derivative thereof, more preferably a derivative of xylylene diisocyanate, and further preferably a polyol modified product (alcohol adduct) of xylylene diisocyanate. , And particularly preferably, a trimethylolpropane adduct of xylylene diisocyanate.
  • the isocyanate compound can contain an aromatic ring-free isocyanate as an optional component as long as the excellent effect of the present invention is not impaired.
  • Aromatic ring-free isocyanate is a polyisocyanate that does not contain an aromatic ring in its molecular skeleton.
  • aromatic ring-free isocyanate examples include a monomer of an aromatic ring-free isocyanate and a derivative of a monomer of an aromatic ring-free isocyanate (hereinafter, referred to as an aromatic ring-free isocyanate derivative).
  • aromatic ring-free isocyanate monomer examples include aliphatic polyisocyanates.
  • aliphatic polyisocyanate examples include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, and 2,2'-dimethylpentane diisocyanate.
  • 2,2,4-trimethylhexanediisocyanate decamethylene diisocyanate, butenediisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecamethylene Triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane, bis ( Isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether- ⁇ , ⁇ '-diisocyanate, lysine isocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6 -Diisocyanate
  • the aliphatic polyisocyanate includes an alicyclic polyisocyanate.
  • alicyclic polyisocyanate examples include isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H 12 MDI), bis (isocyanatomethyl) cyclohexane (H 6 XDI), 1,3-cyclohexanediisocyanate, and 1,4-cyclohexane.
  • IPDI isophorone diisocyanate
  • H 12 MDI dicyclohexylmethane diisocyanate
  • H 6 XDI bis (isocyanatomethyl) cyclohexane
  • 1,3-cyclohexanediisocyanate 1,4-cyclohexane.
  • Diisocyanate 1,3-bis (isocyanatoethyl) cyclohexane, 1,4-bis (isocyanatoethyl) cyclohexane, methylcyclohexanediisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, dimerate diisocyanate, 2,5-diisocyanate Natomethylbicyclo [2,2,1] -heptane, 2,6-diisocyanatomethylbicyclo [2,2,1] -heptane (NBDI), 2-isocyanatomethyl 2- (3-isocyanatopropyl)- 5-Isocyanatomethylbicyclo-[2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo-[2,2,1] -heptane, 2-Isocyanatomethyl 3-
  • IPDI isophorone diisocyanate
  • H 12 MDI dicyclohexylmethane diisocyanate
  • H 6 XDI bis (isocyanatomethyl) cyclohexane
  • aromatic ring-free isocyanate monomers can be used alone or in combination of two or more.
  • aromatic ring-free isocyanate derivative examples include a modified product obtained by modifying the above-mentioned aromatic ring-free isocyanate monomer by a known method, similarly to the aromatic ring-containing isocyanate derivative.
  • aromatic ring-free isocyanate derivative examples include multimers, allophanate-modified products, polyol-modified products, biuret-modified products, urea-modified products, oxadiazine-trione-modified products, and carbodiimide-modified products.
  • aromatic ring-free isocyanate derivatives can be used alone or in combination of two or more.
  • aromatic ring-free isocyanates can be used alone or in combination of two or more.
  • the content ratio of the aromatic ring-free isocyanate is appropriately set according to the purpose and application.
  • the content ratio of the aromatic ring-free isocyanate is, for example, with respect to 100 parts by mass of the total amount of the polyisocyanate compound (aromatic ring-containing isocyanate and aromatic ring-free isocyanate) from the viewpoint of adhesion and gas barrier property. , 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.
  • the content ratio of the aromatic ring-containing isocyanate is, for example, 70 parts by mass or more, preferably 80 parts by mass or more, more preferably 90 parts by mass or more, particularly, with respect to 100 parts by mass of the total amount of the polyisocyanate compound. It is preferably 100 parts by mass.
  • the isocyanate compound preferably does not contain an aromatic ring-free isocyanate.
  • the isocyanate compound preferably contains only an aromatic ring-containing isocyanate, more preferably contains only an aromatic ring-containing isocyanate derivative, and more preferably contains only a xylylene diisocyanate derivative.
  • the polyisocyanate component can contain an organic solvent.
  • the above isocyanate compound can be diluted with an organic solvent.
  • Examples of the organic solvent include alkyl esters.
  • Examples of the alkyl ester include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate and the like.
  • organic solvents can be used alone or in combination of two or more.
  • an alkyl ester is preferably mentioned, and ethyl acetate is more preferable, from the viewpoint of handleability and workability.
  • the solid content concentration is appropriately set according to the purpose and application.
  • the solid content concentration (content ratio of the isocyanate compound) of the polyisocyanate component is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 100% by mass or less, preferably 80. It is less than mass%.
  • the polyol component contains a polyol compound as an active ingredient.
  • the polyol compound contains an acrylic polyol as an essential component.
  • Acrylic polyol is a macropolyol.
  • the macropolyol is an organic compound having two or more hydroxyl groups and having a number average molecular weight of 400 or more, preferably 500 or more, for example, 100,000 or less.
  • Acrylic polyol is a polymer of a monomer composition containing a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer and not containing (meth) acrylonitrile.
  • (meth) acrylonitrile indicates acrylonitrile and / or methacrylonitrile.
  • (meth) acrylic indicates acrylic and / or methacrylic.
  • (meth) acrylate indicates acrylate and / or methacrylate.
  • the monomer composition that is the raw material of the acrylic polyol does not contain (meth) acrylonitrile, the solubility of the acrylic polyol in the alkyl ester can be improved, and as a result, the coating composition is excellent in handleability and workability. Can be obtained.
  • Examples of the hydroxyl group-containing polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl. Examples thereof include (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate.
  • hydroxyl group-containing polymerizable monomers can be used alone or in combination of two or more.
  • 2-hydroxyethyl (meth) acrylate is preferable, and 2-hydroxyethyl acrylate is more preferable, from the viewpoint of gas barrier property and retort resistance.
  • Examples of the carboxy group-containing polymerizable monomer include monocarboxylic acids, dicarboxylic acids, and salts thereof.
  • Examples of the monocarboxylic acid include (meth) acrylic acid.
  • Examples of the dicarboxylic acid include itaconic acid, maleic acid, fumaric acid, itaconic anhydride, maleic anhydride, fumaric anhydride and the like.
  • carboxy group-containing polymerizable monomers can be used alone or in combination of two or more.
  • carboxy group-containing polymerizable monomer examples include (meth) acrylic acid and itaconic acid, more preferably (meth) acrylic acid, and further preferably acrylic acid.
  • the monomer composition can contain a copolymerizable monomer copolymerizable with a hydroxyl group-containing polymerizable monomer and / or a carboxyl group-containing polymerizable monomer.
  • copolymerizable monomer examples include (meth) acrylic acid ester, aromatic vinyl monomer, amino group-containing polymerizable monomer, glycidyl group-containing polymerizable monomer, sulfonic acid group-containing polymerizable monomer, and acetoacetoxy group-containing polymerizable monomer. , Phosphoric acid group-containing compounds, vinyl esters, heterocyclic vinyl compounds, vinylidene halide compounds, ⁇ -olefins, dienes and the like.
  • Examples of the (meth) acrylic acid ester include an alkyl ester having 1 to 12 carbon atoms of (meth) acrylic acid. More specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n- Amil (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) Examples thereof include acrylate, cyclohexyl (meth) acrylate, phenyl (
  • acrylic acid esters can be used alone or in combination of two or more.
  • Examples of the (meth) acrylic acid ester are preferably methyl (meth) acrylate and n-butyl (meth) acrylate, and more preferably methyl methacrylate and n-butyl acrylate.
  • aromatic vinyl monomer examples include styrene and ⁇ -methylstyrene.
  • aromatic vinyl monomers can be used alone or in combination of two or more.
  • the aromatic vinyl monomer is preferably styrene.
  • amino group-containing polymerizable monomer examples include 2-aminoethyl (meth) acrylate, 2- (N-methylamino) ethyl (meth) acrylate, and 2- (N, N-dimethylamino) (meth) acrylate. ) Ethyl and the like.
  • amino group-containing polymerizable monomers can be used alone or in combination of two or more.
  • Examples of the glycidyl group-containing polymerizable monomer include glycidyl (meth) acrylate.
  • glycidyl group-containing polymerizable monomers can be used alone or in combination of two or more.
  • Examples of the sulfonic acid group-containing polymerizable monomer include allyl sulfonic acid, methallyl sulfonic acid, and acrylamide t-butyl sulfonic acid.
  • Examples of the salt include alkali metal salts such as sodium salt and potassium salt of the sulfonic acid group-containing polymerizable monomer, for example, ammonium salt and the like. Specific examples thereof include sodium allyl sulfonate, sodium methallyl sulfonate, ammonium methallyl sulfonate and the like.
  • sulfonic acid-containing polymerizable monomers can be used alone or in combination of two or more.
  • acetoxy group-containing polymerizable monomer examples include acetoxyethyl (meth) acrylate.
  • acetoxy group-containing polymerizable monomers can be used alone or in combination of two or more.
  • Examples of the phosphoric acid group-containing compound include 2-metacloyloxyethyl acid phosphate and the like.
  • phosphate group-containing compounds can be used alone or in combination of two or more.
  • vinyl esters examples include vinyl acetate and vinyl propionate.
  • vinyl esters can be used alone or in combination of two or more.
  • N-substituted unsaturated carboxylic acid amide examples include N-methylol (meth) acrylamide.
  • N-substituted unsaturated carboxylic acid amides can be used alone or in combination of two or more.
  • heterocyclic vinyl compound examples include vinylpyrrolidone.
  • heterocyclic vinyl compounds can be used alone or in combination of two or more.
  • halogenated vinylidene compound examples include vinylidene chloride and vinylidene fluoride.
  • halogenated vinylidene compounds can be used alone or in combination of two or more.
  • ⁇ -olefins examples include ethylene and propylene.
  • ⁇ -olefins can be used alone or in combination of two or more.
  • diene examples include butadiene.
  • dienes can be used alone or in combination of two or more.
  • copolymerizable monomers can be used alone or in combination of two or more.
  • Preferred examples of the copolymerizable monomer include (meth) acrylic acid ester and aromatic vinyl monomer.
  • the monomer composition preferably contains a hydroxyl group-containing polymerizable monomer, a carboxyl group-containing polymerizable monomer, a (meth) acrylic acid ester and / or an aromatic vinyl monomer, and more preferably a hydroxyl group-containing polymerization. It contains a sex monomer, a carboxyl group-containing polymerizable monomer, a (meth) acrylic acid ester, and an aromatic vinyl monomer.
  • the content ratio of the hydroxyl group-containing polymerizable monomer is, for example, 1 part by mass or more, preferably 1 part by mass or more, based on 100 parts by mass of the total amount of the monomer composition, from the viewpoint of adhesion and gas barrier property of the polyurethane layer described later. 5, 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and from the viewpoint of handleability of the acrylic polyol, for example, 99.99 parts by mass or less, preferably 60 parts by mass or more.
  • it is more preferably 40 parts by mass or less, still more preferably 23 parts by mass or less.
  • the content ratio of the carboxy group-containing polymerizable monomer is, for example, 0. 01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.7 parts by mass or more, for example, 99 parts by mass or less, preferably 5 parts by mass.
  • mass or less more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.
  • the mass ratio of the content of the carboxy group-containing monomer to the content of the hydroxyl group-containing monomer is, for example, 0.01 or more, preferably 0.01 or more, from the viewpoint of handleability and workability. , 0.03 or more, for example, 0.2 or less, preferably 0.1 or less.
  • the content ratio of the (meth) acrylic acid ester is appropriately set so that the glass transition temperature of the acrylic polyol is in the range described later.
  • the content ratio (total amount) of the (meth) acrylic acid ester is, for example, 1 part by mass or more, preferably 5 parts by mass, based on 100 parts by mass of the total amount of the monomer composition from the viewpoint of blocking resistance and adhesion. It is 7 parts or more, for example, 70 parts by mass or less, preferably 50 parts by mass or less.
  • the content ratio of the aromatic vinyl monomer is appropriately set so that the glass transition temperature of the acrylic polyol is in the range described later.
  • the content ratio of the aromatic vinyl monomer is, for example, 1 part by mass or more, preferably 20 parts by mass or more, and for example, 50 parts by mass or less, preferably 50 parts by mass, based on 100 parts by mass of the total amount of the monomer composition. It is 40 parts by mass or less.
  • the acrylic polyol can be obtained, for example, by blending the above-mentioned monomer composition with a polymerization initiator and polymerizing the monomer composition in a solvent.
  • the solvent is not particularly limited, and examples thereof include the above-mentioned alkyl esters.
  • the solvent is preferably ethyl acetate.
  • the polymerization initiator is not particularly limited, and examples thereof include a water-soluble initiator, an oil-soluble initiator, a redox-based initiator, and the like, preferably a water-soluble initiator and an oil-soluble initiator.
  • water-soluble initiator examples include persulfate, hydrogen peroxide, organic hydroperoxide, 4,4'-azobis (4-cyanovaleric acid) acid and the like.
  • oil-soluble initiator examples include benzoyl peroxide, azobisisobutyronitrile, and the like.
  • These polymerization initiators can be used alone or in combination of two or more.
  • the mixing ratio of the polymerization initiator is appropriately set according to the purpose and application.
  • the amount of the polymerization initiator is, for example, 0.05 parts by mass or more, for example, 10 parts by mass or less, preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of the monomer composition.
  • the polymerization temperature is, for example, 30 ° C. or higher, preferably 50 ° C. or higher, and for example, 95 ° C. or lower, preferably 85 ° C. or lower.
  • the polymerization time is, for example, 1 hour or more, preferably 2 hours or more, for example, 30 hours or less, preferably 20 hours or less.
  • a known additive can be added from the viewpoint of improving the production stability.
  • the additive examples include a pH adjuster, a metal ion encapsulant, a molecular weight adjuster (chain transfer agent), a neutralizer, and the like.
  • the amount of additive added and the timing of addition are appropriately set according to the purpose and application.
  • an acrylic polyol can be obtained as a polymer of the monomer composition.
  • the acrylic polyol may be obtained as a solution of the above solvent.
  • the solid content concentration of the solution is, for example, 3% by mass or more, preferably 5% by mass or more, and for example, less than 100% by mass, preferably 90% by mass or less.
  • the glass transition temperature of the acrylic polyol is, for example, ⁇ 50 ° C. or higher, preferably ⁇ 25 ° C. or higher, more preferably 0 ° C. or higher, and further, from the viewpoint of blocking resistance of the polyurethane layer described later. It is preferably 20 ° C. or higher, particularly preferably 40 ° C. or higher, and from the viewpoint of handleability and workability of the acrylic polyol, for example, 100 ° C. or lower, preferably 90 ° C. or lower, more preferably 80 ° C. or lower, More preferably, it is 70 ° C. or lower.
  • the glass transition temperature of the acrylic polyol is calculated by a known method according to the formulation of the monomer composition and the FOX formula.
  • the number average molecular weight of the acrylic polyol is, for example, 2000 or more, preferably 6000 or more, more preferably 10,000 or more, from the viewpoints of gas barrier property, retort resistance, handleability and workability. For example, it is 100,000 or less, preferably 50,000 or less, and more preferably 20,000 or less.
  • the number average molecular weight of the acrylic polyol is calculated by gel permeation chromatography (GPC) as a standard polystyrene-equivalent molecular weight.
  • polyol compound can contain other macropolyols and low molecular weight polyols as optional components as long as the excellent effects of the present invention are not impaired.
  • macropolyols are macropolyols excluding acrylic polyols.
  • macropolyols examples include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, and polymerizable monomer-modified polyols.
  • These other macro polyols can be used alone or in combination of two or more.
  • the low molecular weight polyol is an organic compound having two or more hydroxyl groups in the molecule and having a molecular weight of 50 or more, 400 or less, preferably 300 or less.
  • Examples of the low molecular weight polyol include dihydric alcohols and trihydric alcohols.
  • Examples of the divalent alcohol include 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
  • Examples include neopentyl glycol.
  • Examples of the trihydric alcohol include glycerin and trimethylolpropane.
  • These low molecular weight polyols can be used alone or in combination of two or more.
  • the content ratio of the optional component is appropriately set according to the purpose and use.
  • the content ratio of the other macropolyol is, for example, less than 50 parts by mass, preferably 40 parts by mass or less, and more preferably 30 parts by mass with respect to 100 parts by mass of the total amount of the polyol compound from the viewpoint of gas barrier property.
  • the amount is 0 parts by mass.
  • the content ratio of the low molecular weight polyol is, for example, less than 50 parts by mass, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less with respect to 100 parts by mass of the total amount of the polyol compound. Particularly preferably, it is 0 parts by mass.
  • the content ratio of the acrylic polyol exceeds, for example, 50 parts by mass, preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and particularly preferably 70 parts by mass or more, based on 100 parts by mass of the total amount of the polyol compound. Is 100 parts by mass.
  • the polyol component does not contain other macropolyols and low molecular weight polyols as active ingredients, but contains only the above acrylic polyols.
  • the polyol component can contain an organic solvent.
  • the above polyol compound can be diluted with an organic solvent.
  • organic solvent examples include the above-mentioned organic solvents. These organic solvents can be used alone or in combination of two or more.
  • an alkyl ester is preferably mentioned, and ethyl acetate is more preferable, from the viewpoint of handleability and workability.
  • the solid content concentration thereof is appropriately set according to the purpose and application.
  • the solid content concentration (content ratio of the polyol compound) of the polyol component is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 100% by mass or less, preferably 80% by mass. % Or less.
  • the coating composition can further contain an additive.
  • the additive examples include an oxygen acid of phosphorus or a derivative thereof, a silane coupling agent, a defoaming agent, an epoxy resin, a catalyst, a coatability improving agent, a leveling agent, and a stabilizer (antioxidant, ultraviolet absorber, etc.). , Plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, antifungal agents and the like.
  • additives can be used alone or in combination of two or more.
  • the additive may be added to, for example, either one or both of the polyisocyanate component and the polyol component, or may be blended separately from the polyisocyanate component and / or the polyol component.
  • the blending amount of the additive is appropriately determined depending on the purpose and use.
  • the content ratio of the polyisocyanate component and the polyol component is adjusted, for example, as the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the polyol component.
  • the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the polyol component is, for example, 0.9 or more, preferably 1.0 or more, from the viewpoint of gas barrier property. , More preferably 1.1 or more, still more preferably 1.2 or more, still more preferably 2.0 or more, particularly preferably 2.5 or more, and from the viewpoint of retort resistance, for example, 10. It is 0 or less, preferably 8.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less, still more preferably 5.0 or less, and particularly preferably 4.5 or less.
  • the coating composition is prepared as, for example, a two-component curable coating agent or a one-component curable coating agent.
  • the above-mentioned polyol component is prepared as the main agent. Further, the above-mentioned polyisocyanate component is prepared as a curing agent. Then, the main agent and the curing agent are blended in the above ratio at the time of use.
  • the one-component curable coating agent examples include a moisture-curable adhesive that cures with moisture or steam (amine vapor, etc.).
  • a one-component curable coating agent contains, for example, a urethane prepolymer having an isocyanate group at the molecular terminal, which is obtained by reacting a polyisocyanate component and the above-mentioned polyol component at the above-mentioned ratios.
  • the urethane prepolymer as a one-component curable coating agent has an isocyanate group at the molecular terminal, and the isocyanate group is cured by reacting with moisture or steam (amine vapor or the like) in the atmosphere. ..
  • the coating agent preferably contains the above-mentioned organic solvent.
  • an alkyl ester is preferably mentioned, and ethyl acetate is more preferable, from the viewpoint of handleability and workability.
  • the organic solvent may be blended with the polyisocyanate component and / or the polyol component, or may be separately blended when the polyisocyanate component and the polyol component are mixed.
  • the content ratio of the organic solvent is appropriately set so that the total amount of the solid content (resin solid content) of the polyisocyanate component and the polyol component becomes a predetermined ratio.
  • the solid content concentration of the coating composition (total amount of polyisocyanate component and polyol component. If an organic solvent is separately mixed when the polyisocyanate component and the polyol component are mixed, the organic solvent is included) is determined. From the viewpoint of handleability and workability, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, for example, 50% by mass or less, preferably 40% by mass or less, More preferably, it is 30% by mass or less.
  • the monomer composition which is a raw material of the acrylic polyol does not contain (meth) acrylonitrile. Therefore, the above-mentioned coating composition is excellent in solubility in an alkyl ester, and as a result, is excellent in handleability and workability.
  • the above coating composition contains an aromatic ring-containing isocyanate as a polyisocyanate component.
  • the acrylic polyol contains a polymer of a monomer composition containing a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer.
  • the above-mentioned coating composition can obtain a laminate having excellent gas barrier properties and retort resistance (heat resistant water).
  • FIG. 1 is a schematic view of a laminated film as a laminated body obtained by using the above coating composition.
  • the laminated film 1 includes a resin film 2, an inorganic thin film layer 3 arranged on one side in the thickness direction of the resin film 2, a polyurethane layer 4 arranged on one side in the thickness direction of the inorganic thin film layer 3, and a polyurethane layer 4. It includes an adhesive layer 5 arranged on one side in the thickness direction and a sealant layer 6 arranged on one side in the thickness direction of the adhesive layer 5.
  • a first film 10 having a resin film 2 an inorganic thin film layer 3 and a polyurethane layer 4 and a second film 11 having a sealant layer 6 are bonded to each other via an adhesive layer 5. It is formed by being done.
  • the first film 10 is formed, for example, by laminating the polyurethane layer 4 on the surface of the inorganic thin film layer 3 laminated on the resin film 2.
  • Examples of the resin film 2 include a plastic film containing a thermoplastic resin.
  • thermoplastic resin examples include polyolefin resin, polyester resin, polyamide resin, polyvinyl resin and the like.
  • thermoplastic resins can be used alone or in combination of two or more.
  • thermoplastic resin examples include polyolefin resin and polyester resin.
  • the resin film 2 preferably contains a polyolefin resin and / or a polyester resin.
  • polystyrene resin examples include polyethylene (PE), polypropylene (PP), polyethylene / polypropylene copolymer (random copolymer / block copolymer), and the like.
  • polyester resin examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polylactic acid and the like.
  • the resin film 2 may be a coextruded film or a composite film to which a plurality of thermoplastic resin films are attached. good.
  • the resin film 2 may be surface-treated, if necessary.
  • Examples of the surface treatment include corona discharge treatment and primer treatment.
  • the resin film 2 may be an unstretched film, or may be a uniaxial or biaxially stretched film.
  • These resin films 2 can be used alone or in combination of two or more.
  • the resin film 2 examples include a plastic film made of a polyester resin and a plastic film made of a polyolefin resin, more preferably a plastic film made of a polyester resin, and further preferably a plastic film made of polyethylene terephthalate. Can be mentioned.
  • the thickness of the resin film 2 is not particularly limited, but is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more, and for example, 200 ⁇ m or less, preferably 100 ⁇ m or less.
  • the inorganic thin film layer 3 is arranged on one side in the thickness direction of the resin film 2, and more specifically, is laminated on the surface of one side of the resin film 2.
  • the inorganic thin film layer 3 is a thin film made of an inorganic material.
  • Examples of the inorganic material include inorganic substances, inorganic oxides, and inorganic nitrogen oxides.
  • Examples of the inorganic substance include magnesium, calcium, barium, titanium, zirconium, aluminum, indium, silicon, germanium, tin and the like.
  • inorganic oxide examples include magnesium oxide, titanium oxide, aluminum oxide, indium oxide, silicon oxide, tin oxide and the like.
  • Examples of the inorganic nitrogen oxide include silicon nitride and the like.
  • These inorganic materials can be used alone or in combination of two or more.
  • aluminum, silicon, aluminum oxide, and silicon oxide are preferable, and aluminum oxide and silicon oxide are more preferable, from the viewpoint of gas barrier properties.
  • the inorganic thin film layer 3 preferably contains aluminum oxide and / or silicon oxide.
  • the inorganic thin film layer 3 is formed on one surface of the resin film 2 by a known method.
  • Examples of the method for forming the inorganic thin film layer 3 include a vapor deposition method (vacuum vapor deposition method, EB vapor deposition method, etc.), a sputtering method, an ion plating method, a laminating method, a plasma vapor deposition method (CVD method, etc.), and the like. Be done.
  • a vapor deposition method is preferably mentioned, and a vacuum vapor deposition method is more preferable, from the viewpoint of production efficiency.
  • the inorganic thin film layer 3 is preferably an inorganic thin-film layer.
  • the thickness of the inorganic thin film layer 3 is not particularly limited, but is, for example, 1 nm or more, preferably 2 nm or more, for example, 500 nm or less, preferably 300 nm or less.
  • the total thickness of the resin film 2 and the thickness of the inorganic thin film layer 3 is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more, and for example, 200 ⁇ m or less, preferably 100 ⁇ m or less.
  • a composite film in which the inorganic thin film layer 3 is laminated on the surface of the resin film 2 (hereinafter, may be referred to as a base film) can also be obtained as a commercially available product.
  • Examples of such commercially available products include Barrier Rocks (registered trademark, manufactured by Toray Film Processing Co., Ltd., alumina-deposited polyethylene terephthalate film) series, Tech Barrier (registered trademark, manufactured by Mitsubishi Chemical Corporation, silica-deposited polyethylene terephthalate film) and the like. Be done.
  • the polyurethane layer 4 contains a cured product of the above-mentioned coating composition.
  • the polyurethane layer 4 is formed, for example, by applying the above coating composition to the inorganic thin film layer 3 and drying and curing (curing) it.
  • the polyisocyanate component (curing agent) and the polyol component (main agent) are blended in the above ratio, and a mixture (coating composition) thereof is applied to the inorganic thin film layer 3.
  • the coating temperature of the coating composition is, for example, 5 ° C. or higher, preferably 10 ° C. or higher, and for example, 50 ° C. or lower, preferably 40 ° C. or lower.
  • the coating amount of the coating composition is, for example, 0.1 g / m 2 or more, preferably 0.3 g / m 2 or more, and for example, 10 g / m 2 or less, preferably 5 g / m 2 or less. Is.
  • the drying temperature of the coating composition is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, and for example, 200 ° C. or lower, preferably 150 ° C. or lower.
  • the drying time is, for example, 10 seconds or more, preferably 30 seconds or more, and for example, 1 hour or less, preferably 30 minutes or less.
  • the curing temperature (curing temperature) is, for example, 5 ° C. or higher, preferably 10 ° C. or higher, and for example, 50 ° C. or lower, preferably 40 ° C. or lower.
  • the curing time is, for example, 10 hours or more, preferably 20 hours or more, and for example, 200 hours or less, preferably 100 hours or less.
  • the polyurethane layer 4 as a cured product of the coating composition is laminated on the inorganic thin film layer 3.
  • the thickness of the polyurethane layer 4 is not particularly limited, but is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more, for example, 200 ⁇ m or less, preferably 100 ⁇ m or less.
  • the first film 10 including the resin film 2, the inorganic thin film layer 3 and the polyurethane layer 4 can be obtained.
  • the thickness of the first film 10 is not particularly limited, but is, for example, 50 ⁇ m or more, preferably 100 ⁇ m or more, and for example, 2000 ⁇ m or less, preferably 1000 ⁇ m or less.
  • the second film 20 includes the sealant layer 6, preferably composed of the sealant layer 6.
  • the sealant layer 6 is a heat-sealing layer that imparts heat-sealing properties to the laminated film 1.
  • sealant layer 6 examples include a thermoplastic polyolefin film.
  • thermoplastic polyolefin film examples include a polyethylene film and an unstretched polypropylene film (CPP film).
  • thermoplastic polyolefin films can be used alone or in combination of two or more.
  • thermoplastic polyolefin film an unstretched polypropylene film (CPP film) is preferable.
  • the thickness of the second film 20 is, for example, 10 ⁇ m or more, preferably 20 ⁇ m or more, and for example, 200 ⁇ m or less, preferably 150 ⁇ m or less.
  • the second film 20 may be surface-treated, if necessary.
  • the surface treatment include corona discharge treatment and primer treatment.
  • the adhesive layer 5 is a layer interposed between the polyurethane layer 4 of the first film 10 and the sealant layer 6 of the second film 20 to bond the first film 10 and the second film 20.
  • the adhesive layer 5 is obtained by applying and drying a known laminated adhesive.
  • laminated adhesive examples include polyolefin adhesives, acrylic adhesives, polyester adhesives, phenol resin adhesives, epoxy adhesives, polyurethane adhesives, rubber adhesives, and silicone adhesives. And so on.
  • These laminated adhesives can be used alone or in combination of two or more.
  • the method for forming the adhesive layer 5 is not particularly limited, but is, for example, laminated on one side of the polyurethane layer 4 of the first film 10 in the thickness direction and / or on the other side of the sealant layer 6 of the second film 20 in the thickness direction. An adhesive is applied, and the first film 10 and the second film 20 are bonded together, dried and cured.
  • a laminating adhesive is applied to one side of either the first film 10 or the second film 20 in the thickness direction.
  • the laminate adhesive is applied to one side of the first film 10 in the thickness direction (that is, the surface of the polyurethane layer 4).
  • the coating temperature of the laminate adhesive is, for example, 35 ° C. or higher, preferably 40 ° C. or higher, for example, 100 ° C. or lower, preferably 90 ° C. or lower, and more preferably 85 ° C. or lower.
  • the amount of the laminate adhesive applied is, for example, 0.5 g / m 2 or more, preferably 1 g / m 2 or more, and for example, 5 g / m 2 or less, preferably 4.5 g / m 2 or less. Is.
  • the laminating device in which the laminating adhesive is used either a forward transfer type coating device or a reverse transfer type coating device (reverse coater) can be used.
  • the coated surface is attached to the other film (preferably the second film 20) and cured (cured) at room temperature or under heating.
  • the curing conditions of the laminated adhesive are appropriately set according to the purpose and application.
  • the adhesive layer 5 is obtained as a cured product of the laminated adhesive.
  • the thickness of the adhesive layer 5 is, for example, 10 ⁇ m or more, preferably 20 ⁇ m or more, and for example, 200 ⁇ m or less, preferably 150 ⁇ m or less.
  • the resin film 2, the inorganic thin film layer 3 arranged on one side in the thickness direction of the resin film 2, the polyurethane layer 4 arranged on one side in the thickness direction of the inorganic thin film layer 3, and the polyurethane layer 4 A laminated film 1 including an adhesive layer 5 arranged on one side in the thickness direction and a sealant layer 6 arranged on one side in the thickness direction of the adhesive layer 5 can be obtained.
  • the thickness of the laminated film 1 is, for example, 20 ⁇ m or more, preferably 30 ⁇ m or more, and for example, 180 ⁇ m or less, preferably 150 ⁇ m or less.
  • Such a laminated film 1 is obtained by using the above coating composition, it is well obtained in workability, and is also excellent in gas barrier property and retort resistance.
  • such a laminated film 1 is suitably used as a packaging material in various industrial fields such as foods, beverages, pharmaceuticals and quasi-drugs.
  • Example 1 Acrylic polyols were prepared according to the formulations shown in Table 1.
  • the monomer composition prepared by the formulation shown in Table 1 was dispersed in ethyl acetate, 1.0 part by mass of azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was 60 ° C. The reaction was carried out for 10 hours. As a result, an acrylic polyol (polyol compound) was obtained.
  • AIBN azobisisobutyronitrile
  • acrylic polyol solution an ethyl acetate solution of acrylic polyol (polyol component (hereinafter referred to as acrylic polyol solution)) was obtained.
  • the glass transition temperature (Tg) of the obtained acrylic polyol was calculated by the formulation of the monomer composition and the FOX formula.
  • the number average molecular weight (Mn) of the acrylic polyol was calculated as a standard polystyrene-equivalent molecular weight by gel permeation chromatography.
  • an alumina-deposited PET film (alumina-deposited polyethylene terephthalate film) was prepared as a base film provided with a resin film and an inorganic thin film layer.
  • the above coating composition was coated on the inorganic thin film layer (alumina side) using a bar coater so as to have a drying thickness of 0.5 g / m 2, and then put into a drying oven set at 110 ° C. It was dried for 1 minute and cured at 40 ° C. for 2 days.
  • an unstretched polypropylene film (Tosero CP RXC-22 (CPP film, # 60), manufactured by Mitsui Chemicals Toshiro Co., Ltd.) as a sealant layer was laminated on the surface of the adhesive and cured at 40 ° C. for 3 days.
  • Acrylic polyol solutions (solid content concentration 50%) were prepared according to the formulations shown in Tables 1 to 3. Further, after mixing 0.7 g of an acrylic polyol solution (solid content concentration 50%) and 8.4 g of ethyl acetate, Takenate D-110N (manufactured by Mitsui Chemicals, Inc., XDI trimethylolpropane adduct, solid content concentration 75%, Ethyl acetate solution) 0.9 g was mixed. Other than that, a coating composition and a laminated film were obtained by the same method as in Example 1.
  • Example 3 An acrylic polyol solution (solid content concentration 50%) was prepared according to the formulation shown in Table 1. Further, after mixing 1.0 g of an acrylic polyol solution (solid content concentration 50%) and 8.3 g of ethyl acetate, Takenate D-110N (manufactured by Mitsui Chemicals, Inc., XDI trimethylolpropane adduct, solid content concentration 75%, Ethyl acetate solution) 0.7 g was mixed. Other than that, a coating composition and a laminated film were obtained by the same method as in Example 1.
  • Example 4 An acrylic polyol solution (solid content concentration 50%) was prepared according to the formulation shown in Table 1. Further, after mixing 1.3 g of an acrylic polyol solution (solid content concentration 50%) and 8.2 g of ethyl acetate, Takenate D-110N (manufactured by Mitsui Chemicals, Inc., XDI trimethylolpropane adduct, solid content concentration 75%, Ethyl acetate solution) 0.5 g was mixed. Other than that, a coating composition and a laminated film were obtained by the same method as in Example 1.
  • Example 5 An acrylic polyol solution (solid content concentration 50%) was prepared according to the formulation shown in Table 1. Further, after mixing 1.0 g of an acrylic polyol solution (solid content concentration 50%) and 8.3 g of ethyl acetate, Takenate D-110N (manufactured by Mitsui Chemicals, Inc., XDI trimethylolpropane adduct, solid content concentration 75%, Ethyl acetate solution) 0.7 g was mixed. Other than that, a coating composition and a laminated film were obtained by the same method as in Example 1.
  • Example 7 An acrylic polyol solution (solid content concentration 50%) was prepared according to the formulation shown in Table 1. Further, after mixing 0.9 g of an acrylic polyol solution (solid content concentration 50%) and 8.4 g of ethyl acetate, Takenate D-110N (manufactured by Mitsui Chemicals, Inc., XDI trimethylolpropane adduct, solid content concentration 75%, Ethyl acetate solution) 0.7 g was mixed. Other than that, a coating composition and a laminated film were obtained by the same method as in Example 1.
  • Example 14 An acrylic polyol solution (solid content concentration 50%) was prepared according to the formulation shown in Table 2. Further, after mixing 0.5 g of an acrylic polyol solution (solid content concentration 50%) and 8.4 g of ethyl acetate, Takenate D-110N (manufactured by Mitsui Chemicals, Inc., XDI trimethylolpropane adduct, solid content concentration 75%, 0.7 g of ethyl acetate solution) and 0.2 g of Takenate T-50 (XDI monomer manufactured by Mitsui Kagaku Co., Ltd.) were mixed. Other than that, a coating composition and a laminated film were obtained by the same method as in Example 1.
  • Example 15 An acrylic polyol solution (solid content concentration 50%) was prepared according to the formulation shown in Table 2. Further, after mixing 0.7 g of an acrylic polyol solution (solid content concentration 50%) and 8.4 g of ethyl acetate, Takenate D-131N (manufactured by Mitsui Chemicals, Inc., isocyanurate modified product of XDI, solid content concentration 75%, acetate). Ethyl solution) 0.9 g was mixed. Other than that, a coating composition and a laminated film were obtained by the same method as in Example 1.
  • Comparative Example 6 An acrylic polyol solution (solid content concentration 50%) was prepared according to the formulation shown in Table 3. Further, after mixing 0.7 g of an acrylic polyol solution (solid content concentration 50%) and 8.4 g of ethyl acetate, Takenate D-160 (manufactured by Mitsui Chemicals, Inc., HDI trimethylolpropane adduct, solid content concentration 75% acetate). Ethyl solution) 0.9 g was mixed. Other than that, a coating composition and a laminated film were obtained by the same method as in Example 1.
  • Example 17 and Comparative Examples 7-10 Example 2, Comparative Examples 1 and 2 and Comparative Example 5 except that a silica-deposited PET film (silica-deposited polyethylene terephthalate film) was used instead of the alumina-deposited PET film (alumina-deposited polyethylene terephthalate film) as the base film.
  • a coating composition and a laminated film were obtained in the same manner as in each of No. 6 and 6.
  • Examples 18 and Comparative Examples 11-14 Example 2 and Comparative Examples 1 and 2 and comparison except that a silica-deposited BOPP film (silica-deposited biaxially stretched polypropylene film) was used instead of the alumina-deposited PET film (alumina-deposited polyethylene terephthalate film) as the base film.
  • the coating composition and the laminated film were obtained in the same manner as in Examples 5 to 6, respectively.
  • the OTR reduction rate due to the retort treatment was calculated from the amount of oxygen permeation before and after the retort treatment based on the following formula.
  • OTR reduction rate oxygen permeation before retort treatment / oxygen permeation after retort treatment
  • the polyurethane layer and the resin film were peeled off in the shear direction at a speed of 300 mm / min by a tensile tester.
  • the blocking property was evaluated based on the following criteria. ⁇ : The strength was 1N or less. ⁇ : The strength was 1N or more, and it could be easily peeled off by hand. X: The strength was 2N or more.
  • AA Acrylic acid St: Styrene MMA: Methyl methacrylate BA: n-butyl acrylate AN: Acrylonitrile HEA: 2-Hydroxyethyl acrylate HEMA: 2-Hydroxyethyl methacrylate OTR: Oxygen permeability D-110N: Takenate D-110N, XDI Trimethylolpropane adduct, solid content concentration 75%, ethyl acetate solution, manufactured by Mitsui Kagaku Co., Ltd.
  • D-131N Takenate D-131N, isocyanurate modified product of XDI, solid content concentration 75%, ethyl acetate solution, manufactured by Mitsui Kagaku Co., Ltd.
  • T-50 Takenate T-50, XDI monomer, Mitsui Kagaku Co., Ltd.
  • D-103H Takenate D-103H, TDI trimethylolpropane adduct, solid content concentration 75%, ethyl acetate solution, Mitsui Kagaku Co., Ltd.
  • AlOxPET Alumina-deposited polyethylene terephthalate film
  • SiOxPET Silica-deposited polyethylene terephthalate film
  • SiOxBOPP Silica-deposited biaxially stretched polypropylene film MF: Substrate cut (base film breakage)
  • the coating composition and laminate of the present invention are suitably used in the fields of food packaging materials, beverage packaging materials, pharmaceutical packaging materials, and quasi-drug packaging materials.
  • Laminate film 2 Resin film 3 Inorganic thin film layer 4 Polyurethane layer 5 Adhesive layer 6 Sealant layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
PCT/JP2021/025283 2020-07-06 2021-07-05 コーティング組成物および積層体 Ceased WO2022009829A1 (ja)

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CN202180042243.XA CN115698202A (zh) 2020-07-06 2021-07-05 涂覆组合物及层叠体
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JP2013188871A (ja) * 2012-03-12 2013-09-26 Toppan Printing Co Ltd ガスバリア積層フィルム
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JP2013188871A (ja) * 2012-03-12 2013-09-26 Toppan Printing Co Ltd ガスバリア積層フィルム
JP2014185317A (ja) * 2013-02-25 2014-10-02 Toyo Ink Sc Holdings Co Ltd 電池用包装材用ポリウレタン接着剤、電池用包装材、電池用容器および電池
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