WO2022239667A1 - 積層体の製造方法 - Google Patents

積層体の製造方法 Download PDF

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Publication number
WO2022239667A1
WO2022239667A1 PCT/JP2022/019237 JP2022019237W WO2022239667A1 WO 2022239667 A1 WO2022239667 A1 WO 2022239667A1 JP 2022019237 W JP2022019237 W JP 2022019237W WO 2022239667 A1 WO2022239667 A1 WO 2022239667A1
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acid
composition
film
adhesive
coating
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English (en)
French (fr)
Japanese (ja)
Inventor
正光 新居
大樹 冨田
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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

Definitions

  • the present invention relates to a method for manufacturing a laminate.
  • Laminates used for various packaging materials, labels, etc. are given design, functionality, storage stability, convenience, transportation resistance, etc. by laminating a wide variety of base materials such as plastic films, metal foils, and paper. be done.
  • a packaging material formed by molding the laminate into a bag shape is used as a packaging material for foods, medicines, detergents, and the like.
  • Patent Document 1 a reactive two-liquid type laminating adhesive (hereinafter referred to as solvent-free adhesive) that does not contain a volatile organic solvent is known (Patent Document 1).
  • An adhesive with oxygen barrier properties is also known (Patent Document 2).
  • a general method for manufacturing a laminate using such an adhesive is a so-called non-solvent lamination method in which two liquids are mixed in advance and applied to a base material, which is then laminated to the other base material.
  • Solvent-free adhesives do not require a drying process and do not emit solvents. They are energy-saving and have low running costs. It has many merits, such as the fact that there is no concern that the solvent will remain in the laminate after being combined.
  • the present invention has been made in view of such problems, and manufactures a laminate that has an excellent curing speed and does not have a pot life problem even when a solventless adhesive having oxygen barrier properties is used.
  • the purpose is to provide a method.
  • the present invention provides the steps of applying a first composition containing a polyisocyanate compound to a first substrate, applying a second composition containing a compound having an active hydrogen group to a second substrate, A step of bonding the first substrate and the second substrate so that the first composition and the second composition are in contact, and reacting the first composition and the second composition and forming an adhesive layer, wherein the adhesive layer has an oxygen permeability of 300 cc/m 2 ⁇ day ⁇ atm or less.
  • FIG. 1 is a schematic diagram of a laminate manufacturing apparatus used in the present invention.
  • FIG. 2 is a schematic diagram showing a main part of a first coating section in the laminate manufacturing apparatus shown in FIG.
  • FIG. 3 is a schematic diagram showing a main part of a second coating section in the laminate manufacturing apparatus shown in FIG.
  • the method for producing a laminate of the present invention includes the steps of applying a first composition containing a polyisocyanate compound to a first substrate, and a second composition containing a compound having an active hydrogen group on a second substrate.
  • a step of applying a substance a step of bonding the first substrate and the second substrate so that the first composition and the second composition are in contact, and the first composition and and reacting with a second composition to form an adhesive layer.
  • the oxygen permeability of the adhesive layer is 300 cc/m 2 ⁇ day ⁇ atm or less.
  • first base material First, the first base material, the second base material, and the adhesive used in the manufacturing method of the present invention will be described.
  • first base material films, sheets, and the like, which are excellent in chemical and physical strength (unless otherwise specified, hereinafter, films and sheets are collectively referred to as films and sheets), paper, and the like can be used without particular limitations.
  • the base material may be a single layer film or a multi-layer laminated film.
  • An inorganic deposition layer may be provided on the single layer or multilayer film. It can be appropriately selected according to usage conditions such as the contents of the packaging material described later, the type, and the presence or absence of heat treatment after the contents are filled.
  • films include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, polybutene, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ionomer, ethylene-( meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-propylene copolymer, methylpentene, polyacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polycarbonate , polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polybutylene Examples include, but are
  • uniaxially or biaxially oriented polyester films such as polyethylene terephthalate and polyethylene naphthalate
  • uniaxially or biaxially oriented polyamide films such as nylon 6, nylon 66, MXD6 (polymetaxylylene adipamide), biaxially oriented polypropylene films , a biaxially oriented polyethylene film and the like
  • uniaxially or biaxially oriented polyester films such as polyethylene terephthalate and polyethylene naphthalate
  • uniaxially or biaxially oriented polyamide films such as nylon 6, nylon 66, MXD6 (polymetaxylylene adipamide)
  • biaxially oriented polypropylene films a biaxially oriented polyethylene film and the like
  • the thickness of the film is not particularly limited, and may be appropriately selected within the range of 1 to 300 ⁇ m from the viewpoint of moldability and transparency. It is preferably in the range of 1 to 100 ⁇ m. If it is less than 1 ⁇ m, the strength will be insufficient, and if it exceeds 300 ⁇ m, the rigidity will be too high, which may make processing difficult.
  • the film that serves as the substrate is subjected to some surface treatment, such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, physical treatment such as glow discharge treatment, or chemical treatment. Chemical treatment such as oxidation treatment or other treatment may be applied.
  • surface treatment such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, physical treatment such as glow discharge treatment, or chemical treatment.
  • Chemical treatment such as oxidation treatment or other treatment may be applied.
  • the film can be produced, for example, by using one or more selected from the resins described above, and by a conventionally known film-forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, and an inflation method. .
  • a conventionally known film-forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, and an inflation method.
  • two or more resins selected from the resins described above can be used, and can be produced by a multi-layer co-extrusion film forming method. From the viewpoint of film strength, dimensional stability, and heat resistance, the film may be stretched uniaxially or biaxially using a tenter system, tubular system, or the like.
  • the film may contain additives as necessary. Specifically, it improves workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, releasability, flame resistance, mold resistance, electrical properties, strength, etc.
  • plastic compounds and additives such as lubricants, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents and pigments can be added. The amount of additive added is adjusted within a range that does not affect other performances.
  • a known paper base material can be used without any particular limitation. Specifically, it is produced by a known paper machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified.
  • natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as Manila hemp pulp, sisal pulp and flax pulp, and pulp obtained by chemically modifying these pulps.
  • the types of pulp that can be used include chemical pulp, ground pulp, chemi-grand pulp, thermomechanical pulp, and the like prepared by sulfate cooking, acid/neutral/alkaline sulfite cooking, soda salt cooking, and the like.
  • various types of commercially available fine paper, coated paper, lined paper, impregnated paper, cardboard, paperboard, etc. can also be used.
  • the inorganic vapor deposition layer can be provided by a conventionally known method directly on the film or paper or via a layer formed using an anchor coating agent or the like.
  • methods for forming the inorganic deposition layer include physical vapor deposition methods (PVD methods) such as vacuum deposition methods, sputtering methods, and ion plating methods, plasma chemical vapor deposition methods, thermal A chemical vapor deposition method (Chemical Vapor Deposition method (CVD method)) such as a chemical vapor deposition method and a photochemical vapor deposition method can be used.
  • PVD methods physical vapor deposition methods
  • CVD method Chemical Vapor Deposition method
  • the inorganic deposition layer can be formed from any material such as various metals and their oxides.
  • aluminum, alumina (aluminum oxide), silica (silicon oxide), combinations thereof (for example, silica and alumina), and the like are preferably used.
  • the film thickness of the inorganic deposition layer is preferably 1 to 200 nm.
  • the thickness thereof is more preferably 1 to 100 nm, more preferably 15 to 60 nm.
  • the inorganic deposition layer is silica, alumina, or a binary deposition layer thereof, the film thickness is preferably 1 to 100 nm, more preferably 10 to 50 nm, and more preferably 20 to 30 nm. .
  • An anchor coat layer may be provided on the film prior to the formation of the inorganic deposition layer.
  • the anchor coat layer can be formed by applying an anchor coat agent on the film and drying it.
  • the adhesion between the film and the inorganic deposited layer can be improved, and the flatness of the inorganic deposited layer formation surface can be improved by the leveling action of the anchor coating agent, resulting in a uniform inorganic deposited layer with few film defects such as cracks. can be formed.
  • anchor coating agents include solvent-soluble or water-soluble polyester resins, isocyanate resins, urethane resins, acrylic resins, vinyl alcohol resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, oxazoline group-containing resins, modified styrene.
  • anchor coating agents include resins, modified silicone resins, alkyl titanates, and the like. These can be used alone or in combination of two or more.
  • the film thickness of the anchor coat layer is not particularly limited, it is preferably about 5 nm to 5 ⁇ m, more preferably 10 nm to 1 ⁇ m. Thereby, a uniform layer with suppressed internal stress can be formed on the film.
  • an anchor coat layer When an anchor coat layer is provided, it is also preferable to perform discharge treatment on the surface of the film prior to forming the anchor coat layer in order to improve the applicability and adhesiveness of the anchor coat agent.
  • the second base material used in the present invention the same material as the first base material can be used.
  • the second substrate is heat-sealable and includes a sealant film that can be thermally melted and fused together.
  • heat-sealable resins include polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-( Olefin resins such as meth)acrylic acid copolymer, ethylene-(meth)ethyl acrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene are treated with acrylic acid, methacrylic acid, maleic anhydride, Modified olefin resins modified with fumaric acid and other unsaturated carboxylic acids, ethylene-(meth)acrylic ester-unsaturated carboxylic acid terpolymers, cyclic polyolefins, cyclic olefin copolymers, polyethylene terephthalate (PET), polyacrylonitrile (PAN) and the
  • the second base material includes an easily peelable sealant film (easy peel film).
  • Easy peel film any of an interfacial peeling type, a cohesive peeling type, and an interlaminar peeling type can be applied, and can be appropriately selected according to the type and required properties of the packaging material described later.
  • the easy peelability index is appropriately set according to the type and required properties of the packaging material. For example, a phase-separated polymer blend in which polypropylene is combined with high-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, or the like can exhibit easy peelability.
  • the film thickness of the sealant film can be arbitrarily selected, but is selected in the range of 5 to 500 ⁇ m, for example, when applied to the packaging material described later. It is more preferably 10 to 250 ⁇ m, even more preferably 15 to 100 ⁇ m. If the thickness is less than 5 ⁇ m, sufficient lamination strength as a packaging material cannot be obtained, and there is a possibility that the puncture resistance and the like may be lowered. If the thickness exceeds 250 ⁇ m, the cost increases, the film becomes hard, and workability deteriorates.
  • the second base material may contain an inorganic deposition layer formed on the film.
  • the inorganic deposition layer can be formed by the same method as exemplified for the first substrate.
  • the adhesive used in the production method of the present invention contains a polyol compound (A) and a polyisocyanate compound (B), and is a multi-liquid solvent-free adhesive layer that forms an adhesive layer by reacting and curing. mold glue. Further, the oxygen permeability of the adhesive layer is 300 cc/m 2 ⁇ day ⁇ atm or less.
  • the oxygen transmission rate of the adhesive layer in this specification is a value obtained by converting the value measured at 23° C. and 0% RH when the coating amount of the adhesive is 3 g/m 2 .
  • polyester polyol (A1) obtained by polycondensation of a polyhydric carboxylic acid containing an ortho-oriented polyhydric carboxylic acid and a polyhydric alcohol as the polyol compound (A)
  • isocyanurate examples include those containing at least one of polyester polyol (A2) having a ring and polyester polyol (A3) having a polymerizable carbon-carbon double bond.
  • the polyisocyanate compound (B) at least one of the polyester polyols (A1) to (A3) and an isocyanate compound are reacted under conditions in which the isocyanate groups are excessive. Examples include those containing polyester polyisocyanate. .
  • Such adhesives tend to have high viscosity, and from the viewpoint of coatability, it is necessary to heat the adhesive before use. For this reason, in the case of using the non-solvent lamination method in which the components of the adhesive are mixed in advance and then applied to the base material, the reaction of the adhesive tends to proceed, and the pot life tends to be shortened. With the production method of the present invention, such an adhesive can be used without worrying about pot life.
  • the ortho-oriented polycarboxylic acid used in the synthesis of the polyester polyol (A1) includes orthophthalic acid or its acid anhydride, naphthalene 2,3-dicarboxylic acid or its acid anhydride, naphthalene 1,2-dicarboxylic acid or its acid anhydrides, anthraquinone 2,3-dicarboxylic acid or its acid anhydride, 2,3-anthracenecarboxylic acid or its acid anhydride, and the like. These compounds may have a substituent at any carbon atom of the aromatic ring.
  • the substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, naphthyl group and the like.
  • the polyvalent carboxylic acid used for synthesizing the polyester polyol (A1) may contain a polyvalent carboxylic acid other than the ortho-oriented polyvalent carboxylic acid.
  • Polycarboxylic acids other than ortho-oriented polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid; maleic anhydride, maleic acid, fumaric acid, and the like.
  • unsaturated bond-containing polycarboxylic acids alicyclic polycarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid and these acid anhydrides or ester-forming derivatives of dicarboxylic acids, aromatic polycarboxylic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids; can be used alone or in combination of two or more. Among them, succinic acid,
  • the ratio of the ortho-oriented polycarboxylic acid to the total amount of the polycarboxylic acid is preferably 40 to 100% by mass.
  • the polyhydric alcohol used to synthesize the polyester polyol (A1) preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, and ethylene glycol. It is more preferable to include
  • Polyhydric alcohols other than the above may be used in combination, such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, and dimethylbutanediol.
  • butylethylpropanediol diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol; glycerin, trimethylolpropane, trimethylolethane, tris(2-hydroxyethyl) isocyanurate, 1 , 2,4-Butanetriol, pentaerythritol, dipentaerythritol and other polyhydric alcohols having a valence of 3 or more, hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and these and aromatic polyhydric phenols such as hydrogenated alicyclic aromatic polyhydric phenols.
  • polyester polyol (A1) has 3 or more hydroxyl groups (referred to as polyester polyol (a1) for convenience), some of the hydroxyl groups may be modified with acid groups.
  • polyester polyols are hereinafter also referred to as polyester polyols (A1').
  • the polyester polyol (A1') is obtained by reacting the polyester polyol (a1) with a polyvalent carboxylic acid or an acid anhydride thereof.
  • the ratio of hydroxyl groups to be modified with polycarboxylic acid is preferably 1/3 or less of the hydroxyl groups provided in the polyester polyol (a1).
  • Polyvalent carboxylic acids used for modification include succinic anhydride, maleic acid, maleic anhydride, fumaric acid, 1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, and 5-norbornene.
  • a polyester polyol (A2) is obtained by reacting a compound having two or more functional groups capable of reacting with at least one of an isocyanuric ring and a carboxyl group or a hydroxyl group, a polycarboxylic acid, and a polyhydric alcohol.
  • Examples of compounds having two or more functional groups capable of reacting with at least one of an isocyanuric ring and a carboxyl group or a hydroxyl group include 1,3,5-tris(aminomethyl)isocyanuric acid, 1,3,5-tris(2-amino ethyl)isocyanuric acid, 1,3-bis(2-aminoethyl)-5-methyl-isocyanuric acid, 1,3-bis(2-aminoethyl)-5-ethyl-isocyanuric acid, 1,3-bis(2 -aminoethyl)-5-propyl-isocyanuric acid, 1,3-bis(2-aminoethyl)-5-butyl-isocyanuric acid, 1,3,5-tris(3-aminopropyl)isocyanuric acid, 1,3 - isocyanuric acids with an amino group such as bis(3-aminopropyl)-5-methyl-isocyanuric acid,
  • 1,3,5-tris(hydroxymethyl)isocyanuric acid 1,3-bis(hydroxymethyl)-5-methyl-isocyanuric acid, 1,3-bis(hydroxymethyl)-5-ethyl-isocyanuric acid, 1, 3-bis(hydroxymethyl)-5-butyl-isocyanuric acid, 1,3-bis(hydroxymethyl)-5-phenyl-isocyanuric acid, 1-(hydroxyethyl)-3,5-bis(hydroxymethyl)-isocyanuric acid acid, 1,3,5-tris(1-hydroxyethyl)isocyanuric acid, 1,3-bis(hydroxymethyl)-5-(2-hydroxypropyl)isocyanuric acid, 1,3-bis(hydroxymethyl)-5 -(2-hydroxy-1-methylpropyl)isocyanuric acid, 1,3-bis(hydroxymethyl)-5-(2-hydroxy-2-methylpropyl)isocyanuric acid, 1,3,5-tris(2-hydroxy ethyl)isocyanuric acid, 1,3-bis(2-hydroxy
  • 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid 1,3-bis(2,3-epoxypropyl)-5-methyl-isocyanuric acid, 1,3-bis(2,3-epoxy propyl)-5-ethyl-isocyanuric acid, 1,3-bis(2,3-epoxypropyl)-5-propyl-isocyanuric acid, 1,3,5-tris(3,4-epoxybutyl)isocyanuric acid, etc. isocyanuric acid having a glycidyl group,
  • 1,3,5-tris(carboxy)isocyanuric acid 1,3,5-tris(carboxymethyl)isocyanuric acid, 1,3-bis(carboxymethyl)-5-methyl-isocyanuric acid, 1,3-bis( carboxymethyl)-5-ethyl-isocyanuric acid, 1,3-bis(carboxymethyl)-5-butyl-isocyanuric acid, 1,3-bis(carboxymethyl)-5-phenyl-isocyanuric acid, 1,3-bis (Carboxyethyl)-5-methyl-isocyanuric acid, 1,3-bis(carboxyethyl)-5-ethyl-isocyanuric acid, 1,3-bis(carboxypropyl)-5-methyl-isocyanuric acid, 1,3- Isocyanuric acid having a carboxyl group such as bis(carboxyethyl)-5-butyl-isocyanuric acid, 1,3,5-tris(carboxypropy
  • polyhydric carboxylic acid and polyhydric alcohol used to synthesize the polyester polyol (A2) the same ones as exemplified for the polyester polyol (A1) can be used. It is preferable to use an ortho-oriented polyvalent carboxylic acid.
  • the polyhydric alcohol preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol.
  • the ratio of the compound having an isocyanuric ring in the raw material of the polyester polyol (A2) is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the content is preferably 60% by mass or less, more preferably 50% by mass or less.
  • the polyester polyol (A3) is obtained by using a component having a polymerizable carbon-carbon double bond as a polyhydric carboxylic acid or polyhydric alcohol.
  • polyvalent carboxylic acids having polymerizable carbon-carbon double bonds examples include maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its acid anhydrides, and 3-methyl-4-cyclohexene. -1,2-dicarboxylic acids and acid anhydrides thereof.
  • Maleic anhydride, maleic acid, and fumaric acid are preferable because it is presumed that the smaller the number of carbon atoms, the less flexible the molecular chain becomes and the more difficult it is for oxygen to permeate.
  • polyhydric alcohols having a polymerizable carbon-carbon double bond examples include 2-butene-1,4-diol.
  • polyhydric carboxylic acids and polyhydric alcohols that do not have a polymerizable carbon-carbon double bond may be used in combination.
  • polyhydric carboxylic acid and polyhydric alcohol those similar to polyester polyols (A1) and (A2) can be used.
  • Polyvalent carboxylic acid is preferably at least one selected from the group consisting of succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid and isophthalic acid, and orthophthalic acid and acid anhydride thereof.
  • At least one polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol is preferably used, and ethylene glycol is more preferably used.
  • the hydroxyl value of the polyester polyols (A1) to (A3) is preferably 20 mgKOH/g or more and 250 mgKOH/g or less. If the hydroxyl value is less than 20 mgKOH/g, the molecular weight is too large and the viscosity increases, requiring a higher coating temperature. If the hydroxyl value exceeds 250 mgKOH/g, the crosslink density of the cured coating film may become too high and the adhesive strength may decrease.
  • the acid value is preferably 200 mgKOH/g or less.
  • the lower limit of the acid value is not particularly limited, it is 20 mgKOH/g or more as an example.
  • the acid value is 20 mgKOH/g or more, good gas barrier properties and initial cohesive strength can be obtained due to intermolecular interactions.
  • the hydroxyl value of the polyester polyol (A) can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070.
  • the polyester polyols (A1) to (A3) have a number average molecular weight of 300 to 5000, because a crosslink density that is excellent in the balance between adhesiveness and gas barrier properties can be obtained. More preferably, the number average molecular weight is 350-3000. The number average molecular weight is obtained by calculation from the obtained hydroxyl value and the designed number of hydroxyl functional groups.
  • the number of functional groups of the designed hydroxyl group is the number of moles of carboxyl groups (O), the number of moles of polyvalent carboxylic acid (P), and the number of moles of carboxyl groups contained in the raw materials of polyester polyols (A1) to (A3). It is calculated by (QO)/(RP) from the number of moles (Q) of the functional group and the number of moles (R) of the compound having a functional group capable of reacting with the carboxyl group.
  • the polyol compound (A) may contain a polyol (A4) other than the polyester polyols (A1) to (A3).
  • polyols (A4) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bis glycols such as hydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol;
  • trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol;
  • High density polyols such as isosorbide, isoidide, isomannide, furandimethanol, trans-tetrahydrofuran-3,4-diol, sorbitol, erythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diol;
  • Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of polymerization initiators such as glycols and trifunctional or tetrafunctional aliphatic alcohols.
  • a polyether urethane polyol obtained by further increasing the molecular weight
  • Polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, and the aforementioned glycols, glycerin, trimethylolpropane, pentaerythritol, etc.
  • polyester polyol (1) which is a reaction product with a polyhydric alcohol
  • Polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a polyvalent carboxylic acid
  • Polyester polyol (3) obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid
  • a polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid
  • polyester polyols (5) which are polymers of hydroxyl acids such as dimethylolpropionic acid and castor oil fatty acids;
  • Polyester polyether polyols obtained by reacting polyester polyols (1) to (5) with the above polyether polyols and aromatic or aliphatic polyisocyanates; Polyester polyurethane polyols obtained by polymerizing polyester polyols (1) to (5) with aromatic or aliphatic polyisocyanates; Castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated castor oil, castor oil-based polyols such as adducts of 5 to 50 moles of alkylene oxide of castor oil, and mixtures thereof.
  • Examples of the polyvalent carboxylic acid used for preparing the polyester polyol (2) include those exemplified as the raw material for the polyester polyol (A1).
  • the blending amount of the polyol (A4) can be appropriately adjusted, but as an example, it is 5% by mass or more and 90% by mass or less of the total amount of the polyester polyols (A1) to (A3) and the polyol (A4).
  • polyisocyanate compound (B) conventionally known compounds can be used without particular limitation, and tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, and hydrogenated xylylene diisocyanate. , isophorone diisocyanate or trimers of these isocyanate compounds, and excess amounts of these isocyanate compounds, for example, ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene.
  • trimethylolpropane trimethylolpropane
  • glycerol pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, metaxylylenediamine and other low-molecular-weight active hydrogen compounds and their alkylene oxide adducts
  • polyester polyols polyethers Examples thereof include adducts obtained by reacting with polyols, polyamides, and other high-molecular-weight active hydrogen compounds.
  • a blocked isocyanate may also be used as the polyisocyanate compound (B).
  • isocyanate blocking agents include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol and chlorophenol; oximes thereof such as acetoxime, methylethylketoxime and cyclohexanone oxime; alcohols such as ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; Lactams such as caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam and ⁇ -propyrolactam, and active methylene compounds such as aromatic amines, imides, acetylacetone
  • the blocked isocyanate can be obtained by addition reaction of the above isocyanate compound and an isocyanate blocking agent by a known and commonly used appropriate method.
  • An isocyanate having an aromatic ring or a derivative thereof is preferably used as the polyisocyanate compound (B) because good gas barrier properties can be obtained.
  • Specific examples of such isocyanate compounds include xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, and isocyanate compounds having a skeleton derived from diphenylmethane diisocyanate.
  • polyester polyisocyanate obtained by reacting at least one of the polyester polyols (A1) to (A3) with an isocyanate compound under conditions in which the isocyanate groups are excessive.
  • the adhesive used in the present invention may contain components other than the polyol compound (A) and polyisocyanate compound (B) described above.
  • Such components include amine compounds (C), monools (D), inorganic fillers, coupling agents, acid anhydrides, oxygen scavengers, phosphoric acids, tackifiers, urethanization catalysts, stabilizers (oxidation inhibitors, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, coloring agents, crystal nucleating agents, antifoaming agents, leveling agents and the like, but are not limited thereto.
  • Examples of the amine compound (C1) include polypropylene glycol ethylenediamine ether, propylene oxide adduct of triethanolamine, N-ethyldiethanolamine, N-methyl-N-hydroxyethyl-N-hydroxyethoxyethylamine, pentakishydroxypropyldiethylenetriamine, tetrakishydroxy
  • Examples include propylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, triethanolamine, amino group-containing aspartic acid esters, and the like.
  • the hydroxyl group of the amine compound (C1) is preferably secondary or tertiary. This makes it possible to achieve both initial cohesive strength and a sufficient pot life. In addition, when the first composition and the second composition are applied separately, the mixed layers after pressure bonding are not hindered.
  • the amino group of the amine compound (C2) is an NH2 group or an NHR group (R is an optionally functional alkyl group or aryl group).
  • R is an optionally functional alkyl group or aryl group.
  • the amine compound (C2) include methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxapyrodundecane, lysine, phenylenediamine, 2,2,4-trimethyl hexamethylenediamine, tolylenediamine, hydrazine, piperazine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, or di-2-hydroxypropylethylenediamine, poly(propylene glycol) diamine, poly(propylene glycol) triamine, poly(propylene glycol) te
  • 1,4-diaminobutane 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, etc.
  • benzyl Amine diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, etc., tetra(aminomethyl)methane, tetrakis ( 2-aminoethylaminomethyl)methane, 1,3-bis(2′-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethy
  • Primary or secondary alkanolamines such as monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine and diisopropanolamine ,
  • C2-3 primary or secondary amines
  • Examples of the tertiary amine compound (C3) having no active hydrogen group include triethylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylvalmitylamine, dimethylstearylamine, dimethylbehenylamine, and dilaurylmonomethyl.
  • amine trioctylamine, triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl Propylenediamine, N,N,N',N',N''-pentamethyldiethylenetriamine, N,N,N',N'',N'-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N', N′′,N′′-pentamethyldipropylenetriamine, N,N,N′,N′-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol , N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,
  • the amine value of the adhesive is preferably 1 mgKOH/g or more and 100 mgKOH/g or less. Thereby, an aging process can be shortened more. More preferably, it is 5 mgKOH/g or more and 80 mgKOH/g or less.
  • the amine value in this specification means the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of the sample, and is not particularly limited, and can be calculated using a known method. can.
  • the chemical structure of the amine compound (C) and, optionally, the average molecular weight, etc. are known, it can be calculated from (number of amino groups per molecule/average molecular weight) x 56.1 x 1000. can.
  • the chemical structure, average molecular weight, etc. of the amine compound are unknown, it can be measured according to a known amine value measuring method such as JISK7237-1995.
  • the adhesive may contain a monool compound (D) having one alcoholic hydroxyl group.
  • the main chain of the monool compound (D) is not particularly limited, and includes vinyl resins having one hydroxyl group, acrylic resins, polyesters, epoxy resins, urethane resins, and the like. Aliphatic alcohols, alkyl alkylene glycols, and the like can also be used.
  • the main chain of the monool compound (D) may be linear or branched.
  • the bonding position of the hydroxyl group is also not particularly limited, but it is preferably present at the end of the molecular chain.
  • monool compounds (D) include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, hepta aliphatic monools such as decanol, stearyl alcohol, nonadecanol, other alkanols (C20-50), oleyl alcohol, and isomers thereof;
  • Aromatic aliphatic monools such as benzyl alcohol,
  • Examples include polyoxyalkylene monools obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using an alkyl compound containing one active hydrogen as an initiator.
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using an alkyl compound containing one active hydrogen as an initiator.
  • the blending amount of the monool compound (D) is appropriately adjusted from the balance of coatability and desired gas barrier properties.
  • the adhesive used in the present invention contains the monool compound (D), from the viewpoint of gas barrier properties, it is, for example, 30% by mass or less of the total amount of the adhesive.
  • Inorganic fillers include silica, alumina, aluminum flakes, and glass flakes.
  • a plate-like inorganic compound as the inorganic filler, since it improves adhesive strength, gas barrier properties, light shielding properties, and the like.
  • Plate-like inorganic compounds include hydrous silicates (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halloysite, kaolinite, endellite, dickite, nacrite, etc., antigorite, chrysotile, etc.), pyrophyllite Light-talc group (pyrophyllite, talc, kerorai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite, etc.), mica or Mica group clay minerals (mica such as muscovite and phlogopite, margarite, tetrasilylic mica, teniolite, etc.), chlorite group (cookieite, sudoite, clinochlore, chamosite, nimite,
  • the plate-like inorganic compound may be an ionic compound having an electric charge between layers, or may be a nonionic compound having no electric charge.
  • the presence or absence of charge between layers does not directly affect the gas barrier property of the adhesive layer.
  • ionic plate-like inorganic compounds and inorganic compounds that swell with water have poor dispersibility in solvent-based adhesives, and when the amount added increases, the adhesive becomes thicker and thixotropic. As a result, the coating suitability may deteriorate. For this reason, it is preferable that the plate-like inorganic compound is non-ionic with no interlayer electrification.
  • the aspect ratio of the plate-like inorganic compound is high in order to improve gas barrier properties due to the labyrinth effect of oxygen. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.
  • the content of the inorganic filler is preferably 50% by mass or less of the total amount of the adhesive. This makes it possible to obtain an adhesive with an excellent balance of gas barrier properties and coatability.
  • the coupling agent examples include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like. Coupling agents are expected to have the effect of improving the adhesiveness to various film materials, especially metal and metal oxide deposited layers.
  • the content of the coupling agent is preferably 5% by mass or less, preferably 0.1% by mass or more and 3% by mass or less, based on the total amount of the adhesive.
  • acid anhydrides examples include phthalic anhydride, succinic anhydride, het acid anhydride, hymic acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydraphthalic anhydride, and tetrabromophthalic acid.
  • oxygen scavengers include hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol and other low-molecular-weight organic compounds that react with oxygen, cobalt, manganese, nickel, iron, copper and the like. Examples include transition metal compounds.
  • Phosphoric acids include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate and the like.
  • the adhesive used in the present invention contains phosphoric acids, the content thereof is preferably 1 ppm or more and 200 ppm or less based on the total amount of the adhesive.
  • Tackifiers include xylene resins, terpene resins, phenol resins, and rosin resins. By adding a tackifier, it can be expected that the adhesiveness to the substrate will be improved.
  • urethanization catalysts examples include metal-based catalysts and aliphatic cyclic amide compounds.
  • a urethanization catalyst can be used individually or in combination of 2 or more types.
  • Metal-based catalysts include metal complex-based, inorganic metal-based, and organic metal-based catalysts.
  • the metal complex catalyst a group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), Co (cobalt) Examples include acetylacetonate salts of metals selected from the above, such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate and the like. From the point of view of toxicity and catalytic activity, iron acetylacetonate (Fe(acac) 3 ) or manganese acetylacetonate (Mn(acac) 2 ) are preferred.
  • inorganic metal-based catalysts examples include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.
  • Organometallic catalysts include organozinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; , dioctyltin dilaurate, dibutyltin oxide, dibutyltin dichloride and other organic tin compounds, nickel octylate, nickel naphthenate and other organic nickel compounds, cobalt octylate, cobalt naphthenate and other organic cobalt compounds, bismuth octylate, neodecanoic acid At least one of organic bismuth compounds such as bismuth and bismuth naphthenate, tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and alcohols having 2 to 10 carbon atoms.
  • Aliphatic cyclic amide compounds include, for example, ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthollactam, ⁇ -capryllactam, ⁇ -propiolactam and the like.
  • ⁇ -caprolactam is more effective in accelerating hardening.
  • plasticizers examples include phthalic acid-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphoric acid-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and carbonate-based plasticizers. plasticizers, and the like.
  • phthalic plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate, octyldecyl phthalate, dimethyl isophthalate, Phthalic ester plasticizers such as di-(2-ethylhexyl) isophthalate and diisooc
  • fatty acid-based plasticizers include adipic acids such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate.
  • adipic acids such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate.
  • azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, diisooctyl azelate, di-n-butyl sebacate, di-(2- ethylhexyl) sebacate, diisononyl sebacate and other sebacic acid plasticizers, e.g.
  • di-n-butyl fumarate, di-(2-ethylhexyl) fumarate and other fumaric acid plasticizers such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Itaconic acid plasticizers such as di-(2-ethylhexyl) itaconate, stearic acid plasticizers such as n-butyl stearate, glycerin monostearate, diethylene glycol distearate, butyl oleate, glyceryl monooleate, Oleic acid plasticizers such as diethylene glycol monooleate, citric acid such as triethyl citrate, tri-n-butyl citrate, acetyltriethyl citrate, acetyltributyl citrate, acetyl tri-(2-ethylhexyl) citrate ric acid
  • aromatic polycarboxylic acid-based plasticizers include tri-n-hexyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, and triisononyl. trimellitate, tridecyl trimellitate, triisodecyl trimellitate and other trimellitic acid plasticizers, e.g., tetra-(2-ethylhexyl) pyromellitate, tetra-n-octyl pyromellitate and other pyromellitic acid plasticizers plasticizers, and the like.
  • Phosphate plasticizers include, for example, triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyldiphenyl phosphate, cresyldiphenyl phosphate, cresylphenyl phosphate, trichlé Zyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, tris(isopropylphenyl) phosphate and the like.
  • polyol plasticizers examples include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate ), glycol-based plasticizers such as dibutylmethylene bisthioglycolate, and glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.
  • glycol-based plasticizers such as dibutylmethylene bisthioglycolate
  • glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.
  • epoxy plasticizers include epoxidized soybean oil, epoxybutyl stearate, di-2-ethylhexyl epoxyhexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate. etc.
  • polyester-based plasticizers examples include adipic acid-based polyesters, sebacic acid-based polyesters, and phthalic acid-based polyesters.
  • Propylene carbonate and ethylene carbonate are examples of carbonate-based plasticizers.
  • plasticizers include partially hydrogenated terphenyl, adhesive plasticizers, diallyl phthalate, polymerizable plasticizers such as acrylic monomers and oligomers, and the like. These plasticizers can be used alone or in combination of two or more.
  • the blending amount is adjusted as appropriate, but as an example, it is 30% by mass or less of the total amount of the adhesive.
  • FIG. 1 is a schematic diagram of a manufacturing apparatus used in the manufacturing method of the present invention.
  • FIG. 2 is a schematic diagram showing the essential parts of the first coating section in the manufacturing apparatus shown in FIG.
  • FIG. 3 is a schematic diagram showing a main part of a second coating section in the manufacturing apparatus shown in FIG. 1.
  • FIG. 1 is a schematic diagram of a manufacturing apparatus used in the manufacturing method of the present invention.
  • FIG. 2 is a schematic diagram showing the essential parts of the first coating section in the manufacturing apparatus shown in FIG.
  • FIG. 3 is a schematic diagram showing a main part of a second coating section in the manufacturing apparatus shown in FIG. 1.
  • the manufacturing apparatus 1 shown in FIG. 1 uses the above-described adhesive to bond the first base material W1 unwound from the roll and the second base material W2 unwound from the roll to form the first base material.
  • This is an apparatus for forming an adhesive layer 10 between a material W1 and a second base material W2 to manufacture a laminate 11a.
  • the manufacturing apparatus 1 includes a first unwinding part 11, a first coating part 12, a second unwinding part 13, a second coating part 14, and a bonding device 15.
  • the first unwinding section 11 delivers the first base material W1 to the first coating section 12 .
  • the first substrate W1 is rotatably mounted on the substrate mounting portion 111 of the first unwinding portion 11 .
  • the first coating unit 12 coats the first base material W1 sent from the first unwinding unit 11 with the first composition containing the polyisocyanate compound (B) among the components of the adhesive described above. It is a thing.
  • the first coating unit 12, as shown in FIG. 2, is a four-squeeze roll type roll coater.
  • the first coating section 12 includes an application roll 121 , a doctor roll 122 , a metering roll 123 , a coating roll 124 and a backing roll 125 .
  • a liquid reservoir 120 is provided at a portion where the application roll 121 and the doctor roll 122 face each other.
  • the application roll 121 is a roll having an outer peripheral surface made of an elastic material such as rubber.
  • the doctor roll 122 is a roll having an outer peripheral surface made of metal (inelastic material). As shown in FIG. 3, the application roll 121 and the doctor roll 122 are rotatably supported by the polyisocyanate coating section 12 so that their rotation axes are parallel to each other. The outer peripheral surface of the application roll 121 and the outer peripheral surface of the doctor roll 122 face each other with a minute gap therebetween.
  • a pair of barrier plates 126 is installed at a predetermined interval in the direction of the rotation axis of the application roll 121 and the doctor roll 122 on the upper portion of the facing portion between the application roll 121 and the doctor roll 122 .
  • a liquid reservoir 120 is formed by the pair of barrier plates 126 , the outer peripheral surface of the application roll 121 , and the outer peripheral surface of the doctor roll 122 .
  • the liquid reservoir 120 temporarily stores the first composition.
  • the first composition is supplied to the liquid reservoir 120 from a first composition supply section (not shown). As a result, the first composition stored in the liquid reservoir 120 is held at a constant amount.
  • the doctor roll 122 preferably has a temperature control section (not shown).
  • the temperature control section keeps the first composition stored in the liquid reservoir section 120 at a constant temperature (for example, 25 to 100° C.) to stabilize the viscosity. Thereby, the outer peripheral surface of the doctor roll 122 is kept at a constant temperature.
  • the application roll 121 and doctor roll 122 rotate downward in the liquid reservoir 120 .
  • the outer peripheral surface of the doctor roll 122 is coated with the first composition that has passed through the minute gaps.
  • the first coating section 12 rotatably supports a metering roll 123, a coating roll 124, and a backing roll 125.
  • the first composition applied to the outer peripheral surface of the doctor roll 122 is transferred to the metering roll 123 .
  • the rotating shaft of the metering roll 123 is arranged parallel to the rotating shaft of the doctor roll 122 .
  • the outer peripheral surface of the metering roll 123 is made of an elastic material such as rubber. The outer peripheral surface of the metering roll 123 is pressed against the outer peripheral surface of the doctor roll 122 .
  • the first composition applied to the outer peripheral surface of the metering roll 123 is transferred to the coating roll 124 .
  • the rotation axis of the coating roll 124 is arranged parallel to the rotation axis of the metering roll 123 .
  • the outer peripheral surface of the coating roll 124 is formed of a metal material. The outer peripheral surface of the coating roll 124 is pressed against the outer peripheral surface of the metering roll 123 .
  • the backing roll 125 is arranged so that the coating roll 124 and the rotating shafts are parallel to each other.
  • the backing roll 125 and the coating roll 124 sandwich and convey the first base material W1.
  • the backing roll 125 assists the transfer of the first composition applied to the outer peripheral surface of the coating roll 124 to the first substrate W1.
  • the outer peripheral surface of the backing roll 125 is made of an elastic material such as rubber.
  • the coating roll 124 preferably has a constant temperature of the outer peripheral surface (eg, 40 to 90°C) by a temperature control unit (not shown). This stabilizes the viscosity of the first composition applied to the first base material W1.
  • the second unwinding section 13 delivers the second base material W2 to the first coating section 14 .
  • the second substrate W2 is rotatably attached to the substrate attachment portion 131 of the second unwinding portion 13 .
  • the second coating unit 14 coats the second substrate W2 delivered from the second unwinding unit 13 with a compound having an active hydrogen group, that is, a polyol compound (A) and an amine compound among the components of the adhesive described above. (C1), a second composition containing at least one of the amine compounds (C2) is applied.
  • the second coating unit 14, as shown in FIG. 3, is a gravure coating machine (gravure coater) that applies the second composition by gravure printing.
  • the second coating section 14 includes a gravure roll 141 , a chamber 142 , an impression cylinder 143 , a coating liquid tank 144 , a pump 145 and a temperature controller 146 .
  • the gravure roll 141 is a metal roll rotatably supported by the second coating section 14 .
  • a plurality of recesses are formed on the surface of the gravure roll 141 by, for example, laser engraving. By changing the volume, opening ratio, depth, etc. of the recesses, the amount of the coating liquid applied to the surface of the gravure roll 141 can be adjusted.
  • the gravure pattern applied to the surface of the gravure roll 141 is not particularly limited, and may be, for example, a honeycomb pattern.
  • chamber 142 is a container that stores the second composition.
  • the chamber 142 is arranged on one radial side of the gravure roll 141 .
  • the chamber 142 has a storage portion 142a that stores the second composition.
  • the storage part 142a is open to the gravure roll 141 side.
  • a part of the outer peripheral surface of the gravure roll 141 is immersed in the second composition stored in the storage section 142a.
  • the reservoir 142a is sealed by a doctor blade 142b, a seal plate 142c and a pair of side plates 142d.
  • the chamber 142 has a plate-like doctor blade 142b.
  • the doctor blade 142b protrudes toward the gravure roll 141 from the upper end of the opening of the reservoir 142a.
  • the material of the doctor blade 142b is not particularly limited, and may be metal or resin, for example, stainless steel.
  • the tip of the doctor blade 142 b is pressed against the outer peripheral surface of the gravure roll 141 .
  • the tip of the doctor blade 142b seals the downstream side of the reservoir 142a in the roll rotation direction.
  • the doctor blade 142b scrapes off the excess second composition adhering to the outer peripheral surface of the gravure roll 141 by rotating the gravure roll 141 and weighs it.
  • the chamber 142 has a plate-like seal plate 142c.
  • the seal plate 142c is made of resin.
  • the seal plate 142c protrudes toward the gravure roll 141 from the lower end of the opening of the reservoir 142a.
  • the tip of the seal plate 142 c is pressed against the outer peripheral surface of the gravure roll 141 .
  • the tip of the seal plate 142c seals the upstream side of the reservoir 142a in the roll rotation direction.
  • the chamber 142 has a side plate 142d made of resin.
  • the side plates 142d are attached to both side surfaces of the chamber 142, that is, both ends of the gravure roll 141 in the rotation axis direction.
  • the side surface of the side plate 142 d on the side of the gravure roll 141 has an arc shape along the shape of the gravure roll 141 and is pressed against the gravure roll 141 .
  • the impression cylinder 143 as shown in FIG. 3, nips and conveys the second base material W2 with the gravure roll 141.
  • the impression cylinder 143 presses the second substrate W2 against the gravure roll 141 to transfer the second composition applied to the outer peripheral surface of the gravure roll 141 onto the second film W2.
  • the coating liquid tank 144 is a container that stores the second composition. As shown in FIG. 3, the coating liquid tank 144 is connected via piping to a pump 145 that causes the second composition to flow into the chamber 142 . Also, the coating liquid tank 144 is connected to the chamber 142 via a pipe. As a result, the second composition overflowing from the reservoir 142 a of the chamber 142 is collected in the coating liquid tank 144 .
  • the pump 145 is connected to the coating liquid tank 144 and the chamber 142 via piping.
  • the pump 145 supplies the second composition stored in the coating liquid tank 144 to the reservoir 142 a of the chamber 142 .
  • a sine pump for example, can be used as the pump 145 .
  • the temperature controller 146 keeps the temperature of the second composition stored in the coating liquid tank 144 constant and stabilizes the viscosity of the second composition.
  • the temperature controller 146 is, for example, a temperature controller for water that heats water, which is a heat medium, with a heater and circulates around the second composition stored in the coating liquid tank 144 .
  • the bonding device 15 includes a bonding section 151 and a winding section 152, as shown in FIG.
  • the bonding part 151 is the first composition-coated surface of the first base material W1 delivered from the first coating part 12, and the second base material W2 delivered from the second coating part 14.
  • the coated surface of the second composition is attached.
  • the winding section 152 winds up the laminated film 11 a bonded by the bonding section 151 .
  • the lamination section 151 has a pair of lamination rolls R1 and R2 as shown in FIG.
  • the lamination rolls R1 and R2 sandwich and bond the first base material W1 and the second base material W2, and convey them.
  • the two laminate rolls R1 and R2 are kept at a constant temperature on the outer peripheral surface by a temperature control unit (not shown). This stabilizes the curing of the adhesive.
  • the lamination unit 151 passes the first base material W1 and the second base material W2 between two laminate rolls R1 and R2 arranged opposite to each other to perform the first coating.
  • the coated surface of the first base material W1 delivered from the unit 12 and the coated surface of the second base material W2 delivered from the second coating unit 14 are brought into contact with each other and bonded together.
  • the bonding portion 151 the first composition applied to the first base material W1 and the second composition applied to the second base material W2 are mixed to cure the adhesive. is started, and the first base material W1 and the second base material W2 are attached and fixed.
  • the winding section 152 winds up the laminate 11 a formed by bonding the first base material W1 and the second base material W2 together in the bonding section 151 .
  • the first base material W1 and the second base material W2 are in contact with each other, and the two laminate rolls R1 and R2 are arranged to face each other. It is sandwiched and passed between two lamination rolls R1 and R2. Then, the first base material W1 and the second base material W2 are laminated together by the pressure from the two laminate rolls R1 and R2.
  • the temperature of the outer peripheral surfaces of the two laminate rolls R1 and R2 is preferably 40°C to 80°C, more preferably 40°C to 60°C.
  • the pressure from the two laminating rolls R1, R2 to the first substrate W1 and the second substrate W2 can be, for example, 3-300 kg/cm 2 .
  • the coated surface of the first base material W1 delivered from the first coating unit 12 and the coated surface of the first substrate W1 delivered from the second coating unit 14 are sandwiched between the two laminate rolls R1 and R2.
  • the coating surface of the second base material W2 contacts.
  • the first composition applied to the first base material W1 and the second composition applied to the second base material W2 are mixed, and curing of the adhesive is started.
  • the laminate 11a having the adhesive layer 10 between the first base material W1 and the second base material W2 is obtained.
  • the laminated body 11 a produced by bonding the first base material W ⁇ b>1 and the second base material W ⁇ b>2 together in the bonding section 151 is conveyed to the winding section 152 .
  • the laminate 11 a transported to the winding section 152 is wound up by the winding section 152 .
  • the substrate conveying speed (the winding speed of the laminate 11a in the winding unit 152) when manufacturing the laminate 11a is set to, for example, 30 to 300 m/min. and preferably 100 to 250 m/min.
  • a laminated body can be manufactured efficiently as a base-material conveyance speed is 30 m/min or more. If the base material conveying speed exceeds 300 m/min, problems such as problems in coating, problems in the transfer itself, and problems in bonding may occur. Therefore, it is preferable that the base material conveying speed is 300 m/min or less.
  • the laminate 11a obtained by the manufacturing method of the present embodiment is obtained by bonding the first base material W1 and the second base material W2 together in the bonding section 151, winding up the winding section 152, and Aging is performed by storing at (25° C.) to 50° C. for 3 to 72 hours.
  • the adhesive is sufficiently hardened and practical physical properties as the adhesive layer 10 are exhibited.
  • the gravure roll 141 may be replaced by a roll coater.
  • a gravure coater is selected as the device for applying the second composition in the second coating unit 14, the viscosity of the second composition is low, and problems such as dripping may occur with a roll coater. Also, it is possible to manufacture a high-quality laminate 11a by improving coating quality without dripping. Moreover, by using a gravure coater, the configuration of the second coating unit 14 can be simplified, and the apparatus for manufacturing the laminate 11a can be miniaturized.
  • the temperature of the second composition stored in the coating liquid tank 144 is adjusted by the temperature adjuster 146. Further, the second composition stored in the reservoir 142a of the chamber 142 and/or the temperature of the gravure roll 141 may be adjusted. As a result, the viscosity of the second composition during coating can be further stabilized, and the coating quality and the quality of the laminate 11a can be further improved.
  • the second composition contains the polyol compound (A) but does not contain other compounds having active hydrogen groups. In one embodiment of the method for producing a laminate of the present invention, the second composition contains at least one of the amine compounds (C1) and (C2) but does not contain other compounds having active hydrogen groups. In one embodiment of the method for producing a laminate of the present invention, the second composition contains a polyol compound (A) and a catalyst. In one embodiment of the method for producing a laminate of the present invention, the second composition contains an amine compound (C) and a catalyst in addition to the polyol compound (A). In one embodiment of the method for producing a laminate of the present invention, the second composition contains an amine compound (C), a monool (D), and a catalyst in addition to the polyol compound (A).
  • the second composition does not contain the polyisocyanate compound (B) in any of the embodiments.
  • the first composition may be contained in either the first composition or the second composition. If the first composition does not contain a compound having an active hydrogen group, it is added to the second composition. It goes without saying that these compositions may appropriately contain each component of the adhesive described above. These first composition and second composition are appropriately combined according to the purpose.
  • [ NCO]/[OH+NH] is preferably used in the range of 1-3.
  • the coating amount of the adhesive (the total coating amount of the first composition and the second composition) is, for example, 0.5 to 5.0 g/m 2 .
  • the coating amount of the first composition and the second composition is preferably 0.2 to 3.0 g/m 2 , more preferably about 0.2 to 2.0 g/m 2 . is preferred.
  • the laminate of the present invention is obtained by laminating a plurality of substrates by the method described above. Further, another base material can be attached to the laminate of the present invention.
  • the adhesive used at this time may be the one described above, or may be a general-purpose two-liquid curing adhesive.
  • a dry lamination method or a non-solvent lamination method may be used, or a separate coating method may be used.
  • Base material 1/adhesive layer 1/sealant film (2) Base material 1/adhesive layer 1/metal vapor deposition unstretched film (3) Base material 1/adhesive layer 1/metal vapor deposition stretched film (4) Transparent vapor deposition stretching Film/adhesive layer 1/sealant film (5) Substrate 1/adhesive layer 1/substrate 2/adhesive layer 2/sealant film (6) Substrate 1/adhesive layer 1/stretched metal deposition film/adhesive layer 2/sealant Film (7) Substrate 1/adhesive layer 1/transparent evaporated stretched film/adhesive layer 2/sealant film (8) Substrate 1/adhesive layer 1/metal layer/adhesive layer 2/sealant film (9) Substrate 1/ Adhesive layer 1/substrate
  • Examples of the base material 1 used in configuration (1) include OPP film, PET film, nylon film, paper, and the like. Further, as the base material 1, a material coated for the purpose of improving gas barrier properties and ink receptivity when providing a printing layer, which will be described later, may be used. Commercial products of the coated base film 1 include K-OPP film and K-PET film.
  • the adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of sealant films include CPP films and LLDPE films. On the surface of the substrate 1 on the side of the adhesive layer 1 (the surface of the coating layer on the side of the adhesive layer 1 when a coated substrate film 1 is used) or the surface opposite to the adhesive layer 1, A printed layer may be provided.
  • the printing layer is formed by general printing methods conventionally used for printing on polymer films and paper using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink.
  • the base material 1 used in configurations (2) and (3) examples include OPP film, PET film, paper, and the like.
  • the adhesive layer 1 is a cured coating film of the adhesive of the present invention.
  • a VM-CPP film obtained by vapor-depositing a metal such as aluminum on a CPP film may be used as the unstretched metal vapor-deposited film, and a VM-OPP film obtained by vapor-depositing a metal such as aluminum on an OPP film may be used as the stretched metal-deposited film. can be done.
  • a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • Examples of transparent vapor-deposited stretched films used in configuration (4) include films obtained by vapor-depositing silica or alumina on OPP films, PET films, nylon films, or the like.
  • a film obtained by coating the deposition layer may be used.
  • the adhesive layer 1 is a cured coating film of the adhesive of the present invention.
  • Examples of the sealant film include those similar to those of the configuration (1).
  • a printed layer may be provided on the adhesive layer 1 side of the transparent vapor deposited stretched film (when using a film having a coated inorganic vapor deposited layer, the surface of the coating layer on the adhesive layer 1 side). The method of forming the printed layer is the same as in configuration (1).
  • Examples of the base material 1 used in configuration (5) include PET film, paper, and the like.
  • Examples of the base material 2 include a nylon film and the like.
  • At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention.
  • Examples of the sealant film include those similar to those of the configuration (1).
  • a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • the same ones as those of configurations (2) and (3) can be mentioned.
  • the metal-deposited oriented film include VM-OPP film and VM-PET film obtained by subjecting an OPP film or PET film to metal deposition such as aluminum.
  • At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention.
  • the sealant film include those similar to those of the configuration (1).
  • a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • Examples of the base material 1 of configuration (7) include PET film, paper, and the like. Examples of the transparent vapor-deposited stretched film include those similar to those of the configuration (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • Examples of the base material 1 of configuration (8) include PET film, paper, and the like. Aluminum foil etc. are mentioned as a metal layer. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • Examples of the substrate 1 of configurations (9) and (10) include PET film, paper, and the like.
  • Examples of the base material 2 include a nylon film and the like. Aluminum foil etc. are mentioned as a metal layer.
  • At least one of the adhesive layers 1, 2 and 3 is a cured coating film of the adhesive of the present invention.
  • Examples of the sealant film include those similar to those of the configuration (1).
  • a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • the packaging material of the present invention is obtained by molding the laminate of the present invention into a bag shape.
  • the laminate of the present invention is folded or overlapped so that the inner layer surface (sealant film surface) faces each other, and the peripheral edge is sealed, for example, by a side seal type, a two-sided seal type, There are three-side seal type, four-side seal type, envelope seal type, palm-joint seal type, pleated seal type, flat-bottom seal type, square-bottom seal type, gusset type, and other heat-sealing methods. be done.
  • the packaging material of the present invention can take various forms depending on the contents, environment of use, and form of use.
  • a self-supporting packaging material (standing pouch) or the like is also possible.
  • a heat sealing method known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing can be used.
  • An easy-opening treatment or resealing means may be provided.
  • the packaging material of the present invention can be used industrially as a packaging material mainly filled with foods, detergents, and medicines. Specific uses include detergents and chemicals such as liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and pharmaceutical tablets. It can also be used as a secondary packaging material for packaging the container described above.
  • Adhesives 1 to 1 were prepared according to the formulations shown in Table 1.
  • the laminates obtained by the methods of Examples 1 to 3 had no problems with the pot life of the adhesive, and exhibited superior gas barrier properties compared to the laminate of Comparative Example 1.
  • the viscosities of the adhesives 1 and 2 increased to a range unsuitable for coating immediately after mixing, and laminates suitable for evaluation could not be obtained.

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PCT/JP2022/019237 2021-05-11 2022-04-28 積層体の製造方法 Ceased WO2022239667A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025246085A1 (zh) * 2024-05-28 2025-12-04 思嘉环保材料科技（上海）有限公司 一种聚酯纤维网布双面复合铝箔保温隔热材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017189878A (ja) * 2016-04-11 2017-10-19 凸版印刷株式会社 バリアフィルム積層体及びその製造方法、波長変換シート、バックライトユニット、並びにエレクトロルミネッセンス発光ユニット
WO2018043469A1 (ja) * 2016-09-05 2018-03-08 Dic株式会社 軟包装用フィルムの製造方法
WO2019181921A1 (ja) * 2018-03-23 2019-09-26 Dic株式会社 接着剤、積層フィルム、及び積層フィルムの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017189878A (ja) * 2016-04-11 2017-10-19 凸版印刷株式会社 バリアフィルム積層体及びその製造方法、波長変換シート、バックライトユニット、並びにエレクトロルミネッセンス発光ユニット
WO2018043469A1 (ja) * 2016-09-05 2018-03-08 Dic株式会社 軟包装用フィルムの製造方法
WO2019181921A1 (ja) * 2018-03-23 2019-09-26 Dic株式会社 接着剤、積層フィルム、及び積層フィルムの製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025246085A1 (zh) * 2024-05-28 2025-12-04 思嘉环保材料科技（上海）有限公司 一种聚酯纤维网布双面复合铝箔保温隔热材料及其制备方法

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