WO2022138188A1 - ガスバリア性積層体、包装材 - Google Patents

ガスバリア性積層体、包装材 Download PDF

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Publication number
WO2022138188A1
WO2022138188A1 PCT/JP2021/045262 JP2021045262W WO2022138188A1 WO 2022138188 A1 WO2022138188 A1 WO 2022138188A1 JP 2021045262 W JP2021045262 W JP 2021045262W WO 2022138188 A1 WO2022138188 A1 WO 2022138188A1
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Prior art keywords
layer
acid
gas barrier
adhesive
film
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PCT/JP2021/045262
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English (en)
French (fr)
Japanese (ja)
Inventor
正光 新居
裕季 小林
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2022542726A priority Critical patent/JP7239069B2/ja
Priority to CN202180073055.3A priority patent/CN116348287A/zh
Publication of WO2022138188A1 publication Critical patent/WO2022138188A1/ja
Anticipated expiration legal-status Critical
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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
    • B32B27/06—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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present invention relates to a gas barrier laminated body and a packaging material obtained by using the gas barrier laminated body.
  • Packaging materials used for packaging foods and daily necessities are required to have functions such as strength, resistance to cracking, and gas barrier properties in order to protect the contents from impacts received during distribution, deterioration due to oxygen and moisture, and the like.
  • functions such as strength, resistance to cracking, and gas barrier properties
  • the non-stretched polyolefin film used for sealing by heat sealing is excellent in heat processability, but has insufficient oxygen barrier property.
  • Nylon film on the other hand, has excellent gas barrier properties, but is inferior in heat seal properties.
  • laminates made by laminating different types of polymer materials are widely used as packaging materials.
  • a product protection function such as impact resistance and gas barrier property
  • a thermoplastic plastic film as an outer layer
  • a sealant function such as impact resistance and gas barrier property
  • a heat as an inner layer.
  • a laminate is known in which a plastic film and an adhesive are used to bond them together to form an outer layer / a printing layer / an adhesive layer (adhesive) / an inner layer.
  • an adhesive used for such a laminate a two-component polyurethane-based adhesive composed of a polyol and an isocyanate is known.
  • Patent Document 3 describes a transparent coating film having a thin film layer of silicon oxide or aluminum oxide formed on at least one surface of a polymer film base material, and a heat-sealing resin film.
  • a barrier laminate characterized by being bonded by a dry laminating method via a barrier adhesive containing one or more particles selected from an inorganic silicon oxide or aluminum oxide material, a polyester polyol, and an isocyanate compound. , And packaging materials using it are described.
  • Gas barrier properties correlate with ambient humidity, for example, olefin films have better gas barrier properties under low humidity than under high humidity, and polyethylene terephthalate rate films have better gas barrier properties under high humidity than under low humidity. Excellent. For this reason, packaging materials using films with a vapor-filmed layer of cracked metal or metal oxide may have a reduced gas barrier property due to changes in ambient humidity, and sufficient gas barrier properties can be obtained in areas with different climates. It may not be possible.
  • the present invention has been made in view of such circumstances, and provides a laminate and a packaging material which are stable and have excellent gas barrier properties regardless of the humidity of the usage environment and even when the humidity fluctuates. With the goal.
  • the present invention has a first base material, a resin layer arranged in contact with the first base material, an inorganic vapor deposition layer arranged in contact with the resin layer, and a gas barrier property arranged in contact with the inorganic vapor deposition layer.
  • the present invention relates to a laminate including an adhesive layer and a resin layer having a thickness of 0.1 ⁇ m or more and 5 ⁇ m or less, and a packaging material obtained by using the laminate.
  • the laminate of the present invention it is possible to stably obtain a laminate and a packaging material having excellent gas barrier properties even under high humidity.
  • the laminate of the present invention is arranged in contact with the first base material, the resin layer arranged in contact with the first base material, the inorganic vapor-deposited layer arranged in contact with the resin layer, and the inorganic vapor-deposited layer. It has a gas barrier resin layer.
  • the first base material can be used without particular limitation as long as it is a film or sheet having excellent chemical and physical strength (the film is also a general term for a film and a sheet unless otherwise specified below). Further, the base material may be a single-layer film or a multilayer laminated film. It can be appropriately selected according to the usage conditions such as the content and type of the packaging material described later, and the presence or absence of heat treatment after filling the content.
  • the first substrate include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, polybutene, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ionomer.
  • Ethylene- (meth) acrylic acid copolymer ethylene- (meth) acrylic acid ester copolymer, ethylene-propylene copolymer, methylpentene, polyacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene Polymers, polycarbonate, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), vinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET) ), Resin films such as polybutylene terephthalate and polyethylene naphthalate, K-coated stretched polypropylene films, K-coated stretched nylon films, and composite films in which two or more of these films are laminated are exemplified, but not limited thereto.
  • uniaxial or biaxially stretched polyester film such as polyethylene terephthalate and polyethylene naphthalate
  • uniaxial or biaxially stretched polyamide film such as nylon 6, nylon 66 and MXD6 (polymethoxylylen adipamide)
  • biaxially stretched polypropylene film Etc. can be preferably used.
  • the film thickness of the film is not particularly limited, and may be appropriately selected in 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 is insufficient, and if it exceeds 300 ⁇ m, the rigidity becomes too high and processing may become difficult.
  • the first base material used 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, and chemicals. It may be subjected to chemical treatment such as oxidation treatment or other treatment. If the adhesion between the first base material and the resin layer described later is poor, a coat layer may be provided using a primer. Conventionally known primers can be used as the primer.
  • the first base material is manufactured by a conventionally known film-forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, etc., using one or more of the above-mentioned resins, for example. can do.
  • a film-forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, etc.
  • it can be produced by a multi-layer co-extrusion film forming method using two or more kinds of resins selected from the above-mentioned resins.
  • the film may be stretched in the uniaxial or biaxial direction by using a tenter method, a tubular method, or the like.
  • the first base material may contain additives as needed. Specifically, the workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold releasability, flame retardancy, antifungal properties, electrical properties, strength, etc. have been improved.
  • plastic compounding agents such as lubricants, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments and the like can be added.
  • the amount of the additive added should be adjusted within a range that does not affect other performance.
  • the resin layer is provided on the first substrate by laminating, co-extruding, spraying, vapor deposition, or coating.
  • the resin used for forming the resin layer include polyester, polyurethane, polyamide, ethylene vinyl alcohol copolymer, polyvinyl alcohol, polyvinyl chloride, acrylic resin, polyalkylimine, acid-modified olefin resin, and the like. Two or more types can be used in combination. Of these, it is preferable to use either or both of an ethylene vinyl alcohol copolymer and polyvinyl alcohol.
  • the ethylene vinyl alcohol copolymer can be obtained by hydrolyzing a copolymer of ethylene and vinyl ester.
  • Vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatic acid, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, etc. Examples thereof include vinyl oleate and vinyl benzoate, and one type or a combination of two or more types can be used. It is preferable to use vinyl acetate.
  • the content of ethylene unit in the ethylene vinyl alcohol copolymer is preferably 20 mol% or more and 60 mol% or less. If it is less than 20 mol%, the bending resistance, the viscosity stability, and the thermal stability at the time of melt molding tend to decrease. If it exceeds 60 mol%, the gas barrier property tends to decrease.
  • ethylene and vinyl esters such as propene, 1-butene, isobutylene, 1,3-butadiene, isopropenyl acetate, 2-propenyl acetate, styrene, ⁇ -methylstyrene, vinyl chloride, acrylonitrile, maleic anhydride, acrylic acid Copolymerization of methyl, methyl methacrylate, N-vinyl-N-methylformamide, vinylacetamide, N-vinylformamide, hydroxyethyl N- (hydroxymethyl) -N-vinylformamide acrylate, methylvinylketone, diacetoneacrylamide, etc.
  • the degree of saponification of the ethylene vinyl alcohol copolymer is preferably 90 mol% or more, preferably 95 mol% or more, because it is excellent in gas barrier property, viscosity stability, thermal stability during melt molding, moisture resistance, and the like. Is more preferable. It may be completely saponified.
  • the degree of saponification can be measured by FTIR using, for example, a Nicolet 5700 FTIR spectrometer controlled by OMNIC software.
  • the melting point of the ethylene vinyl alcohol copolymer is preferably less than 180 ° C, preferably 130 ° C or higher.
  • the glass transition temperature is preferably 45 ° C. or higher and 65 ° C. or lower.
  • Polyvinyl alcohol can be obtained by hydrolyzing a vinyl ester copolymer as described above.
  • the degree of saponification is preferably 90 mol% or more, and more preferably 95 mol% or more. It may be completely saponified.
  • the melting point of polyvinyl alcohol is preferably 200 ° C. or higher.
  • the glass transition temperature of polyvinyl alcohol is preferably 65 ° C. or higher and 85 ° C. or lower.
  • the glass transition temperature and melting point of ethylene vinyl alcohol copolymer and polyvinyl alcohol are measured as follows. Using a differential scanning calorimetry device (DSC-7000 manufactured by SII Nanotechnology Co., Ltd., hereinafter referred to as DSC), raise 5 mg of the sample from 30 ° C to 10 ° C / min under a nitrogen stream of 20 mL / min to T1 ° C. After warming, hold for 10 minutes, then cool to T 2 ° C at 10 ° C / min to remove thermal history.
  • DSC-7000 differential scanning calorimetry device
  • the temperature was raised again to T 3 ° C at 10 ° C / min to measure the DSC curve, and the baseline on the low temperature side in the measurement results observed in the second temperature raising step was measured.
  • the intersection of the straight line extended to the high temperature side and the tangent line drawn at the point where the slope of the curve of the stepped portion of the glass transition is maximized is defined as the glass transition point, and the temperature at this time is defined as the glass transition temperature.
  • the maximum peak temperature of the endothermic curve observed in the second temperature raising step is defined as the melting point.
  • T 2 is sufficiently lower than the glass transition temperature of the sample, and T 1 and T 3 are temperatures at least 30 ° C. or higher above the melting point of the sample.
  • T 1 is 200 ° C.
  • T 2 is ⁇ 80 ° C.
  • T 3 is 200 ° C., which are appropriately adjusted according to the sample to be measured.
  • the film thickness of the resin layer is 0.1 ⁇ m or more. It is more preferably 0.3 ⁇ m or more, more preferably 0.4 ⁇ m or more, and more preferably 0.5 ⁇ m or more because the smoothness of the resin layer on the inorganic vapor deposition layer side is improved and the gas barrier property is less likely to be lowered. Is more preferable.
  • the upper limit is not particularly limited, but as the film thickness of the resin layer becomes thicker, the synergistic effect with the gas barrier adhesive described later becomes saturated. Therefore, as an example, it is 5 ⁇ m or less, more preferably 3 ⁇ m or less, and 1.5 ⁇ m. The following is more preferable.
  • the surface of the resin layer (the surface in contact with the inorganic vapor deposition layer described later) is physically subjected to some surface treatment such as corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, etc. Treatment, chemical treatment such as oxidation treatment using chemicals, and other treatments may be performed.
  • some surface treatment such as corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, etc.
  • Treatment, chemical treatment such as oxidation treatment using chemicals, and other treatments may be performed.
  • the inorganic vapor deposition layer is a layer having a gas barrier property that prevents the permeation of oxygen gas and water vapor gas, and is a vapor deposition layer made of an inorganic substance or an inorganic oxide.
  • the inorganic substance or the inorganic oxide include aluminum, alumina, silica and the like, and these may be used alone, or two or more kinds may be used in combination as in the case of binary vapor deposition of silica and alumina.
  • Two or more inorganic vapor deposition layers may be provided. When two or more inorganic vapor deposition layers are provided, they may have the same composition or different compositions. From the viewpoint of gas barrier property, it is preferable to use aluminum.
  • the inorganic vapor deposition layer can be provided on the above-mentioned resin layer by a conventionally known method.
  • the method for forming the inorganic vapor deposition layer include a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, a plasma chemical vapor deposition method, and heat.
  • PVD method physical vapor deposition method
  • CVD method Chemical Vapor Deposition method
  • the film thickness of the inorganic thin-film deposition layer is preferably 1 to 200 nm.
  • the film thickness is more preferably 1 to 100 nm, more preferably 15 to 60 nm, and even more preferably 10 to 40 nm.
  • the inorganic vapor deposition layer is a silica or alumina vapor deposition layer, the film thickness is preferably 1 to 100 nm, more preferably 10 to 50 nm, and even more preferably 20 to 30 nm.
  • the gas barrier adhesive layer is a cured coating film of a gas barrier adhesive, and is a layer for laminating an inorganic vapor-deposited layer and another layer.
  • the gas barrier adhesive layer is arranged in contact with the inorganic vapor deposition layer.
  • the gas barrier adhesive is a coating film coated at 3 g / m 2 (solid content) having an oxygen barrier property of 300 cc / m 2 / day / atm or less at 23 ° C. and 0% RH, or water vapor.
  • Gas barrier adhesives preferably used in the present invention include a polyol composition (X) containing at least one of the following polyester polyols (A) (A1) to (A3), and at least two isocyanate groups in one molecule.
  • a polyol composition (X) containing at least one of the following polyester polyols (A) (A1) to (A3), and at least two isocyanate groups in one molecule.
  • examples thereof include a two-component adhesive comprising a polyisocyanate composition (Y) containing a compound having a above (hereinafter, also simply referred to as an isocyanate compound (B)).
  • Polyester polyol (A1) obtained by polycondensing a polyvalent carboxylic acid containing an ortho-oriented polyvalent carboxylic acid and a polyhydric alcohol.
  • Polyester polyol having an isocyanul ring (A2) (3) Polyester polyol having a polymerizable carbon-carbon double bond (A3)
  • Examples of the ortho-orientation polyvalent carboxylic acid used for the synthesis of the polyester polyol (A1) include orthophthalic acid or an acid anhydride thereof, naphthalene 2,3-dicarboxylic acid or an acid anhydride thereof, naphthalene 1,2-dicarboxylic acid or its acid anhydride. Examples thereof include acid anhydride, anthraquinone 2,3-dicarboxylic acid or an acid anhydride thereof, and 2,3-anthracenecarboxylic acid or an acid anhydride thereof. These compounds may have a substituent on any carbon atom of the aromatic ring.
  • Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group.
  • substituent include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group or a naphthyl group.
  • the polyvalent carboxylic acid used for the synthesis of the polyester polyol (A1) may contain a polyvalent carboxylic acid other than the ortho-oriented polyvalent carboxylic acid.
  • examples of the polyvalent carboxylic acid other than the ortho-oriented polyvalent carboxylic acid include aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecandicarboxylic acid; maleic anhydride, maleic acid, fumaric acid and the like.
  • the ratio of the ortho-oriented polyvalent carboxylic acid to the total amount of the polyvalent carboxylic acid is preferably 40 to 100% by mass. ..
  • the polyhydric alcohol used for the synthesis of 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 is preferably used. It is more preferable to include it.
  • the polyhydric alcohol may be used in combination with a polyhydric alcohol other than the above, for example, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol.
  • Butylethyl propanediol diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and other aliphatic diols; glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1 , 2,4-Butantriol, pentaerythritol, dipentaerythritol and other trihydric polyhydric alcohols, hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol and these.
  • Examples of the ethylene oxide extension product, aromatic polyhydric phenol such as hydrogenated alicyclic group, and the like can be exemplified.
  • polyester polyol (A1) has three or more hydroxyl groups (referred to as polyester polyol (a1) for convenience), a part of the hydroxyl groups may be modified with an acid group.
  • a polyester polyol will also be referred to as a polyester polyol (A1') below.
  • 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 the hydroxyl group modified with the polyvalent carboxylic acid is preferably 1/3 or less of the hydroxyl group contained in the polyester polyol (a1).
  • Polyvalent carboxylic acids used for modification include succinic anhydride, maleic acid, maleic anhydride, fumaric acid, 1,2-cyclohexanedicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, and 5-norbornene.
  • Examples thereof include, but are not limited to, -2,3-dicarboxylic acid anhydride, phthalic anhydride, 2,3-naphthalenedicarboxylic acid anhydride, trimellitic acid anhydride, oleic acid, and sorbic acid.
  • the polyester polyol (A2) is obtained, for example, by reacting a triol having an isocyanul ring with a polyvalent carboxylic acid containing an ortho-oriented aromatic polyvalent carboxylic acid and a polyhydric alcohol.
  • a triol having an isocyanul ring examples include alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris (2-hydroxyethyl) isocyanuric acid and 1,3,5-tris (2-hydroxypropyl) isocyanuric acid. And so on.
  • the ortho-oriented aromatic polyvalent carboxylic acid, polyvalent carboxylic acid, and polyhydric alcohol the same ones as those of the polyester polyol (A1) can be used.
  • triol compound having an isocyanul ring 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is preferably used.
  • ortho-oriented aromatic polyvalent carboxylic acid it is preferable to use orthophthalic acid anhydride. It is preferable to use ethylene glycol as the polyhydric alcohol.
  • the polyester polyol (A3) is obtained by using a component having a polymerizable carbon-carbon double bond as a polyvalent carboxylic acid and a polyhydric alcohol.
  • Examples of the polyvalent carboxylic acid having a polymerizable carbon-carbon double bond include maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its acid anhydride, and 3-methyl-4-cyclohexene. Examples thereof include -1,2-dicarboxylic acid and its acid anhydride.
  • Maleic anhydride, maleic acid, and fumaric acid are preferable because it is presumed that the smaller the number of carbon atoms is, the less flexible the molecular chain is and the more difficult it is for oxygen to permeate.
  • Examples of the polyhydric alcohol having a polymerizable carbon-carbon double bond include 2-butene-1,4-diol and the like.
  • a polyvalent carboxylic acid or a polyhydric alcohol having no polymerizable carbon-carbon double bond may be used in combination.
  • a polyvalent carboxylic acid and a polyhydric alcohol the same ones as those of the polyester polyols (A1) and (A2) can be used.
  • the polyvalent carboxylic acid it is preferable to use 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 its acid anhydride. It is more preferable to use at least one of.
  • polyhydric alcohol it is preferable to use at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, and it is more preferable to use ethylene guclikol.
  • the hydroxyl value of the polyester polyol (A) is preferably 20 mgKOH / g or more and 250 mgKOH / g or less.
  • the hydroxyl value is smaller than 20 mgKOH / g, the viscosity of the polyol composition (A) becomes high because the molecular weight is too large, and it is necessary to raise the coating temperature when applied as a solvent-free adhesive, for example.
  • the hydroxyl value exceeds 250 mgKOH / g, the crosslink density of the cured coating film becomes too high, and the adhesive strength may decrease.
  • the acid value is preferably 200 mgKOH / g or less.
  • the acid value exceeds 200 mgKOH / g, the reaction between the polyol composition (X) and the polyisocyanate composition (Y) becomes too fast, and the coatability may decrease.
  • the lower limit of the acid value is not particularly limited, but as an example, it is 20 mgKOH / g or more.
  • the acid value is 20 mgKOH / g or more, good gas barrier properties and initial cohesive force can be obtained by the interaction between molecules.
  • 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 number average molecular weight of the polyester polyol (A) is 300 to 5000 because a crosslink density that is excellent in the balance between adhesiveness and gas barrier property can be obtained. More preferably, the number average molecular weight is 350 to 3000. The number average molecular weight is calculated from the obtained hydroxyl group value and the number of functional groups of the designed hydroxyl group.
  • the glass transition temperature of the polyester polyol (A) is preferably ⁇ 30 ° C. or higher and 80 ° C. or lower, more preferably 0 ° C. or higher and 60 ° C. or lower, from the viewpoint of the balance between the adhesion to the substrate and the gas barrier property, 25. It is more preferably ° C. or higher and 60 ° C. or lower.
  • the polyester polyol (A) may be a polyester polyurethane polyol having a number average molecular weight of 1000 to 15000 by urethane elongation of polyester polyols (A1) to (A3) by reaction with a diisocyanate compound. Since the urethane-extended polyester polyol has a molecular weight component having a certain weight or more and a urethane bond, it has an excellent gas barrier property, an excellent initial cohesive force, and an excellent adhesive for laminating.
  • the isocyanate compound (B) conventionally known ones can be used without particular limitation, and tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydride xylylene diisocyanate, Isophorone diisocyanates or trimerics of these isocyanate compounds, and excess amounts of these isocyanate compounds, such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, Low molecular weight active hydrogen compounds such as trimethylolpropane, glycerol, pent
  • polyester polyols (A1) to (A3) examples thereof include an adduct body obtained by reacting with a high molecular weight active hydrogen compound of polyols and polyamides.
  • blocked isocyanate may be used as the isocyanate compound.
  • the isocyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol, acetoxime, methylethylketooxime, cyclohexanone oxime, and methanol.
  • Alcohols such as ethanol, propanol and butanol, halogen-substituted alcohols such as ethylene chlorhydrin and 1,3-dichloro-2-propanol, tertiary alcohols such as t-butanol and t-pentanol, ⁇ - Examples include lactams such as caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propyrolactam, and other active methylene compounds such as aromatic amines, imides, acetylacetone, acetoacetic acid ester, and malonic acid ethyl ester. , Mercaptans, imines, ureas, diaryl compounds, sodium bicarbonate and the like.
  • the blocked isocyanate is obtained by subjecting the above-mentioned isocyanate compound and an isocyanate blocking agent to an addition reaction by an appropriate method known and commonly used.
  • an isocyanate compound having a skeleton derived from xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate because good gas barrier properties can be obtained.
  • an isocyanate compound examples include a trimer of diisocyanate, a burette compound synthesized by a reaction with an amine, and an adduct compound formed by a reaction with an alcohol.
  • the adhesive is a solvent type
  • an adduct formed by reacting with an alcohol appropriately selected from the above low-molecular-weight active hydrogen compounds can be used, and among them, ethylene oxide adduct of trimethylolpropane, glycerol, triethanolamine, and m-xylylenediamine can be used.
  • An adduct body with an object is preferable.
  • the polyisocyanate composition (Y) contains an epoxy compound. It may be included.
  • the epoxy compound include bisphenol A diglycidyl ether and its oligomer, hydride bisphenol A diglycidyl ether and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid di.
  • Glycidyl ester tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl Examples thereof include propylene urea, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycid
  • epoxy curing accelerator When an epoxy compound is used, a widely known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing as long as the object of the present invention is not impaired.
  • composition (X) When a composition containing a polyol having a polymerizable carbon-carbon double bond such as the polyester polyol (A3) is used as the polyol composition (X), in order to promote the polymerization of the carbon-carbon double bond.
  • a known polymerization catalyst can be used in combination, and an example thereof is a transition metal complex.
  • the transition metal complex is not particularly limited as long as it is a compound having an ability to oxidatively polymerize a polymerizable double bond.
  • metals such as cobalt, manganese, lead, calcium, cerium, zirconium, zinc, iron, copper, octyl acid, naphthenic acid, neodecanoic acid, stearic acid, resin acid, tall oil fatty acid, tung oil fatty acid, linseed oil fatty acid, A salt with soybean oil fatty acid or the like can be used.
  • the blending amount of the transition metal complex is preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass with respect to the resin solid content contained in the polyol composition (X).
  • the equivalent ratio of the hydroxyl group contained in the polyol composition (X) to the isocyanate group contained in the polyisocyanate composition (Y) is 1/0. It is preferable to mix it so as to be 5 to 1/10, and more preferably to mix it so as to be 1/1 to 1/5. If the isocyanate compound is excessive, the excess isocyanate compound remaining in the cured coating film of the adhesive may bleed out from the adhesive layer. On the other hand, if the reactive functional group contained in the polyisocyanate composition (Y) is insufficient, the adhesive strength may be insufficient.
  • the gas barrier adhesive may contain various additives as long as the adhesiveness and the gas barrier property are not impaired.
  • Inorganic filler may be used as such an additive.
  • the inorganic filler include silica, alumina, aluminum flakes, glass flakes and the like.
  • Plate-like inorganic compounds include hydrous silicate (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halosite, kaolinite, enderite, dikite, naphthyl, etc., antigolite, chrysotile, etc.), pyrophylli.
  • Light-Tark (pyrophyllite, talc, kerolai, etc.), smectite clay minerals (montmorillonite, biderite, nontronite, saponite, hectrite, soconite, stibnsite, etc.), vermiculite clay minerals (vermiculite, etc.), mica or Mica clay minerals (white mica, gold mica and other mica, margarite, tetrasilic mica, teniolite, etc.), green mudstones (cookate, sudoite, clinochloa, chamosite, nimite, etc.), hydrotalcite, plate-like sulfuric acid Examples include barium, boehmite, and aluminum polyphosphate. These minerals may be natural clay minerals or synthetic clay minerals. The plate-like inorganic compound may be used alone or in combination of two or more.
  • the plate-like inorganic compound may be an ionic compound having an electric charge between layers, or 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 have swelling properties with respect to water are inferior in dispersibility in solvent-type adhesives, and if the amount added is increased, they may thicken with the adhesive or become thixotropic. Therefore, the coating suitability may decrease. Therefore, the plate-like inorganic compound is preferably nonionic without interlayer electrification.
  • the average particle size of the plate-shaped inorganic compound is not particularly limited, but as an example, it is preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more. If it is smaller than 0.1 ⁇ m, the detour route of oxygen molecules does not become long, and improvement of gas barrier property cannot be expected sufficiently.
  • the upper limit of the average particle size is not particularly limited, but if the particle size is too large, defects such as streaks may occur on the coated surface depending on the coating method. Therefore, as an example, the average particle size is preferably 100 ⁇ m or less, and preferably 20 ⁇ m or less.
  • the average particle size of the plate-shaped inorganic compound means the particle size having the highest frequency of appearance when the particle size distribution of the plate-shaped inorganic compound is measured by a light scattering type measuring device.
  • the aspect ratio of the plate-like inorganic compound is preferably high in order to improve the gas barrier property due to the maze effect of oxygen. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.
  • the blending amount of the plate-shaped inorganic compound is arbitrary, but as an example, when the total mass of the solid content of the polyol composition (X), the polyisocyanate composition (Y), and the plate-shaped inorganic compound is 100 mass, the plate-shaped inorganic compound is formed.
  • the blending amount of the inorganic compound is 5 to 50 parts by mass.
  • the gas barrier adhesive may contain an adhesion promoter.
  • the adhesion accelerator include a silane coupling agent such as a hydrolyzable alkoxysilane compound, a titanate-based coupling agent, an aluminum-based coupling agent, and an epoxy resin. Silane coupling agents and titanate-based coupling agents can be expected to have the effect of improving the adhesiveness to various film materials.
  • the gas barrier adhesive may contain a known acid anhydride.
  • the acid anhydride include phthalic acid anhydride, succinic acid anhydride, het acid anhydride, hymic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, hexahydraphthalic acid anhydride, and tetrapromphthalic acid.
  • a compound or the like having an oxygen trapping function may be further added.
  • the compound having an oxygen trapping function include low molecular weight organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, and pyrogallol, and cobalt, manganese, nickel, and iron.
  • examples thereof include transition metal compounds such as copper.
  • the gas barrier adhesive may contain a compound represented by the following general formula (1) or (2).
  • R 1 to R 3 are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth) acryloyl group, a phenyl group which may have a substituent, and a (meth) acryloyloxy group. It is a group selected from an alkyl group having 1 to 4 carbon atoms having a hydrogen atom, at least one of which is a hydrogen atom, and n represents an integer of 1 to 4).
  • R 4 to R 5 are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth) acryloyl group, a phenyl group which may have a substituent, and a (meth) acryloyloxy group. It is a group selected from an alkyl group having 1 to 4 carbon atoms, where m and l are integers of 1 to 4, p is an integer of 0 to 30, q is an integer of 0 to 30, and p and q are. Except when both are 0.)
  • Specific examples of the compounds represented by the above general formulas (1) and (2) include phosphoric acid, pyrophosphate, triphosphate, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate and 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 blending amount of the compound represented by the general formula (1) or (2) is preferably 0.005 to 10% by mass, preferably 0.01 to 1% by mass, based on the total solid content of the gas barrier adhesive. It is more preferable to have.
  • a tackifier such as xylene resin, terpene resin, phenol resin, rosin resin may be added as needed.
  • the blending amount thereof is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the polyol composition (X) and the polyisocyanate composition (Y).
  • active energy rays can also be used as a method for reacting the polymerizable carbon-carbon double bond.
  • a known technique can be used as the active energy ray, and it can be cured by irradiating it with ionizing radiation such as an electron beam, ultraviolet rays, or ⁇ -rays.
  • ionizing radiation such as an electron beam, ultraviolet rays, or ⁇ -rays.
  • a known ultraviolet irradiation device equipped with a high-pressure mercury lamp, an excimer lamp, a metal halide lamp, or the like can be used.
  • a light (polymerization) initiator that generates radicals or the like by irradiation with ultraviolet rays is added to 100 parts by mass of the polyester polyol (A2). It is preferable to add to some extent.
  • Radical-generating photo (polymerization) initiators include hydrogen abstraction types such as benzyl, benzophenone, Michler's ketone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone, and benzoin ethyl ether, diethoxyacetophenone, benzylmethylketal, and hydroxy.
  • examples thereof include photocleavable types such as cyclohexylphenyl ketone and 2-hydroxy-2-methylphenyl ketone. Among these, one can be used alone or a plurality of them can be used in combination.
  • the gas barrier adhesive may contain a stabilizer (antioxidant, heat stabilizer, ultraviolet absorber, etc.), a plasticizer, an antistatic agent, a lubricant, an antiblocking agent, a colorant, a crystal nucleating agent, and the like. ..
  • a stabilizer antioxidant, heat stabilizer, ultraviolet absorber, etc.
  • plasticizer an antistatic agent, a lubricant, an antiblocking agent, a colorant, a crystal nucleating agent, and the like. ..
  • the gas barrier adhesive used in the present invention may be in either a solvent type or a solventless type.
  • the solvent-based adhesive is a method in which an adhesive is applied to a base material, then heated in an oven or the like to volatilize the organic solvent in the coating film, and then bonded to another base material, so-called dry. A form used in the laminating method.
  • the solvent used examples include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, cyclohexane and the like.
  • MEK methyl ethyl ketone
  • One or both of the polyol composition (X) and the polyisocyanate composition (Y) contains the above-mentioned organic solvent.
  • the solvent used as the reaction medium in the production of the constituent components of the polyol composition (X) or the polyisocyanate composition (Y) may be further used as a diluent during painting.
  • the solvent-free adhesive is used in the so-called non-solvent laminating method, which is a method in which an adhesive is applied to a base material and then bonded to another base material without heating in an oven or the like to volatilize the solvent.
  • non-solvent laminating method is a method in which an adhesive is applied to a base material and then bonded to another base material without heating in an oven or the like to volatilize the solvent.
  • Neither the polyol composition (X) nor the polyisocyanate composition (Y) is substantially free of the organic solvents described above.
  • the constituent components of the polyol composition (X) or the polyisocyanate composition (Y) and the organic solvent used as the reaction medium in the production of the raw material thereof could not be completely removed, and the polyol composition (X) or the polyisocyanate composition ( When a small amount of organic solvent remains in Y), it is understood that the organic solvent is not substantially contained.
  • the polyol composition (X) contains a low molecular weight alcohol
  • the low molecular weight alcohol reacts with the polyisocyanate composition (Y) and becomes a part of the coating film, so that it is not necessary to volatilize after coating. Therefore, such a form is also treated as a solvent-free adhesive.
  • the gas barrier adhesive is a solvent type
  • the gas barrier adhesive is applied to either the inorganic vapor deposition layer or the printing layer described later using a roll such as a gravure roll, and the organic solvent is applied by heating in an oven or the like. After volatilizing, the other is bonded to obtain the laminate of the present invention. It is preferable to perform an aging treatment after laminating.
  • the aging temperature is preferably room temperature to 80 ° C., and the aging time is preferably 12 to 240 hours.
  • the gas barrier adhesive is a solvent-free type
  • a gas barrier adhesive that has been preheated to about 40 ° C to 100 ° C is applied to either the inorganic vapor deposition layer or the printing layer using a roll such as a gravure roll. Immediately after that, the other is bonded to obtain the laminate of the present invention. It is preferable to perform an aging treatment after laminating.
  • the aging temperature is preferably room temperature to 70 ° C., and the aging time is preferably 6 to 240 hours.
  • the amount of the gas barrier adhesive applied is adjusted as appropriate.
  • the solid content is adjusted to be 1 g / m 2 or more and 10 g / m 2 or less, preferably 1 g / m 2 or more and 5 g / m 2 or less.
  • the amount of the adhesive applied is, for example, 1 g / m 2 or more and 10 g / m 2 or less, preferably 1 g / m 2 or more and 5 g / m 2 or less.
  • the laminate of the present invention may contain other layers, if necessary, in addition to the above-mentioned structure.
  • An embodiment of the laminate of the present invention (hereinafter, also referred to as a first embodiment) is shown in FIG.
  • the laminate has a first base material layer, a resin layer, an inorganic thin-film deposition layer, and a gas barrier adhesive layer, and further, a heat seal layer is provided on a surface opposite to the resin layer of the first base material.
  • the sealant layer in the first embodiment is a layer containing a heat-sealing resin that can be fused to each other by heat. In order to distinguish it from the sealant layer in other embodiments, the sealant layer in the first embodiment will be referred to as the sealant layer (1) below.
  • the sealant layer (1) is formed by applying a heat-sealing agent containing a heat-sealing resin and a solvent to a first base material and drying the solvent.
  • heat-sealing resin examples include celacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrified cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, rubber chloride, and cyclized rubber.
  • thermoplastic resins such as resins, urethane resins, ethylene-vinyl alcohol resins, styrene maleic acid resins, caseins, and alkyd resins, and these may be used alone or in combination of two or more.
  • the type in which these resins are dissolved in an organic solvent the type in which they are dissolved in water or an aqueous organic solvent, or an acrylic emulsion, a urethane emulsion, a polyvinyl alcohol resin, an ethylene-vinyl alcohol emulsion, or an ethylene- Any form may be used, such as an emulsion type in which a methacrylic acid-based emulsion, a polyolefin-based emulsion, an ethylene vinyl acetate-based emulsion, or the like is dispersed in water or an aqueous organic solvent.
  • the organic solvent is not particularly limited, but is, for example, aromatic hydrocarbons such as toluene, xylene, sorbesso # 100 and sorbesso # 150, aliphatic hydrocarbons such as hexane, heptane, octane and decane, methyl acetate and acetic acid.
  • aromatic hydrocarbons such as toluene, xylene, sorbesso # 100 and sorbesso # 150
  • aliphatic hydrocarbons such as hexane, heptane, octane and decane, methyl acetate and acetic acid.
  • ester-based organic solvents such as ethyl, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate.
  • aqueous organic solvent examples include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone and cyclohaxanone, ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether and ethylene.
  • Glycol monopropyl ether ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl
  • glycol ethers such as ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono, di) methyl ether.
  • the heat-sealing agent may contain components other than the heat-sealing resin and the solvent.
  • components include waxes, fillers, defoamers, viscosity modifiers, leveling agents, tackifiers, preservatives, antibacterial agents, rust inhibitors, antioxidants and the like.
  • a known method can be used as the method for applying the heat sealant.
  • Machines can be used.
  • a drying step may be provided in an oven or the like after coating.
  • the film thickness of the heat seal layer (coating amount (solid content) of the heat sealant) may be arbitrary, and as an example, it is more preferably 5 to 10 g / m 2 than 2 to 12 g / m 2 .
  • the second base material layer As the second base material layer, a film similar to that used for the first base material layer can be used.
  • the printing layer is a layer on which characters, figures, symbols, and other desired patterns are printed on the surface of the second base material layer on the gas barrier adhesive layer side using liquid ink.
  • liquid ink is a general term for solvent-based inks used for gravure printing or flexographic printing. It may be a so-called clear ink containing a resin, a colorant and a solvent as essential components, or a so-called clear ink containing the resin and the solvent and substantially free of the colorant.
  • the printed layer may be provided on the entire surface of the second base material on the gas barrier adhesive layer side, or may be provided only on a part of the printed layer. The printed layer is bonded to the inorganic vapor-filmed layer via the above-mentioned gas barrier adhesive layer.
  • the resin used for the liquid ink is not particularly limited, and for example, acrylic resin, polyester resin, styrene resin, styrene-maleic acid resin, maleic acid resin, polyamide resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, etc.
  • Colorants used in liquid inks include titanium oxide, petals, antimony red, cadmium red, cadmium yellow, cobalt blue, navy blue, ultramarine, carbon black, graphite and other inorganic pigments, soluble azo pigments, insoluble azo pigments, and azo lakes.
  • examples thereof include pigments, condensed azo pigments, copper phthalocyanine pigments, organic pigments such as condensed polycyclic pigments, and extender pigments such as calcium carbonate, cadmium, barium sulfate, aluminum hydroxide, and talc.
  • the organic solvent used for the liquid ink preferably does not contain an aromatic hydrocarbon-based organic solvent. More specifically, alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol and butanol, ketone-based organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like.
  • alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol and butanol
  • ketone-based organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like.
  • Ester-based organic solvents aliphatic hydrocarbon-based organic solvents such as n-hexane, n-heptane, and n-octane, and alicyclic hydrocarbon-based organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane. Etc., and one type or a combination of two or more types can be used.
  • a vapor deposition layer of silica, alumina, or an inorganic oxide obtained by binary vapor deposition thereof may be provided directly on the second substrate or via a primer layer.
  • a gas barrier coat layer may be provided on the vapor-filmed layer of the inorganic oxide. Conventionally known ones can be used as the primer layer, the vapor-deposited layer of the inorganic oxide, and the gas barrier coat layer.
  • the print layer may be omitted.
  • the printed layer may be provided on the surface of the second base material layer opposite to the gas barrier adhesive layer.
  • the second base material may be in direct contact with the gas barrier adhesive layer, or between the second base material and the gas barrier adhesive layer, either an inorganic oxide vapor-deposited layer or a gas barrier coat layer, or Both may be provided.
  • the vapor-filmed layer of the inorganic oxide is provided, it may be provided directly on the second substrate or may be provided via a primer.
  • FIG. 1 Another embodiment of the laminate of the present invention (hereinafter, also referred to as a second embodiment) is shown in FIG.
  • the laminate has a first base material layer, a resin layer, an inorganic vapor deposition layer, and a gas barrier adhesive layer, and an adhesive is applied to the surface of the first base material opposite to the resin layer.
  • the sealant layer bonded via the sealant layer has a printing layer and a second base material layer on the surface of the gas barrier adhesive layer opposite to the inorganic vapor deposition layer.
  • the second base material and the printing layer are the same as those in the first embodiment.
  • the sealant layer in the second embodiment is a layer (sealant film) containing a heat-sealing resin that can be melted by heat and fused to each other.
  • the sealant layer in the second embodiment will be referred to as the sealant layer (2) below.
  • Suitable resins for the sealant film include polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- ( Acrylic acid, methacrylic acid, maleic anhydride, olefinic resins such as meth) acrylic acid copolymer, ethylene- (meth) ethyl acrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene.
  • Modified olefin resin modified with fumaric acid and other unsaturated carboxylic acids ternary copolymer of ethylene- (meth) acrylic acid ester-unsaturated carboxylic acid, cyclic polyolefin, cyclic olefin copolymer, polyethylene terephthalate (PET), polyacrylonitrile (PAN) and the like.
  • a resin film, sheet, or other coating film made of one or more of these resins can be used as a sealant film.
  • any unstretched, uniaxially stretched, or biaxially stretched film can be used as the sealant film.
  • the stretched film stretched in the biaxial direction is vertically stretched 2 to 4 times by, for example, a roll stretching machine at 50 to 100 ° C., and further laterally stretched 3 to 5 times by a tenter stretching machine in an atmosphere of 90 to 150 ° C. Subsequently, it is obtained by heat treatment with a tenter stretching machine in an atmosphere of 100 to 240 ° C.
  • simultaneous biaxial stretching and sequential biaxial stretching may be used.
  • An easily peelable sealant film may be used for the sealant layer.
  • the easily peelable sealant film any of the interfacial peeling type, the coagulation peeling type, and the delamination type can be applied, and can be appropriately selected according to the type of the packaging material and the required characteristics described later.
  • the index of easy peelability is appropriately set according to the type of packaging material and the required characteristics, but as an example, the sealing strength is 2 to 20 N / 15 mm.
  • easy peelability can be exhibited by a phase-separated polymer blend in which polypropylene is combined with high-density polyethylene, low-density polyethylene, an ethylene-vinyl acetate copolymer, or the like.
  • the film thickness of the sealant film can be arbitrarily selected, but when applied to a packaging material described later, for example, it is selected in the range of 5 to 500 ⁇ m. It is more preferably 10 to 250 ⁇ m, and even more preferably 15 to 100 ⁇ m. If it is less than 5 ⁇ m, sufficient laminating strength as a packaging material cannot be obtained, and there is a possibility that puncture resistance and the like may be lowered. If it exceeds 250 ⁇ m, the cost will increase and the film will become hard, resulting in poor workability.
  • the sealant layer (2) may be provided with an inorganic vapor deposition layer on at least one surface of the sealant film.
  • Such an inorganic thin-film deposition layer can be formed by the same material and method as the inorganic thin-film deposition layer provided on the base material.
  • a barrier coat layer may be further provided on the inorganic vapor deposition layer provided on the sealant film.
  • the adhesive layer is a cured coating film of a laminating adhesive.
  • the sealant layer (2) is bonded to the first base material via the adhesive layer.
  • the adhesive used may be the above-mentioned gas barrier adhesive or a general-purpose laminating adhesive having no gas barrier property.
  • a laminating adhesive a two-component curable type containing a polyol composition and a polyisocyanate composition can be exemplified, and either a solvent type or a solventless type can be preferably used.
  • the laminating adhesive may be applied to the first base material layer side and then bonded to the heat seal layer, or may be applied to the heat seal layer side and then bonded to the first base material. May be good.
  • the method of applying the adhesive for laminating, the aging conditions, and the amount of application may be the same as those of the gas barrier adhesive layer.
  • the laminate has a first base material layer, a resin layer, an inorganic vapor deposition layer, and a gas barrier adhesive layer, and further has a sealant layer on the surface of the gas barrier adhesive layer opposite to the inorganic vapor deposition layer. It has a printed layer and a second base material layer bonded to each other on the surface opposite to the resin layer of the first base material via an adhesive. Each layer is the same as in the second embodiment.
  • the unstretched sealant film is easy to stretch and it is difficult to apply the adhesive.
  • the gas barrier adhesive is a solvent type
  • the sealant film may be deformed while passing through a drying device for volatilizing the solvent of the adhesive layer. Therefore, in the third embodiment, the gas barrier adhesive is usually applied on the inorganic thin-film deposition layer. In this case, when applying the gas barrier adhesive, it rubs against the roller, and although it is not as good as the sealant film, the first base material layer is deformed as it passes through the drying device and cannot follow it. The inorganic vapor deposition layer is damaged. However, in the present invention, it is possible to suppress the deterioration of the gas barrier property even when the inorganic thin-film deposition layer is damaged.
  • the gas barrier adhesive layer between the second base material layer and the print layer (when no print layer is provided or the print layer is the first base material) is used.
  • a primer layer, an inorganic oxide vapor deposition layer, and a gas barrier coat layer can be provided between the second base material layer and the gas barrier adhesive layer).
  • the laminate of the present invention can be used as a multi-layer packaging material for the purpose of protecting foods, pharmaceuticals and the like.
  • its layer structure may change depending on the contents, usage environment, and usage pattern.
  • the packaging material of the present invention is obtained, for example, by laminating the heat-sealing layers of the laminate of the present invention facing each other and then heat-sealing the peripheral end portions thereof.
  • the laminated body of the present invention is bent or overlapped so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral end thereof is, for example, a side seal type or a two-way seal type.
  • the packaging material of the present invention can take various forms depending on the contents, the environment in which it is used, and the form in which it is used. Self-supporting packaging materials (standing pouches), etc. are also possible.
  • a heat sealing method a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.
  • the opening After filling the packaging material of the present invention with the contents from the opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention.
  • the contents to be filled include rice confectionery, bean confectionery, nuts, biscuits and cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snack confectionery and other confectionery, bread, snack noodles, instant noodles, dried noodles, pasta.
  • the packaging material of the present invention can also be used as a packaging material for pharmaceuticals such as cigarettes, disposable body warmers, infusion packs, cosmetics, and vacuum heat insulating materials.
  • the packaging material of the present invention may be a lid material using the laminate of the present invention.
  • Adhesive 1 (Preparation of Polyol Composition X1)
  • a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snyder tube, and a condenser 879.37 parts of ethylene glycol, 1580.52 parts of phthalic anhydride, and 0.10 parts of titanium tetraisopropoxide were charged and rectified.
  • the internal temperature was maintained at 200 ° C. by gradually heating so that the temperature of the upper part of the tube did not exceed 100 ° C.
  • Polyisocyanate composition Y1 Mitsui Chemicals'"TakenateD-110N" (trimethylolpropane adduct non-volatile component of metaxylylene diisocyanate 75.0% NCO% 11.5%) was used as the polyisocyanate composition Y1.
  • Adhesive 2 Polyisocyanate composition Y2
  • 36 parts of 4,4-diphenylmethane diisocyanate and 19 parts of 2,4'-diphenylmethane diisocyanate were placed in a reaction vessel equipped with a stirrer, a thermometer and a nitrogen gas introduction tube, stirred under nitrogen gas, and heated to 60 ° C. .. 11 parts of polypropylene glycol having a number average molecular weight of 400 (hereinafter abbreviated as "PPG"), 22 parts of PPG having a number average molecular weight of 1000, and 11 parts of PPG having a number average molecular weight of 2000 were added dropwise in several times.
  • the urethanization reaction was terminated by stirring for 5 to 6 hours.
  • the NCO group content of the obtained polyisocyanate was 13.5%. This was designated as the polyisocyanate composition Y2.
  • Adhesive 3 Polyol composition X3 Put 73.98 parts of castor oil and 51.02 parts of polypropylene glycol (molecular weight about 4000) in a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, a cooling condenser, and a dropping funnel, and stir while heating at 70 ° C. 2.55 parts of milionate MN (mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) was added dropwise using a dropping funnel and further stirred for 4 hours to obtain a polyol composition X3. The hydroxyl value was 115.0 mgKOH / g.
  • Polyisocyanate composition X3 Put 114.00 parts of myionate MN (mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) in a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, a cooling condenser, and a dropping funnel. Stir while heating to 70 ° C., 28.16 parts of polypropylene glycol (molecular weight about 400) and 58.44 parts of polypropylene glycol (molecular weight about 1000) are added dropwise using a dropping funnel over 2 hours, and further stirred for 4 hours. The polyisocyanate composition Y3 was obtained. The NCO% measured according to JIS-K1603 was 13.5%.
  • Example 1 Using the OPP film 1 having a film thickness of 18 ⁇ m, a laminated body in which a resin layer and an aluminum-deposited layer were laminated was obtained according to a conventional method. Next, the adhesive 1 was applied to the OPP film 2 having a thickness of 20 ⁇ m so as to have a coating film amount of 3.0 g / m 2 (solid content) using a bar coater, and a diluting solvent was used with a dryer set at a temperature of 70 ° C. Was volatilized and dried to form an adhesive layer. After the aluminum-deposited layer and the OPP film 2 were bonded to each other via the adhesive layer, they were aged at 40 ° C.
  • the thickness of the resin layer was 1 ⁇ m, and an ethylene vinyl alcohol copolymer having a saponification degree of 95% or more, an ethylene ratio of 48 mol%, a glass transition temperature of 50 ° C., and a melting point of 157 ° C. was used.
  • Comparative Example 1 A laminate of Comparative Example 1 was obtained in the same manner as in Example 1 except that the adhesive 3 was used instead of the adhesive 1.
  • Example 2 Using the OPP film 1 having a thickness of 25 ⁇ m, a resin layer and an aluminum vapor-deposited layer were formed on one surface according to a conventional method, and a heat seal layer having a thickness of 0.5 ⁇ m was formed on the other surface. A laminate was obtained. Next, the adhesive 1 was applied to the OPP film 2 having a thickness of 20 ⁇ m so as to have a coating amount of 3.0 g / m 2 (solid content) using a bar coater, and a diluting solvent was used with a dryer set at a temperature of 70 ° C. Was volatilized and dried to form an adhesive layer.
  • Example 2 After the aluminum-deposited layer and the OPP film 2 were bonded to each other via the adhesive layer, they were aged at 40 ° C. for 2 days to obtain the laminate of Example 2. As the resin layer, the same ethylene vinyl alcohol copolymer as in Example 1 was used.
  • Comparative Example 2 A laminate of Comparative Example 2 was obtained in the same manner as in Example 2 except that the adhesive 3 was used instead of the adhesive 1.
  • Example 3 Using the OPP film 1 having a film thickness of 18 ⁇ m, a laminated body in which a resin layer and an aluminum layer were laminated was obtained according to a conventional method. Next, the adhesive 2 was applied to the OPP film 2 having a thickness of 19 ⁇ m so as to have a coating film amount of 3.0 g / m 2 (solid content) using a bar coater, and a diluting solvent was used with a dryer set at a temperature of 70 ° C. Was volatilized to form an adhesive layer. The aluminum vapor deposition layer and the OPP film 2 were bonded to each other via the adhesive layer.
  • an adhesive layer was formed on the OPP film 1 in the same manner as above, and the film was bonded to an LLDPE film having a film thickness of 40 ⁇ m via the adhesive layer, and then aged at 40 ° C. for 2 days.
  • a laminate was obtained.
  • a resin layer having a film thickness of 0.34 ⁇ m was formed using polyvinyl alcohol, and subsequently, an aluminum vapor-deposited layer having a film thickness of 40 nm was formed on the resin layer.
  • the film thickness of the resin layer was 0.34 ⁇ m, and polyvinyl alcohol having a saponification degree of 99.5% was used.
  • Comparative Example 3 A laminate of Comparative Example 3 was obtained in the same manner as in Example 3 except that the adhesive 3 was used instead of the adhesive 2.
  • Example 4 Using the OPP film 1 having a film thickness of 18 ⁇ m, a laminated body in which a resin layer and an aluminum layer were laminated was obtained according to a conventional method. Next, the adhesive 1 was applied to the OPP film 2 having a film thickness of 30 ⁇ m so as to have a coating film amount of 3.0 g / m 2 (solid content) using a bar coater, and a diluting solvent was used with a dryer set at a temperature of 70 ° C. Was volatilized to form an adhesive layer. The aluminum vapor deposition layer and the OPP film 2 were bonded to each other via the adhesive layer.
  • an adhesive layer was formed on the OPP film 1 in the same manner as above, and the film was bonded to a CPP film having a film thickness of 25 ⁇ m via the adhesive layer, and then aged at 40 ° C. for 2 days. A laminate was obtained.
  • the film thickness of the resin layer was 0.6 ⁇ m, and the same polyvinyl alcohol as in Example 3 was used.
  • Comparative Example 4 A laminate of Comparative Example 4 was obtained in the same manner as in Example 4 except that the adhesive 3 was used instead of the adhesive 1.
  • Example 5 Using the OPP film 1 having a film thickness of 18 ⁇ m, a laminated body in which the same resin layer and aluminum layer as in Example 4 were laminated was obtained according to a conventional method. Next, the adhesive 3 was applied to the OPP film 2 having a film thickness of 30 ⁇ m so as to have a coating film amount of 3.0 g / m 2 (solid content) using a bar coater, and a diluting solvent was used with a dryer set at a temperature of 70 ° C. Was volatilized to form an adhesive layer. The OPP film 1 and the OPP film 2 were bonded together via the adhesive layer.
  • an adhesive layer was formed on the aluminum-deposited layer in the same manner as above except that the adhesive 1 was used, and after being bonded to a CPP film having a thickness of 25 ⁇ m via the adhesive layer, the temperature was 40 ° C. for 2 days. Aging was performed to obtain a laminated body of Example 5.
  • Comparative Example 5 A laminate of Comparative Example 5 was obtained in the same manner as in Example 5 except that the adhesive 3 was used instead of the adhesive 1.
  • Comparative Example 7 A laminate of Comparative Example 7 was obtained in the same manner as in Comparative Example 6 except that the adhesive 3 was used instead of the adhesive 1.
  • an adhesive layer was formed on the aluminum-deposited layer in the same manner as above, bonded to a CPP film having a film thickness of 25 ⁇ m via the adhesive layer, and then aged at 40 ° C. for 2 days. A laminate was obtained.
  • Comparative Example 9 A laminate of Comparative Example 9 was obtained in the same manner as in Comparative Example 8 except that the adhesive 3 was used instead of the adhesive 1.
  • the laminate of the present invention showed excellent gas barrier properties even under high humidity and after a bending test.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
PCT/JP2021/045262 2020-12-22 2021-12-09 ガスバリア性積層体、包装材 Ceased WO2022138188A1 (ja)

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JP2000006304A (ja) * 1998-04-24 2000-01-11 Toppan Printing Co Ltd バリア―性積層体およびこれを用いた包装材料およびこれを用いた包装体
JP2000025145A (ja) * 1998-04-24 2000-01-25 Toppan Printing Co Ltd バリア―性積層体およびこれを用いた包装材料およびこれを用いた包装体
JP2012096551A (ja) * 2006-11-16 2012-05-24 Mitsubishi Plastics Inc ガスバリアフィルム積層体
JP2012076288A (ja) * 2010-09-30 2012-04-19 Dainippon Printing Co Ltd ガスバリア性フィルム積層体、及び包装袋
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