WO2022124313A1 - ガスバリア性積層体およびそれを用いた包装体 - Google Patents

ガスバリア性積層体およびそれを用いた包装体 Download PDF

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Publication number
WO2022124313A1
WO2022124313A1 PCT/JP2021/044989 JP2021044989W WO2022124313A1 WO 2022124313 A1 WO2022124313 A1 WO 2022124313A1 JP 2021044989 W JP2021044989 W JP 2021044989W WO 2022124313 A1 WO2022124313 A1 WO 2022124313A1
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WIPO (PCT)
Prior art keywords
gas barrier
water
layer
metal alkoxide
soluble polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2021/044989
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English (en)
French (fr)
Japanese (ja)
Inventor
里佳 石井
裕美子 小島
茂実 杉山
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Toppan Inc
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Toppan Inc
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Priority to JP2022568296A priority Critical patent/JPWO2022124313A1/ja
Publication of WO2022124313A1 publication Critical patent/WO2022124313A1/ja
Priority to US18/206,384 priority patent/US12612231B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging

Definitions

  • the present disclosure relates to a gas barrier laminate used in the packaging field of foods, non-foods, pharmaceuticals, etc., and is a gas barrier laminate having high gas barrier resistance and aiming to reduce the environmental load, and the gas barrier laminate thereof. It relates to the package used.
  • Packaging materials used for packaging foods, non-foods, pharmaceuticals, etc. are made of oxygen and water vapor that permeate the packaging materials in order to suppress deterioration of the contents and maintain their functions and properties, and other gases that change the contents. It is used as one function to prevent the influence.
  • Aluminum foil may be used as a material for this purpose. However, although aluminum foil is lighter than glass bottles and plastic bottles, it has a high specific gravity, so it requires energy to transport products filled with contents, and waste packaging materials are incinerated. In the case of such waste, the suitability for the environment has been an issue, such as the generation of a large amount of incineration ash.
  • a method of forming a metal such as aluminum or a metal oxide as a thin film on a base material to develop gas barrier properties and a wet coating method of a material having high gas barrier properties are known. According to these methods, a laminated body having a high gas barrier property can be obtained, and the same property can be obtained with a smaller amount of material, so that it can be said that the laminate has higher aptitude from the environmental point of view.
  • Patent Document 1 uses a coating layer formed by heating and drying a coating liquid containing a hydroxyl group-containing polymer compound, a metal alkoxide and a hydrolyzate thereof on a plastic substrate as a gas barrier layer. Proposed.
  • thermoplastic resin used as the heat seal layer, a polyethylene resin having a low melting point and good workability, a polypropylene resin, an olefin resin such as an ethylene-vinyl acetate copolymer, or the like is used.
  • the thickness of the heat seal layer is designed depending on the type and weight of the contents, but is generally 30 ⁇ m or more due to the processing limitation of the heat seal layer.
  • this heat seal layer with the base material of the laminated body, a dry laminating method or an extrusion laminating method is often used, and in each case, a solvent-based adhesive is used.
  • the heat-sealed layer is indispensable for manufacturing an airtight packaging bag, but has a problem that it has a large environmental load in terms of the amount of thermoplastic resin used and the use of organic solvent.
  • Patent Document 1 After forming the coating layer of Patent Document 1, it was necessary to apply water by spraying or gravure coating in order to improve the denseness of the coating layer. Further, since the thin film layer made of aluminum oxide is provided as the base of the coating layer, the composition and process are complicated, and the manufacturing energy is large.
  • the gas barrier layer disclosed in Patent Documents 2 and 3 is designed assuming a film such as polyethylene as a heat seal layer, and when a water-based heat seal varnish is used as a seal layer, the following problems are solved.
  • a water-based heat seal varnish is wet-coated on a gas barrier layer formed by a water-based wet coating
  • the processing conditions are narrow to prevent the coating liquid from repelling, and the underlying gas barrier layer is redissolved or swollen to cause a gas barrier.
  • the sex was not stable.
  • the crosslink density of the gas barrier layer is increased in order to prevent redissolution and swelling, the film becomes hard and brittle, and the gas barrier property tends to deteriorate.
  • the layer thickness of the heat seal varnish becomes small, the effect that the seal layer protects the mechanical deterioration of the gas barrier layer is reduced, and there is also a problem that the seal layer is easily deteriorated.
  • the present disclosure provides a gas barrier laminated body having high environmental suitability for both the manufacturing method and the constituent materials and having high mechanical strength, and a package using the same.
  • the present disclosure relates to a gas barrier laminate having an aqueous gas barrier layer suitable for an aqueous heat seal varnish as a heat seal layer.
  • one aspect of the present disclosure is a gas barrier laminate in which at least a gas barrier layer and a seal layer are laminated in this order on a substrate, and the gas barrier layer is generally a water-soluble polymer.
  • a coating solution containing a metal alkoxide represented by the formula M (OR 1 ) n (M: metal element, R1 : alkyl group, n: oxidation number of metal element) or a hydrolyzate thereof heat-drying is performed.
  • the content of the water-soluble polymer is 50 wt% or more based on the total mass of the solid content of the coating liquid, and the total content of the metal alkoxide and its hydrolysis is the solid content of the coating liquid.
  • the content of the water-soluble polymer is 70 wt% or more based on the total mass of the solid content of the coating liquid, and the total content of the metal alkoxide and its hydrolysis is the total mass of the solid content of the coating liquid. It may be 5 to 30 wt% with reference to.
  • the gas barrier layer contains a scaly filler, the scaly filler has a particle size of 0.2 to 10 ⁇ m, an aspect ratio of 50 or more, and a total content of the metal alkoxide and its hydrolyzate and the scaly filler. , 5 to 30 wt% based on the total mass of the solid content of the coating liquid.
  • the metal alkoxide may be tetraethoxysilane.
  • the scaly filler is a silica filler having a silanol group on the surface, and the amount of the silanol group may be 10 to 70 ⁇ mol / m 2 .
  • the water-soluble polymer contains polyvinyl alcohol, and the polyvinyl alcohol may have a saponification degree of 90% or more and a polymerization degree of 500 or more.
  • the gas barrier laminate may include a thin-film deposition layer containing a metal or a metal oxide between the substrate and the gas barrier layer.
  • the substrate may be paper.
  • Another aspect of the present disclosure is a package characterized by using the above-mentioned gas barrier laminate.
  • FIG. 1 is a schematic cross-sectional view showing a laminated structure of a gas barrier laminated body 1 according to an embodiment of the present disclosure.
  • the gas barrier laminate 1 is formed by laminating a gas barrier layer 3 and a seal layer 4 on a base material 2 in this order.
  • the gas barrier layer 3 in the present disclosure includes a water-soluble polymer and a general formula M (OR 1 ) n (M: metal element, R 1 : an alkyl group such as CH 3 , C 2 H 5 and n: oxidation number of the metal element). It is a layer formed by heating and drying a coating liquid containing a metal alkoxide represented by (1) or a hydrolyzate of the metal alkoxide.
  • the gas barrier layer 3 may be a cured product of a composition containing a water-soluble polymer and a metal alkoxide represented by the general formula M (OR 1 ) n or a hydrolyzate of the metal alkoxide.
  • the gas barrier layer 3 may be a composite obtained by heating and drying a coating liquid containing a water-soluble polymer and a metal alkoxide represented by the general formula M (OR 1 ) n or a hydrolyzate of the metal alkoxide.
  • water-soluble polymer examples include polyvinyl alcohol, poly (vinyl alcohol-co-ethylene), polyvinylpyrrolidone, starch, cellulose, methyl cellulose, carboxymethyl cellulose, sodium alginate, and polyacrylic acid.
  • the water-soluble polymer may particularly contain polyvinyl alcohol (PVA).
  • PVA is generally obtained by saponifying polyvinyl acetate, and can be used from partially saponified PVA in which tens of percent of acetic acid groups remain to fully saponified PVA in which only a few percent of acetic acid groups remain. ..
  • PVA may have a saponification degree of 90% or more from the viewpoint of having a large number of hydroxyl groups and having excellent gas barrier properties. Further, PVA may have a degree of polymerization of 500 or more from the viewpoint of excellent toughness and gas barrier property of the film when the gas barrier layer is formed.
  • the content of the water-soluble polymer is 60 wt% or more, 70 wt% or more, 75 wt% based on the total mass of the solid content of the coating liquid forming the gas barrier layer from the viewpoint of excellent water vapor transmission rate even after bending. As mentioned above, it may be 80 wt% or more, 85 wt% or more, 90 wt% or more, or 95 wt% or more.
  • the content of the water-soluble polymer is 95 wt% or less, 90 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less, or 70 wt% or less, based on the total mass of the solid content of the coating liquid forming the gas barrier layer. May be.
  • the content of the water-soluble polymer may be 50 to 95 wt%, 70 to 95 wt%, or 80 to 95 wt% based on the total mass of the solid content of the coating liquid forming the gas barrier layer.
  • the metal alkoxide represented by the general formula M (OR 1 ) n (M: metal element, R 1 : alkyl group such as CH 3 , C 2 H 5 ; n: oxidation number of metal element) in the present disclosure is hydrolyzed. It can later be condensed to form a glass-like film.
  • the metal alkoxide and its hydrolyzate can also be crosslinked with a water-soluble polymer having a hydroxyl group to enhance the water resistance of the water-soluble gas barrier film.
  • tetraethoxysilane [Si (OC 2 H 5 ) 4 ], triisopropoxyaluminum [Al (O-2'-C 3 H 7 ) 3 ], etc. can be used, but gas barrier properties and coatings can be used. It may be tetraethoxysilane because of its workability.
  • Examples of the metal element M of the metal alkoxide include Si, Ti, Al, Zr and the like.
  • the metal element M of the metal alkoxide may be Si or Al.
  • the number of carbon atoms of the alkyl group R 1 may be 1 to 8, 2 to 6, 2 to 4, or 2 to 3.
  • the total content of the metal alkoxide and its hydrolysis is 5 to 50 wt% based on the total mass of the solid content of the coating liquid forming the gas barrier layer.
  • the total content of the metal alkoxide and its hydrolysis is 40 wt% or less, 30 wt% or less, 25 wt% or less, 20 wt% or less, 15 wt% or less, or 10 wt% based on the total mass of the coating liquid forming the gas barrier layer.
  • the total content of the metal alkoxide and its hydrolysis may be 10 wt% or more, 15 wt% or more, 20 wt% or more, or 25 wt% or more based on the total mass of the solid content of the coating liquid forming the gas barrier layer. good.
  • the total content of the metal alkoxide and its hydrolysis may be 5 to 40 wt%, 5 to 30 wt%, or 5 to 20 wt% based on the total mass of the solid content of the coating liquid forming the gas barrier layer.
  • the gas barrier layer 3 in the present disclosure includes a water-soluble polymer and a general formula M (OR 1 ) n (M: metal element, R 1 : an alkyl group such as CH 3 , C 2 H 5 and n: oxidation number of the metal element). It may be a composite formed by heating and drying a coating liquid containing a metal alkoxide represented by and a hydrolyzate of the metal alkoxide.
  • the mass ratio of the water-soluble polymer to the metal alkoxide and its hydrolyzate in the coating liquid is, for example, 5: 5 to 9.5: 0.5 (preferably 7: 3 to 9.5: 0.5). It contains a non-volatile component.
  • the mass ratio of the water-soluble polymer to the metal alkoxide and its hydrolyzate (the mass-based content of the water-soluble polymer / the mass-based content of the metal alkoxide and its hydrolyzate) is, for example, 1 to 19. (Preferably 2.3 to 19).
  • the mass ratio of the water-soluble polymer is equal to or higher than the above-mentioned mass ratio, that is, when the mass ratio is 1 or more (preferably 2.3 or higher)
  • the gas barrier layer mainly composed of the water-soluble polymer has.
  • the amount of the soft component is sufficiently large, the number of cross-linking points starting from the metal alkoxide does not increase too much, the gas barrier layer is prevented from becoming too hard, and the deterioration of the gas barrier property due to bending or tension of the laminate is easily suppressed. Become. Further, when the mass ratio of the water-soluble polymer is not more than the above-mentioned mass ratio, that is, when the mass ratio is 19 or less, the number of cross-linking points starting from the metal alkoxide does not become too small, and the film is made of water. It is possible to suppress the decrease in gas barrier property due to swelling.
  • the mass ratio of the water-soluble polymer to the metal alkoxide and its hydrolyzate is, for example, 8: 2 or more and 9.5: 0.5 or less. More specifically, the mass ratio of the water-soluble polymer to the metal alkoxide and its hydrolyzate is 1.5 to 19, 2.3 to 19, 3 to 19, 4 to 19, 5.7 to 19 or 9. It may be ⁇ 19.
  • the physical characteristics of the film formed by heating and drying the coating liquid can be adjusted in detail. It will be possible.
  • a filler may be added to the gas barrier layer according to the embodiment of the present disclosure while maintaining the composition ratio of the water-soluble polymer, the metal alkoxide and the hydrolyzate thereof.
  • the granular filler can increase the strength of the gas barrier layer, and the scaly filler can improve the gas barrier property.
  • the gas barrier layer may contain a scaly filler.
  • the material of the scaly filler that can be used in the present disclosure is not particularly limited, and for example, kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, etc. Examples thereof include titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, silica (for example, colloidal silica), and satin white.
  • the particle size of the scaly filler may be 0.2 to 10 ⁇ m, 0.2 to 5 ⁇ m, or 0.2 to 1 ⁇ m.
  • the particle size of the filler means a number average particle size and can be measured with an electron microscope.
  • the aspect ratio of the scaly filler may be 50 or more, 80 or more, or 100 or more, and may be 500 or less, 400 or less, or 300 or less.
  • the aspect ratio of the scaly filler may be 50-500, 80-400, or 100-300.
  • the aspect ratio of the filler is defined as the ratio of the maximum length of the filler to the minimum length in the direction perpendicular to the direction having the maximum length when the filler is observed under a microscope.
  • the presence of the scaly filler in the water-soluble polymer such as PVA can increase the water resistance of the film in the same manner as the metal alkoxide such as tetraethoxysilane. Further, by using a filler having a high aspect ratio, it is possible to improve the gas barrier property by the maze effect.
  • the particle size of the scaly filler is 0.2 ⁇ m or more, the effect of improving the gas barrier property due to the maze effect can be sufficiently obtained, and the gas barrier property of the entire film can be easily improved.
  • the particle size of the scaly filler is 10 ⁇ m or less, the processability is excellent, defects are less likely to occur in the film, and the gas barrier property is less likely to deteriorate.
  • the aspect ratio of the filler is 50 or more, the maze effect can be sufficiently obtained and the gas barrier property can be easily improved.
  • the content of the scaly filler in the gas barrier layer may be 1 to 20 wt%, 2 to 15 wt%, or 3 to 10 wt% based on the total mass of the solid content of the coating liquid forming the gas barrier layer.
  • the content of the scaly filler in the gas barrier layer is 5 to 30 wt% based on the total mass of the solid content of the coating liquid forming the gas barrier layer together with the metal alkoxide and its hydrolyzate in the gas barrier layer. It may be 20 wt% or 5 to 15 wt%.
  • the total content of the scaly filler, the metal alkoxide and its hydrolyzate is within the above range, the gas barrier layer does not become too hard and cracks are less likely to occur in the gas barrier layer, so that the gas barrier property is lowered. It becomes difficult to do.
  • the scaly filler may be a silica filler (silica particles) having a silanol group on the surface from the viewpoint of gas barrier property and water resistance.
  • the amount of silanol groups on the surface of the silica filler may be 10 to 70 ⁇ mol / m 2 , 15 to 60 ⁇ mol / m 2 , or 20 to 45 ⁇ mol / m 2 .
  • the SiO 2 purity of the silica particles may be, for example, 95 wt% or more, or 98 wt% or more.
  • the silanol group on the surface of the scaly silica filler and the silanol group in the water-soluble polymer adhere to each other by hydrogen bonds, so that the water resistance and gas barrier property are further improved.
  • the thickness of the gas barrier layer may be 0.1 to 50 ⁇ m, 0.2 to 20 ⁇ m, or 0.5 to 10 ⁇ m.
  • various plastic films and papers can be used as the base material that can be used in the present disclosure.
  • a film made of biodegradable plastic a film made of biomass plastic, or paper is used as a base material, it is decomposed by microorganisms even if it is left in the environment as garbage, and it is manufactured from natural products, so it is suitable for environmental load. be.
  • the thickness of the base material may be 3 ⁇ m or more, 6 ⁇ m or more, or 10 ⁇ m or more, and may be 200 ⁇ m or less, 100 ⁇ m or less, or 50 ⁇ m or less.
  • the thickness of the substrate may be 3 to 200 ⁇ m or 10 to 50 ⁇ m.
  • the seal layer according to the present disclosure contains a heat seal varnish, and the heat seal varnish is not particularly limited except that it is water-based.
  • the water-based heat-sealed varnish may be any one in which the heat-sealed varnish component is dispersed in an aqueous solvent (for example, water).
  • an acrylic resin emulsion, a styrene-acrylic emulsion, an ionomer-based emulsion, or a polyolefin dispersed in an aqueous solvent for example, an acrylic resin emulsion, a styrene-acrylic emulsion, an ionomer-based emulsion, or a polyolefin dispersed in an aqueous solvent.
  • a system emulsion or the like can be used.
  • an aqueous polyolefin resin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic acid anhydride group and a carboxylic acid ester may be used.
  • a biodegradable heat sealant such as polylactic acid-based or polybutylene succinate-based may be used.
  • the heat seal layer may contain other components in addition to the above components.
  • other components include a silane coupling agent, an organic titanate, an acrylic resin, a polyester, a polyurethane, a polycarbonate, a polyurea, a polyamide, a polyolefin-based emulsion, a polyimide, a melamine resin, and a phenol resin.
  • the amount of these other components added may be 50 wt% or more, 70 wt% or more, 90 wt% or more, or 100 wt% with respect to the above heat-sealed varnish component. good.
  • the thickness of the heat seal layer may be, for example, 0.05 ⁇ m or more, 0.5 ⁇ m or more, or 1 ⁇ m or more, and may be 20 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less.
  • the thickness of the heat seal layer is 1 to 5 ⁇ m, it is possible to provide a laminate in which sufficient heat seal strength can be obtained and at the same time, it is resistant to bending and the amount of plastic is reduced.
  • the gas barrier laminate according to the embodiment of the present disclosure may include a vapor-deposited layer containing a metal or a metal oxide between the base material and the gas barrier layer.
  • a plastic film is used as the base material
  • transparency is maintained by using a vapor-deposited layer made of a metal oxide such as aluminum oxide.
  • an opaque base material such as paper is used as the base material
  • the thickness of the vapor-film layer may be 0.01 to 1 ⁇ m, 0.02 to 0.5 ⁇ m, or 0.04 to 0.1 ⁇ m.
  • the thin-film deposition layer can be formed by, for example, a vacuum vapor deposition method, a plasma assist method, an ion beam assist method, a sputtering method, a reactive vapor deposition method, or the like.
  • the thin-film deposition layer may be formed by a vacuum vapor deposition method from the viewpoint of excellent productivity, and may be formed by a plasma assist method from the viewpoint of excellent adhesion between the thin-film deposition layer and the base material layer and from the viewpoint of improving the denseness of the vapor-film deposition layer.
  • It may be formed by an ion beam assist method, or may be formed by a reactive vapor deposition method in which various gases such as oxygen are blown from the viewpoint of excellent transparency of the vapor deposition film.
  • the gas barrier laminate may be provided with an anchor coat layer on the substrate for smoothing improvement and adhesion improvement prior to vapor deposition.
  • the anchor coat layer is formed by, for example, applying a (meth) acrylic primer solution containing a (meth) acrylic resin or the like onto a substrate by a method such as a gravure coat, a roll coat, or a bar coat, and drying the solution. be able to.
  • the gas barrier layer and the seal layer in the present disclosure can be formed by a conventionally known means such as a dipping method, a roll coating method, a screen printing method, a spray method, and a gravure printing method.
  • a conventionally known means such as a dipping method, a roll coating method, a screen printing method, a spray method, and a gravure printing method.
  • the surface of the substrate Prior to coating, the surface of the substrate may be subjected to surface treatment such as corona treatment or atmospheric pressure plasma treatment.
  • the packaging bag using the gas barrier laminate according to the embodiment of the present disclosure can contain the contents such as foods and pharmaceuticals as the contents. Especially suitable for packaging confectionery and the like as food.
  • the packaging bag according to the present embodiment can maintain high gas barrier properties even in a shape having a bent portion.
  • the gas barrier laminate according to the present disclosure can be used as various packages such as a three-way seal pouch, a four-way seal pouch, a pillow package, a gusset package, and a standing pouch.
  • ⁇ Base material> The following three types of base materials were prepared.
  • PET Biaxially stretched PET film (thickness 12 ⁇ m). The corona-treated surface was processed in a post-process.
  • PET / AlO An aluminum oxide thin film layer having a thickness of 40 nm was formed on a biaxially stretched PET film (thickness 12 ⁇ m) by a vacuum vapor deposition method using an electron beam heating method using Al as a vapor deposition source. The aluminum oxide thin film layer was processed in a post-process.
  • a paper substrate of paper / AlO: 50 g / m 2 was subjected to a primer treatment, and an aluminum oxide thin film layer was formed on the treated surface in the same manner as the above PET / AlO, and a post-process process was performed therein.
  • ⁇ Gas barrier layer> The following two types of water-soluble polymers (A) were prepared.
  • PAA A 5 wt% aqueous solution of polyacrylic acid (molecular weight 5000) was prepared.
  • TEOS A hydrolyzed solution having a solid content of 3 wt% (SiO2 equivalent) obtained by adding 89.6 g (0.05 N) of hydrochloric acid to 10.4 g of tetraethoxysilane and stirring for 30 minutes to hydrolyze.
  • MTMOS A hydrolyzed solution having a solid content of 3 wt% (SiO 2 equivalent) obtained by adding 80 g (0.05 N) of hydrochloric acid to 10 g of methyltrimethoxysilane and stirring for 30 minutes to hydrolyze.
  • NCO A 3 wt% aqueous solution of 1,3,5-tris (3-trialkoxy serial kill) isocyanurate.
  • Montmorinite Silicate filler
  • Kunipia F manufactured by Kunimine Kogyo Co., Ltd.
  • Silanol group-containing silica filler Sun Green LFS manufactured by AGC SI Tech Co., Ltd. (particle size 0.5 ⁇ m, aspect ratio 120).
  • ⁇ Seal layer> The following three types of heat seal varnish were prepared.
  • Zyxen AC Water-based varnish manufactured by Sumitomo Seika Co., Ltd.
  • the base material, gas barrier layer, and seal layer of the gas barrier laminate were prepared according to the combinations shown in Table 1.
  • ⁇ Liquid preparation method> The metal alkoxide (B) was added to the water-soluble polymer solution (A) according to the combination shown in Table 1, and the mixture was stirred for 30 minutes to obtain a coating liquid having a solid content of 3 wt%.
  • the filler (C) When the filler (C) is added, it is first added to a water-soluble polymer solution and stirred for 30 minutes, then the metal alkoxide (B) is added in the same manner as above, and after stirring for 30 minutes, a solid content of 3 wt% is applied. Obtained liquid.
  • the compounding ratio in Table 1 is the mass ratio of the solid content of each component.
  • ⁇ Painting of gas barrier layer> The prepared coating liquid was applied onto the substrate by a bar coater and dried in an oven at 120 ° C. for 30 seconds to form a gas barrier layer having a film thickness of 1 ⁇ m.
  • ⁇ Coating the seal layer> A heat seal varnish was applied on the gas barrier layer on the substrate by a bar coater, and dried in an oven at 120 ° C. for 30 seconds. The thickness of the seal layer formed by the water-based varnish or the solvent-based varnish was 3 ⁇ m.
  • the laminated body was observed in a range of 100 mm 2 from the surface of the seal layer with a loupe having a magnification of 10 times, and the number of cracks was counted.
  • Table 2 shows the evaluation results for each laminated body. According to the examples, it can be seen that a gas barrier laminate suitable for use as a package is obtained.
  • gas barrier laminate 1 ... gas barrier laminate, 2 ... base material, 3 ... gas barrier layer, 4 ... seal layer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
PCT/JP2021/044989 2020-12-07 2021-12-07 ガスバリア性積層体およびそれを用いた包装体 Ceased WO2022124313A1 (ja)

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