Classifications

• • 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
• • 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
  • 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

Definitions

• the present invention relates to a gas barrier laminate and a packaging material obtained using the gas barrier laminate.
• Packaging materials used for packaging food, daily necessities, medicines, etc. are required to have functions such as strength, resistance to cracking, and gas barrier properties in order to protect the contents from shocks received during distribution, deterioration due to oxygen and moisture, etc.
• a gas barrier laminated film in which a vapor deposition layer made of an inorganic compound such as aluminum oxide is used as the first layer, and a coating agent mainly composed of a water-soluble polymer and an aqueous solution containing at least one of (a) one or more alkoxides and/or their hydrolysates or (b) tin chloride, or a water/alcohol mixed solution, is applied, and a gas barrier coating formed by heating and drying is laminated as the second layer.
• Patent Document 1 See, for example, Patent Document 1.
• the gas barrier film disclosed in Patent Document 1 is often used as a packaging material by, for example, laminating a heat-sealable thermoplastic resin layer or a printed layer on the gas barrier coating layer or on the substrate 2, or by laminating multiple resins via adhesive layers.
• a gas barrier film composed only of an olefin-based resin
• a gas barrier film which comprises a polyolefin film layer of a first substrate, a polyolefin film layer of a second substrate, and a polyolefin film sealant layer in this order, and the polyolefin film of the first substrate layer or the second substrate layer has an inorganic oxide layer on at least one surface, and exhibits a specific heat shrinkage rate, so that even if the main component is a polyolefin-based film, when it is made into a packaging bag, a laminate capable of high-temperature retort treatment is obtained (see, for example, Patent Document 2).
• Patent Document 2 describes that it is preferable to provide an anchor coating agent such as a polyester-based polyurethane resin or a polyether-based polyurethane resin between the polyolefin film and the inorganic oxide layer in order to improve the adhesion of the olefin-based resin, which has poor adhesion (see paragraphs 0022 to 0023 of Patent Document 2).
• this method requires a step of applying an anchor coating agent before providing an inorganic oxide layer on the polyolefin film, and is therefore not suitable for obtaining a recyclable packaging material having gas barrier properties by combining, for example, a general-purpose plastic film such as an olefin film having an inorganic oxide layer.
• the object of the present invention is to provide a gas barrier laminate and packaging material that maintain good adhesion and gas barrier properties even when combined with a plastic film such as an olefin film having a general-purpose inorganic oxide layer, and that is suitable for obtaining a packaging material that is also recyclable.
• a gas barrier laminate comprising (A) a general-purpose layer made of a substrate having an inorganic layer formed on at least one surface thereof, (B) a layer containing 50 mass% or more of an organometallic compound having a metal species of a Group 4 element, which is provided so as to be in contact with the surface of the substrate on which the inorganic layer is formed, and (C) a layer containing a water-soluble polymer and a metal alkoxide and/or a hydrolyzate thereof, which is provided so as to be in contact with the resin layer (B).
• the layer consisting of a substrate having an inorganic layer formed on at least one surface thereof is not particularly limited, and a commercially available product may be used, or a substrate having an inorganic layer such as a vapor deposition layer formed by a general-purpose method may be used.
• the layer used in this application is provided so as to contact the surface of the substrate on which the inorganic layer is formed, and contains 50 mass % or more of an organometallic compound having a metal species of a Group 4 element, thereby providing excellent adhesion to (C) a layer containing a water-soluble polymer and a metal alkoxide and/or a hydrolyzate thereof that exhibits gas barrier properties and is provided thereon.
• the present invention is a gas barrier laminate, (A) a layer made of a substrate having an inorganic layer formed on at least one surface thereof; (B) a layer provided in contact with the surface of the base material on which the inorganic layer is formed, the layer having an organometallic compound having a Group 4 element as a metal species in an amount of 50 mass% or more based on the total solid content; (C) a layer provided in contact with the resin layer (B), the layer comprising a water-soluble polymer and a metal alkoxide and/or a hydrolysate thereof;
• the present invention provides a gas barrier laminate comprising:
• the present invention also provides a packaging material using the gas barrier laminate described above.
• the present invention makes it possible to provide a gas barrier laminate that maintains good adhesion and gas barrier properties even when combined with a plastic film such as an olefin film having a general-purpose inorganic oxide layer, and is also suitable for producing recyclable packaging materials.
• the gas barrier laminate of the present invention has (A) a layer made of a substrate having an inorganic layer formed on at least one surface thereof (hereinafter, sometimes referred to as layer (A)).
• the substrate used in the (A) layer is not particularly limited in terms of its material, manufacturing method, or shape within the scope in which the effects of the present invention can be obtained, but in most cases, a film shape (sometimes called a sheet, but in the present invention, called a film) is used.
• olefin-based resins such as polyethylene (PE), polypropylene (PP), cyclic olefin polymer (COP), and cyclic olefin copolymer (COC), polyester, acrylic, polycarbonate, cellulose ester, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), nylon (NY), and materials containing biomass-derived components.
• olefin-based resins such as polyethylene (PE), polypropylene (PP), cyclic olefin polymer (COP), and cyclic olefin copolymer (COC)
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• NY nylon
• any film made of a thermoplastic resin mainly composed of an olefin-based resin can be used without any particular limitation.
• the olefin resin include polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear (linear) low-density polyethylene, polypropylene (PP), ethylene-propylene copolymers, ⁇ -olefin polymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-acrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-ethyl acrylate copolymers, cyclic olefin resins, ionomer resins, and polymethylpentene; and modified olefin resins obtained by modifying olefin resins with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, or other unsaturated carboxylic acids.
• olefin-based resins such as polyethylene (PE), polypropylene (PP), cyclic olefin polymer (COP), and cyclic olefin copolymer (COC), and polyethylene (PE) and polypropylene (PP) are most preferable.
• the substrate used in the (A) layer is not particularly limited, and may be a substrate having a thickness that is generally used for packaging foods, daily necessities, medicines, etc. From the viewpoint of formability and transparency, a film having a thickness in the range of 1 ⁇ m to 500 ⁇ m is sufficient, preferably 1 ⁇ m to 300 ⁇ m, and more preferably 1 ⁇ m to 100 ⁇ m. If the thickness is less than 1 ⁇ m, the strength is insufficient, and if it exceeds 500 ⁇ m, the rigidity becomes too high, which may make processing difficult.
• the method for producing these substrates is not particularly limited, and they can be produced by various film-forming methods such as melt extrusion molding, solution casting molding, and calendar molding, and these may be further subjected to biaxial or uniaxial stretching treatment. Furthermore, films that have been subjected to various surface treatments as necessary may be used.
• the (A) layer is a layer having a substrate layer with an inorganic layer formed on at least one side, and the inorganic layer is formed on a part or the entire surface of at least one side of the substrate.
• the inorganic substances forming these inorganic layers are not particularly limited as long as the effects of the present invention can be obtained, but it is preferable to use one or more selected from metals and metal oxides such as aluminum oxide, silicon oxide, aluminum, zinc oxide, magnesium oxide, calcium oxide, and zirconium oxide, and it is particularly preferable to use one or more selected from aluminum oxide, silicon oxide, aluminum, zinc oxide, and magnesium oxide, as these exhibit good barrier properties.
• the method for forming the inorganic layer is not particularly limited as long as the effects of the present invention can be obtained, but it can be formed by deposition processing, sputtering processing, CVD processing, and coating processing, and it is particularly preferable to use deposition processing and sputtering processing because they can form the inorganic layer uniformly.
• the gas barrier laminate of the present invention comprises a layer (B) that is provided so as to be in contact with the surface of the base material on which the inorganic layer is formed and that contains 50 mass % or more of an organometallic compound having a metal species of a Group 4 element (hereinafter, sometimes referred to as layer (B)).
• layer (B) may be laminated so that at least a part of it is in direct contact with the inorganic layer provided on layer (A).
• the organometallic compound used in the present invention which contains a Group 4 element as the metal species
• specific examples of the Group 4 element metal species include titanium, zirconium, hafnium, and rutherfordium. Among these, titanium or zirconium is preferable.
• Organometallic compounds containing these Group 4 elements as metal species include metal alkoxides and/or their oligomers and/or their hydrolysates, metal acylates, metal complexes, coupling agents, etc. These organometallic compounds may be used alone or in combination of two or more.
• the metal alkoxide and/or its oligomer and/or its hydrolysate may be one or more compounds selected from metal alkoxides and their hydrolysates in which the hydroxyl group of the hydroxide of the metal species is substituted with an alkoxyl group represented by -OC3H7 , -OC4H9 , -OCH2CH ( C2H5 ) C4H9 , -OCH( CH3 ) 2 , -OCnH2n +1, etc.
• metal alkoxide and its hydrolysate used in the present invention examples include tetraisopropyl titanate, tetra - n-butyl titanate, butyl titanate dimer, tetraoctyl titanate, butyl titanate oligomer, tetraisopropyl zirconate, tetra-n-butyl zirconate, etc.
• metal alkoxides selected from tetra-n-butyl titanate and tetra-n-butyl zirconate and/or hydrolysates thereof.
• metal acylates that can be used include titanium isostearate, zirconium isoctylate, and zirconium stearate.
• Metal complexes are sometimes called chelating agents.
• Specific examples include titanium tetraalkylates such as titanium tetrapropylate and titanium tetrabutylate, titanium alkylacetoacetates such as titanium bis(acetylacetate)dipropylate, and zirconium tetraalkylates such as zirconium tetrabutylate.
• Coupling agents include titanium coupling agents such as isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, and bis(dioctyl pyrophosphate)ethylene titanate.
• Zirconium coupling agents include zirconium acetate, ammonium zirconium carbonate, and zirconium fluoride.
• the preferred lower limit of the content of the organometallic compound having a Group 4 element as the metal species relative to the total solid content of the (B) layer is 50 mass%, 55 mass%, or 60 mass%.
• the preferred upper limit of the content is 100% relative to the total solid content.
• Layer (B) can be obtained, for example, by a coating method.
• a coating method There are no particular limitations on the coating method, and any known, commonly used coating method can be used. Examples include spraying, spin coating, dip coating, roll coating, blade coating, doctor roll, doctor blade, curtain coating, slit coating, screen printing, inkjet, and dispensing methods.
• a solvent can be used to improve the suitability for coating.
• the solvent is preferably an organic solvent, and examples of the solvent include alcohol-based organic solvents such as ethanol, n-propanol, isopropyl alcohol, and butanol; ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based organic solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; 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.
• alcohol-based organic solvents such as ethanol, n
• the coating amount of the organometallic compound having a Group 4 element as a metal species is not particularly limited as long as the effects of the present invention can be obtained, but it is preferably coated in an amount of 0.001 to 0.5 g/ m2 calculated as solid content, and particularly preferably 0.003 to 0.2 g/m2 in order to obtain good barrier properties.
• the drying process may be at room temperature, or may involve forced drying such as heating in an oven, reducing pressure, or blowing air.
• Layer (B) in the present invention contains 50% by mass or more of an organometallic compound having a Group 4 element as the metal species relative to the total solid content, but additives such as stabilizers, resins that serve as binder components, coupling agents, plasticizers, dispersants, surfactants, stabilizers, thickeners, defoamers, wetting agents, hardeners, antiblocking agents, lubricants, preservatives, and inorganic fillers may also be blended within the range in which the effects of the present invention can be obtained.
• additives such as stabilizers, resins that serve as binder components, coupling agents, plasticizers, dispersants, surfactants, stabilizers, thickeners, defoamers, wetting agents, hardeners, antiblocking agents, lubricants, preservatives, and inorganic fillers may also be blended within the range in which the effects of the present invention can be obtained.
• the layer (B) contains a stabilizer.
• acetylacetone, dehydroacetic acid, benzoylacetone, ethyl acetoacetate, diacetyl and other diketones carboxylic acids such as acetic acid, hydroxycarboxylic acids such as citric acid, malic acid, tartaric acid, mandelic acid, lactic acid, glycolic acid, hydroxyisobutyric acid, hydroxyacetone, hydroxycarbonyls such as acetoin, cellosolves such as methoxyethanol, dimethoxyethane, glycols such as ethylene glycol, substituted glycol, pentaethylene glycol, hydrazones such as acetolhydrazone, acetoinhydrazone, imines such as diethanolamine, monoketones such as acetone, and the like can be used, and among them, it is preferable to select from acetylacetone, benzoylacetone, citric acid, malic acid, mandelic acid, and acetone.
• carboxylic acids
• binder resins include polyvinyl butyral resin, polyvinyl acetal resins such as polyvinyl acetal resin, acrylic resin, polyester resin, styrene resin, styrene-maleic acid resin, maleic acid resin, polyamide resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin, chlorinated polypropylene resin, cellulose-based resin, epoxy resin, alkyd resin, rosin-based resin, rosin-modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, and petroleum resin.
• binder resins include polyvinyl butyral resin, polyvinyl acetal resins such as polyvinyl acetal resin, acrylic resin, polyester resin, styrene resin, styrene-male
• the coupling agent may be any of the known and commonly used ones, such as silane coupling agents, titanium coupling agents, zirconium coupling agents, aluminum coupling agents, etc.
• silane coupling agent such as epoxy group-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and N-phenyl- ⁇ -aminopropyltrimethoxysilane; (meth)acryloyl group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane;
• Aluminum coupling agents include acetoalkoxyaluminum diisopropylate, aluminum diisopropoxymonoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate, etc.
• Silane compounds include alkoxysilanes, silazanes, siloxanes, etc.
• Alkoxysilanes include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, etc.
• Silazanes include hexamethyldisilazane, etc.
• Siloxanes include hydrolyzable group-containing siloxanes, etc.
• the gas barrier laminate of the present invention has a layer (C) that is provided so as to be in contact with the layer (B) and contains a water-soluble polymer and a metal alkoxide and/or a hydrolysate thereof (hereinafter, sometimes referred to as layer (C)).
• layer (C) it is sufficient that layer (C) is laminated so that at least a part of layer (C) is in direct contact with layer (B).
• the water-soluble polymer used in the gas barrier laminate of the present invention is not particularly limited as long as the effects of the present invention can be obtained, and one or more water-soluble polymers selected from vinyl alcohol polymers such as polyvinyl alcohol, ethylene-vinyl alcohol polymers, vinylpyrrolidone polymers, acrylic acid polymers, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, etc. can be used. Since suitable gas barrier properties can be obtained, it is preferable to use one or more selected from vinyl alcohol polymers, ethylene-vinyl alcohol polymers, vinylpyrrolidone polymers, and acrylic acid polymers.
• vinyl alcohol polymers such as polyvinyl alcohol, ethylene-vinyl alcohol polymers, vinylpyrrolidone polymers, acrylic acid polymers, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, etc.
• vinyl alcohol polymers such as polyvinyl alcohol, ethylene-vinyl alcohol polymers, vinylpyrrolidone polymers, acrylic acid polymers, starch
• metal alkoxide and/or hydrolysate thereof used in the gas barrier laminate of the present invention is not particularly limited as long as the effects of the present invention can be obtained, but metal alkoxides and/or hydrolysates thereof having one or more metal species selected from silicon, aluminum, titanium, and zirconia as the metal species are preferred, and it is more preferred to have one or more metal species selected from silicon and aluminum as the metal species, as this will result in good gas barrier properties.
• metal alkoxides and/or hydrolysates thereof may be one or more compounds selected from metal alkoxides in which the hydroxyl group of the hydroxide of the above-mentioned metal species is substituted with an alkoxyl group represented by -OCH3 , -OC2H5 , -OC3H7 , -OCnH2n +1, etc., and hydrolysates thereof.
• Alkoxysilanes such as tetraethoxysilane (TEOS), tetramethoxysilane, tetraproxisilane, tetrabutoxysilane, etc.
• metal alkoxides and/or hydrolysates thereof used in the present invention can be used as the metal alkoxides and/or hydrolysates thereof used in the present invention, and one or more metal alkoxides and/or hydrolysates thereof selected from tetraethoxysilane and tetramethoxysilane are particularly preferred because they provide good gas barrier properties.
• a sol by mixing a water-soluble polymer, a metal alkoxide and/or a hydrolysate thereof, water, and one or more organic solvents selected from the group consisting of water-soluble organic solvents such as methanol, ethanol, isopropanol, and 1-propanol, and to coat the obtained sol on layer (B) and dry it to gel and solidify it, thereby forming layer (C) containing a water-soluble polymer and a metal alkoxide and/or a hydrolysate thereof.
• water-soluble organic solvents such as methanol, ethanol, isopropanol, and 1-propanol
• the method for applying the mixed sol is not particularly limited, and any known and commonly used application method can be used. Examples include spraying, spin coating, dip coating, roll coating, blade coating, doctor roll, doctor blade, curtain coating, slit coating, screen printing, inkjet, and dispensing methods. In particular, application by the roll coating method using a gravure coater is preferred because it forms a good coating film.
• the amount of the mixed sol to be applied is not particularly limited as long as the effects of the present invention can be obtained, but it is preferable to apply the sol in an amount of 0.1 to 0.5 g/ m2 , and it is particularly preferable to apply the sol in an amount of 0.2 to 0.4 g/ m2 because this forms a good coating film.
• the drying process may be room temperature drying, or forced drying such as heating using an oven, reducing pressure, or blowing air.
• the (C) layer in the present invention may contain a wetting agent such as a silane coupling agent or a surfactant, as long as the effects of the present invention are achieved.
• a wetting agent such as a silane coupling agent or a surfactant
• the (B) layer and the (C) layer may be combined in such a way that they form a strong film through a polycondensation reaction using the sol-gel method. If necessary, various catalysts and solvents may be added, and heating and drying may also be performed.
• the method for providing the (C) layer so that it is in contact with the (B) layer is not particularly limited, but may be a general-purpose method, such as a method in which the (B) layer is formed on the (A) layer by coating, and then the (C) layer is continuously formed by coating, or a method in which the (B) layer is formed on the (A) layer by coating, and then wound up, and then unwound, and then the (C) layer is formed on the (B) layer by coating, etc.
• the resin layer which is the base material used in the layer (A) but does not have an inorganic layer formed thereon, as described in the layer (A), may be, for example, an olefin resin such as polyethylene (PE), polypropylene (PP), cyclic olefin polymer (COP), cyclic olefin copolymer (COC), polyester, acrylic, polycarbonate, cellulose ester, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), nylon (NY), or a material containing a biomass-derived component.
• any film made of a thermoplastic resin mainly composed of an olefin resin may be used without any particular limitation.
• the olefin resin include polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene, polypropylene, ethylene-propylene copolymers, ⁇ -olefin polymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-acrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-ethyl acrylate copolymers, cyclic olefin resins, ionomer resins, and polymethylpentene; and modified olefin resins obtained by modifying olefin resins with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, or other unsaturated carboxylic acids.
• polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density poly
• olefin resins such as polyethylene (PE), polypropylene (PP), cyclic olefin polymers (COP), and cyclic olefin copolymers (COC), because the effects of the present invention are significantly obtained, and polyethylene (PE) and polypropylene (PP) are the most preferable.
• the substrate may be, for example, wood, metal, metal oxide, a resin film other than the resin shown in the layer (A), paper, silicon or modified silicon, or a substrate obtained by bonding different materials.
• the shape of the substrate and the substrate may be any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape having a curvature over the entire surface or part thereof.
• the hardness, thickness, etc. of the substrate when the laminate according to the present invention is used as a packaging material, paper, plastic, metal, metal oxide, etc. may be used as the substrate.
• Print layer From the viewpoint of recycling, it is preferable that the layer structure is as simple as possible, but from the viewpoint of distribution of the packaging material, printing is often required to display the contents of the packaging material or the description or name of the product. Liquid inks such as gravure printing inks and flexographic printing inks are often used as printing inks for this purpose.
• the printed layer is a layer on which characters, figures, symbols, and other desired patterns are printed using liquid ink or the like.
• the laminate may be provided at any position.
• liquid ink is a general term for solvent-based inks used in gravure printing or flexographic printing. It may contain resin, colorant, and solvent as essential components, or it may be a so-called clear ink that contains resin and solvent but does not substantially contain colorant.
• the resins used in the liquid ink are not particularly limited, and examples include acrylic resin, polyester resin, styrene resin, styrene-maleic acid resin, maleic acid resin, polyamide resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin, chlorinated polypropylene resin, cellulose-based resin, epoxy resin, alkyd resin, rosin-based resin, rosin-modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, etc., and one or more of these can be used in combination.
• at least one or two or more selected from polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, and cellulose-based resin are used.
• Colorants used in liquid inks include inorganic pigments such as titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite; organic pigments such as soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments; and extender pigments such as calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, and talc.
• inorganic pigments such as titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite
• organic pigments such as soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments
• the organic solvent used in the liquid ink preferably does not contain aromatic hydrocarbon organic solvents. More specifically, examples of the organic solvents include alcohol organic solvents such as methanol, ethanol, n-propanol, isopropyl alcohol, and butanol; ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester organic solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; aliphatic hydrocarbon organic solvents such as n-hexane, n-heptane, and n-octane; and alicyclic hydrocarbon organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane. These can be used alone or in combination of two or more.
• alcohol organic solvents such as
• Examples of functional coating layers include coating agents containing various additives.
• additives include modifiers, coupling agents, silane compounds, phosphate compounds, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, oxygen scavengers (compounds having oxygen scavenging function), tackifiers, etc.
• additives include modifiers, coupling agents, silane compounds, phosphate compounds, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, oxygen scavengers (compounds having oxygen scavenging function), tackifiers, etc.
• additives include modifiers, coupling agents, silane compounds, phosphate compounds, organic fillers, inorganic
• the modifier may be any known or commonly used compound, such as a diol, an amine compound, a carbodiimide, or an isocyanate.
• Coupling agents include those that are well known and commonly used, such as silane coupling agents, titanium coupling agents, zirconium coupling agents, and aluminum coupling agents.
• silane coupling agent such as epoxy group-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and N-phenyl- ⁇ -aminopropyltrimethoxysilane; (meth)acryloyl group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane;
• Titanium coupling agents include, for example, isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, and bis(dioctyl pyrophosphate)ethylene titanate.
• zirconium coupling agents examples include zirconium acetate, ammonium zirconium carbonate, and zirconium fluoride.
• Aluminum coupling agents include acetoalkoxyaluminum diisopropylate, aluminum diisopropoxymonoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate, etc.
• Silane compounds include alkoxysilanes, silazanes, siloxanes, etc.
• Alkoxysilanes include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, etc.
• Silazanes include hexamethyldisilazane, etc.
• Siloxanes include hydrolyzable group-containing siloxanes, etc.
• inorganic fillers include inorganic substances such as metals, metal oxides, resins, and minerals, as well as composites of these.
• specific examples of inorganic fillers include silica, alumina, titanium, zirconia, copper, iron, silver, mica, talc, aluminum flakes, glass flakes, and clay minerals.
• Examples of compounds with oxygen scavenging capabilities include low molecular weight organic compounds that react with oxygen, such as hindered phenol compounds, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, and pyrogallol, as well as transition metal compounds such as cobalt, manganese, nickel, iron, and copper.
• Tackifiers include xylene resin, terpene resin, phenol resin, rosin resin, etc. Adding a tackifier can improve adhesion to various substrates immediately after application.
• the amount of tackifier added is preferably 0.01 to 5 parts by mass per 100 parts by mass of the total resin composition.
• an adhesive that can be used in a general-purpose lamination method can be used for the purpose of laminating the gas barrier laminate of the present invention, particularly with a second substrate, etc.
• the lamination method include dry lamination, wet lamination, non-solvent lamination, and extrusion lamination.
• the adhesive used in the dry lamination may be, for example, a one-component or two-component curing or non-curing type vinyl, (meth)acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, or other solvent, water-based, or emulsion type adhesive.
• a two-component curing adhesive of polyol and isocyanate compound may be used as a two-component curing adhesive.
• the lamination adhesive may be applied by, for example, a direct gravure roll coating method, a gravure offset roll coating method, a kiss coating method, a reverse roll coating method, a Fountain method, a transfer roll coating method, or other methods.
• pressure-sensitive adhesives include rubber-based adhesives obtained by dissolving polyisobutylene rubber, butyl rubber, or mixtures of these in organic solvents such as benzene, toluene, xylene, or hexane, or these rubber-based adhesives mixed with tackifiers such as abiethylene acid rosin ester, terpene-phenol copolymer, or terpene-indene copolymer, or acrylic-based adhesives obtained by dissolving acrylic copolymers with a glass transition point of -20°C or less, such as 2-ethylhexyl acrylate-n-butyl acrylate copolymer or 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate copolymer, in an organic solvent.
• the gas that the gas barrier laminate of the present invention can block is mainly oxygen, but other examples include inert gases such as carbon dioxide, nitrogen, and argon, alcohol components such as methanol, ethanol, and propanol, phenols such as phenol and cresol, and aroma components made of low molecular weight compounds, for example, the smells of soy sauce, sauce, miso, limonene, menthol, methyl salicylate, coffee, cocoa, etc.
• inert gases such as carbon dioxide, nitrogen, and argon
• alcohol components such as methanol, ethanol, and propanol
• phenols such as phenol and cresol
• aroma components made of low molecular weight compounds for example, the smells of soy sauce, sauce, miso, limonene, menthol, methyl salicylate, coffee, cocoa, etc.
• the gas barrier laminate of the present invention can be used as a multi-layer packaging material for protecting foods, medicines, etc.
• the layer structure can be changed depending on the contents, the environment of use, and the form of use.
• the package of the present invention may be appropriately provided with an easy-opening treatment or a resealing means.
• Contents to be filled into the packaging material of the present invention include, for example, foods such as rice crackers, bean snacks, nuts, biscuits and cookies, wafer snacks, marshmallows, pies, semi-dried cakes, candies, snack foods, and other confectioneries; bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, porridge, packaged rice cakes, and cereal foods, as well as other staple foods; pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, wild vegetable products, jams, peanut cream, salads, frozen vegetables, and processed potato products, as well as processed livestock products such as ham, bacon, sausages, processed chicken products, and corned beef, These include fish ham and sausages, fish paste products, fishery products such as kamaboko, nori seaweed, tsukudani (food boiled in soy sauce), dried bonito flakes, shiokara (salted fish), smoked salmon, and spicy cod ro
• non-food items including tobacco, disposable hand warmers, medicines such as infusion packs, liquid laundry detergent, liquid kitchen detergent, liquid bath detergent, liquid bath soap, liquid shampoo, liquid conditioner, cosmetics such as lotion and milky lotion, vacuum insulation materials, batteries, etc.
• TEOS tetraethoxysilane
• KBE-04 Shin-Etsu Chemical Co., Ltd.
• a coating agent (b-1) was applied onto the prepared (A) layer using bar coater #2, and the dilution solvent was evaporated using a dryer set at a temperature of 50° C. to obtain a (B-1) layer. Thereafter, a coating liquid (c) was applied using bar coater #3, and dried for 1 minute in a hot air dryer set at 80° C. to form a (C) layer, which was a gas barrier laminate.
• Example 2 The same procedure as in Example 1 was carried out except that the composition of the coating liquid (b-1) in Example 1 was changed as shown in Tables 1 to 3, to obtain gas barrier laminates and packaging materials of Examples 2 to 22, respectively.
• the raw materials used in Tables 1 to 3 are as follows.
• Butyl titanate dimer (TA-23, Matsumoto Fine Chemical Co., Ltd.) Normal butyl zirconate (ZA-65, Matsumoto Fine Chemical Co., Ltd.) Titanium acetylacetonate (TC-100, Matsumoto Fine Chemical Co., Ltd.) Titanium tetraacetylacetonate (TC-401, Matsumoto Fine Chemical Co., Ltd.) Zirconium monoacetylacetonate (ZC-540, Matsumoto Fine Chemical Co., Ltd.) Citric acid (Citric acid, Kanto Chemical Co., Ltd.) Malic acid (Malic acid, Kanto Chemical Co., Ltd.) Mandelic acid (Mandelic acid, Kanto Chemical Co., Ltd.) Acetone (Acetone, Kanto Chemical Co., Ltd.) Polyvinyl butyral (BL-1, Sekisui Chemical Co., Ltd.) 3-Glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co.,
• Comparative Example 1 A gas barrier laminate and a packaging material of Comparative Example 1 were obtained in the same manner as in Example 1, except that the layer (B) of Example 1 was not provided and the layer (C) was formed on the layer (A).
• Example 2 (Comparative Examples 2 to 6) The same procedure as in Example 1 was carried out except that the composition of the coating liquid (b-1) in Example 1 was changed as shown in Table 4, to obtain gas barrier laminates and packaging materials of Comparative Examples 2 to 6, respectively.

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• 2023
  • 2023-10-19 TW TW112139875A patent/TW202436093A/zh unknown
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