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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
• • 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
  • 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 disclosure relates to a laminated film for preventing permeation of gas such as oxygen in various fields such as food, pharmaceuticals, sanitary products, agricultural products, electronic equipment, and optical equipment, and a method for manufacturing the same.
• gas barrier films having gas barrier properties include films coated with a barrier resin such as vinylidene chloride copolymer (PVDC) and inorganic deposition films deposited with inorganic components.
• PVDC vinylidene chloride copolymer
• the aluminum vapor-deposited film had insufficient oxygen barrier properties. Therefore, in order to improve the barrier property, a laminated film is known in which a coating film containing a water-soluble polymer and a layered inorganic compound is formed before vapor deposition of aluminum.
• Patent Document 1 discloses that a coating film containing a layered inorganic compound and a water-soluble polymer as main components and further containing an amine compound is formed on at least one side of an olefin resin substrate. , discloses a gas barrier film having a layer of metal and/or metal oxide on the coating.
• Patent Document 2 a coated layer containing a resin material having a polar group is interposed on a stretched polypropylene resin layer, and a deposited film containing an inorganic oxide is laminated.
• a multi-layer substrate is disclosed.
• JP-A-10-166516 Japanese Patent Application Laid-Open No. 2021-24136
• an object of the present disclosure is to provide a laminated film with excellent gas barrier properties and interlayer adhesion, and a method for producing the same.
• the present inventors have found that at least one surface of a substrate layer containing an olefin resin contains a water-soluble vinyl polymer and a polyalkyleneimine resin, and a large amount of The inventors have found that gas barrier properties and interlayer adhesion can be improved by sequentially laminating an intermediate layer that does not contain a layered inorganic compound and an inorganic layer, and have completed the present invention.
• the laminated film as aspect [1] of the present disclosure includes a substrate layer containing an olefin resin, and laminated on at least one surface of this substrate layer, and a water-soluble vinyl polymer and a polyalkyleneimine resin and an intermediate layer in which the ratio of the layered inorganic compound is 0 to 15 parts by mass with respect to 100 parts by mass of the water-soluble vinyl polymer; and an inorganic layer laminated on the intermediate layer.
• aspects [2] of the present disclosure is an aspect in which, in the aspect [1], the olefin-based resin is a polypropylene-based resin, and the substrate layer is a stretched film.
• Aspect [3] of the present disclosure is an aspect in which the inorganic layer contains a metal in the aspect [1] or [2].
• Aspect [4] of the present disclosure is any one of Aspects [1] to [3], wherein the inorganic layer is at least one selected from the group consisting of an aluminum vapor deposition film, an alumina vapor deposition film and a silica vapor deposition film. It is an aspect.
• Aspect [5] of the present disclosure is an aspect in which the intermediate layer does not contain a layered inorganic compound in any one of the aspects [1] to [4].
• Aspect [6] of the present disclosure is the aspect of any one of the aspects [1] to [5], wherein the proportion of the polyalkyleneimine-based resin is 1 to 1 to 100 parts by mass of the water-soluble vinyl polymer. In this embodiment, the content is 50 parts by mass.
• Aspect [7] of the present disclosure is an aspect in which, in any one of Aspects [1] to [6], the oxygen permeability of the laminated film is 150 ml/(m 2 ⁇ 24 h ⁇ MPa) or less.
• the intermediate layer lamination step is a step of coating at least one surface of the base layer with a liquid composition for forming an intermediate layer. good.
• the inorganic layer laminating step is a step of vapor-depositing a metal and/or an inorganic compound for forming an inorganic layer on the intermediate layer.
• an intermediate layer containing a water-soluble vinyl-based polymer and a polyalkyleneimine-based resin and not containing a large amount of a layered inorganic compound and an inorganic layer are sequentially formed on at least one surface of a substrate layer containing an olefin-based resin. Since it is laminated, gas barrier properties and interlayer adhesion can be improved. In terms of gas barrier properties, it is possible to improve not only water vapor barrier properties (moisture resistance), but also oxygen barrier properties, which were difficult with vapor-deposited aluminum films. Furthermore, whitening and the like can be suppressed, and the appearance can be improved. In particular, when the inorganic layer contains metal, the light shielding property can also be improved.
• the laminated film (gas barrier film) of the present disclosure comprises a substrate layer containing an olefin resin, and an intermediate layer laminated on at least one surface of the substrate layer and containing a water-soluble vinyl polymer and a polyalkyleneimine resin. and an inorganic layer laminated on the intermediate layer.
• the olefin resin contained in the substrate layer includes olefin homopolymers and copolymers such as polyethylene resins and polypropylene resins. Among these, polypropylene-based resins are preferable because they can improve gas barrier properties and packaging properties.
• the polypropylene-based resin may be a propylene homopolymer (propylene homopolymer) or a propylene copolymer (propylene-based copolymer).
• monomers copolymerizable with propylene include, for example, ⁇ -olefins (ethylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-pentene, 3-methyl -1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 3-ethyl-1-pentene, 3-methyl-1-butene, 4-methyl-1-hexene, 4,4 -dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene , 1-octadecene, 1- eicosene ), alkadienes (1,4-hexadiene, 1,7-octa
• copolymers include block copolymerization, random copolymerization, alternating copolymerization, and graft copolymerization. Among these, random copolymerization and alternating copolymerization are usually used.
• the polypropylene-based resin may be an atactic polymer, but a polymer having a stereoregular structure such as isotactic or syndiotactic is preferable from the viewpoint of improving heat resistance, and an isotactic polymer is preferred. Especially preferred.
• the polypropylene resin may be a polymer using a Ziegler catalyst or the like, but since it is a polymer with a low molecular weight tack component and a narrow molecular weight distribution, a metallocene resin using a metallocene catalyst is preferred. preferable.
• the number average molecular weight of the polypropylene resin is, for example, 10,000 to 500,000, preferably 15,000 to 300,000, more preferably 20,000 to 100,000.
• the number average molecular weight of the polypropylene resin is measured by the GPC method at a measurement temperature of 140 ° C., using orthodichlorobenzene as a solvent and a column (Shodex GPC AD-806MS), polystyrene can be measured by universal calibration with reference to
• the melting point (or softening point) of polypropylene resin is, for example, 120 to 180°C, preferably 130 to 175°C, more preferably 150 to 170°C.
• the melting point of the polypropylene resin can be measured based on the melting peak temperature with a differential scanning calorimeter DSC.
• polypropylene resins can be used alone or in combination of two or more.
• crystalline polypropylene-based resins particularly polypropylene homopolymers (for example, crystalline polypropylene homopolymers) are preferred.
• the base material layer may be formed of a resin composition containing an olefin resin.
• the resin composition includes thermoplastic resins other than olefin resins (chlorine-containing resins, styrene resins, petroleum resins, etc.), conventional additives (e.g., heat stabilizers, antioxidants, stabilizers such as ultraviolet absorbers, preservatives, bactericides, plasticizers, lubricants, coloring agents, viscosity modifiers, leveling agents, surfactants, antistatic agents, etc.).
• thermoplastic resins other than olefin resins chlorine-containing resins, styrene resins, petroleum resins, etc.
• conventional additives e.g., heat stabilizers, antioxidants, stabilizers such as ultraviolet absorbers, preservatives, bactericides, plasticizers, lubricants, coloring agents, viscosity modifiers, leveling agents, surfactants, antistatic agents, etc.
• the total proportion of the thermoplastic resin other than the olefinic resin and the additive is 50 parts by mass or less, preferably 30 parts by mass or less (for example, 0.01 to 30 parts by mass), more preferably 100 parts by mass of the olefinic resin. It is 10 parts by mass or less (for example, 0.1 to 10 parts by mass).
• the base material layer is preferably an olefin-based resin film, and particularly preferably a polypropylene-based resin film.
• the base material layer may be a non-stretched film, but is preferably a stretched film, particularly preferably a biaxially stretched film, in terms of improving mechanical properties and suppressing curling.
• the stretching ratio in the film drawing direction (MD direction) is, for example, 2 to 10 times, preferably 3 to 9 times, more preferably 4 to 8 times. be.
• the draw ratio in the film width direction (TD direction) is, for example, 5 to 20 times, preferably 6 to 15 times, more preferably 7 to 13 times.
• the substrate layer is subjected to surface treatment (e.g., corona discharge treatment, glow discharge treatment, plasma treatment, reverse sputtering treatment, flame treatment, chromic acid treatment, solvent treatment, surface roughening, etc.) in order to improve adhesion with the intermediate layer.
• surface treatment e.g., corona discharge treatment, glow discharge treatment, plasma treatment, reverse sputtering treatment, flame treatment, chromic acid treatment, solvent treatment, surface roughening, etc.
• treatment e.g., corona discharge treatment, glow discharge treatment, plasma treatment, reverse sputtering treatment, flame treatment, chromic acid treatment, solvent treatment, surface roughening, etc.
• treatment e.g., ozone, ultraviolet irradiation treatment, etc.
• the average thickness of the substrate layer is, for example, 3 to 200 ⁇ m, preferably about 5 to 150 ⁇ m, more preferably 10 to 100 ⁇ m.
• the intermediate layer may be laminated on at least one side of the base layer, and may be laminated on both sides, but from the viewpoint of productivity, it is preferably laminated on one side.
• the water-soluble vinyl polymer contained in the intermediate layer includes, for example, a vinyl alcohol polymer.
• vinyl alcohol polymers include homopolymers such as polyvinyl alcohol (or saponified products of polyvinyl acetate), and C 2-3 olefin-vinyl alcohol copolymers such as ethylene-vinyl alcohol copolymers. I can give an example.
• water-soluble vinyl polymers can be used alone or in combination of two or more.
• polyvinyl alcohol and ethylene-vinyl alcohol copolymers having a low ethylene content for example, ethylene content of 30 mol % or less, preferably 10 mol % or less, particularly polyvinyl alcohol, are preferred from the viewpoint of gas barrier properties.
• the degree of saponification of the vinyl alcohol polymer can be selected from the range of 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and more preferably 98 mol% or more ( 99 mol % or more), for example, 90 to 99.9 mol %, preferably 95 to 99.8 mol %, more preferably 97 to 99.5 mol %.
• the degree of polymerization of the water-soluble vinyl polymer is, for example, 200 or more (eg, 200 to 5,000), preferably 200 to 4,000, more preferably 250 to 3,000, and more preferably 300 to 1,000. be. If the degree of polymerization is too low, the adhesion between layers may deteriorate.
• the degree of polymerization may be a viscosity-average degree of polymerization, which can be measured by a conventional method.
• the viscosity (4% by mass aqueous solution, 20° C.) of the water-soluble vinyl polymer (especially vinyl alcohol polymer) can be selected, for example, from a range of about 0.1 to 100 mPa ⁇ s, for example, 0.5 to 30 mPa ⁇ s. s, preferably 1 to 10 mPa ⁇ s, more preferably 1.5 to 7 mPa ⁇ s, more preferably 2 to 5 mPa ⁇ s, most preferably 3 to 4 mPa ⁇ s. If the viscosity is too low, the adhesion between layers may deteriorate.
• the viscosity can be measured as the viscosity of a 4% by mass aqueous solution at 20°C using a Brookfield viscometer.
• polyalkyleneimine-based resin contained in the intermediate layer examples include homo- or co-poly C1 such as polyethyleneimine-based resin, polypropyleneimine-based resin, polyisopropyleneimine-based resin, polybutyleneimine-based resin, and polyisobutyleneimine-based resin.
• homo- or co-poly C1 such as polyethyleneimine-based resin, polypropyleneimine-based resin, polyisopropyleneimine-based resin, polybutyleneimine-based resin, and polyisobutyleneimine-based resin.
• -6 alkyleneimine resins especially homo- or copoly C 2-4 alkyleneimine resins).
• polyalkyleneimine-based resins are modified polyalkyleneimine-based resins modified with isocyanate compounds (e.g., alkyl isocyanates such as octadecyl isocyanate) and epoxy compounds (e.g., C 2-4 alkylene oxides such as ethylene oxide and propylene oxide).
• isocyanate compounds e.g., alkyl isocyanates such as octadecyl isocyanate
• epoxy compounds e.g., C 2-4 alkylene oxides such as ethylene oxide and propylene oxide
• these polyalkyleneimine resins may be in the form of salts or complexes (in particular, metal salts such as aluminum salts).
• polyalkyleneimine resins can be used alone or in combination of two or more.
• poly-C 2-4 alkyleneimine resins such as polyethyleneimine resins and polypropyleneimine resins are preferred, and polyethyleneimine resins such as polyethyleneimine are particularly preferred.
• the number average molecular weight of the polyalkyleneimine resin is, for example, 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10,000 to 300,000, more preferably 30,000 to 100,000, most preferably 50,000 to 80,000.
• the number average molecular weight of the polyalkyleneimine resin can be measured using polystyrene as a standard in the GPC method.
• the polyalkyleneimine-based resin may be synthesized by a conventional method [ring-opening polymerization of alkyleneimine (eg, ethyleneimine, etc.)], or a commercially available product may be used.
• alkyleneimine eg, ethyleneimine, etc.
• the ratio of the polyalkyleneimine resin is, for example, 0.1 to 50 parts by mass, preferably 0.3 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the water-soluble vinyl resin. , more preferably 0.8 to 5 parts by weight, most preferably 1 to 3 parts by weight. If the proportion of the polyalkyleneimine-based resin is too small, the interlayer adhesion may deteriorate, and if it is too large, the gas barrier properties may deteriorate.
• the intermediate layer may be formed of a resin composition containing a water-soluble vinyl polymer and a polyalkyleneimine resin, and may further contain a layered inorganic compound in order to improve gas barrier properties.
• layered inorganic compounds include swelling hydrous silicates such as smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite, etc.), and kaolin.
• swelling hydrous silicates such as smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite, etc.), and kaolin.
• layered inorganic compounds may be natural or synthetic.
• layered inorganic compounds can be used alone or in combination of two or more.
• smectite group clay minerals particularly montmorillonite, are preferred.
• the shape of the layered inorganic compound is usually plate-like or flat, and the planar shape is not particularly limited, and may be amorphous.
• the average particle size of the layered inorganic compound (average particle size of planar shape) is, for example, 0.01 to 5 ⁇ m, preferably 0.1 to 3 ⁇ m, more preferably 0.5 to 2 ⁇ m.
• the proportion of the layered inorganic compound is small in order to improve the homogeneity of the intermediate layer.
• the ratio of the layered inorganic compound is 0 to 15 parts by mass, preferably 0 to 10 parts by mass, particularly preferably 0 to 5 parts by mass, and more preferably 0 to 3 parts by mass, based on 100 parts by mass of the water-soluble vinyl polymer. part by weight, more preferably 0 to 1 part by weight, most preferably 0 to 0.1 part by weight.
• the intermediate layer (resin composition forming the intermediate layer) preferably does not substantially contain a layered inorganic compound, and particularly does not contain a layered inorganic compound, from the viewpoint of improving gas barrier properties and interlayer adhesion. preferable.
• the resin composition may further contain other resin components in addition to the water-soluble vinyl-based polymer and the polyalkyleneimine-based resin.
• Other resin components include, for example, olefin resins (polyethylene resins, etc.), chlorine-containing resins, styrene resins, petroleum resins, water-soluble polysaccharides (water-soluble cellulose derivatives, water-soluble starch, chitosan, etc.). be done.
• the total proportion of the other resin components is 50 parts by mass or less (for example, 1 to 50 parts by mass), preferably 30 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the water-soluble vinyl resin.
• the resin component may be only the water-soluble vinyl-based resin and the polyalkyleneimine-based resin.
• the resin composition may further contain conventional additives.
• Usual additives include, for example, isocyanate compounds (aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane-4,4'-diisocyanate and their derivatives), stabilizers ( heat stabilizers, antioxidants, ultraviolet absorbers, etc.), preservatives, bactericides, plasticizers, lubricants, colorants, viscosity modifiers, leveling agents, surfactants, antistatic agents, and the like.
• isocyanate compounds aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane-4,4'-diisocyanate and their derivatives
• stabilizers heat stabilizers, antioxidants, ultraviolet absorbers, etc.
• preservatives
• the total proportion of these additives is 50 parts by mass or less, preferably 30 parts by mass or less (for example, 0.01 to 30 parts by mass), more preferably 10 parts by mass or less with respect to 100 parts by mass of the water-soluble vinyl polymer. (eg 0.1 to 10 parts by mass).
• the intermediate layer may have an average thickness of 0.05 ⁇ m or more, for example, 0.05 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m, more preferably 0.3 to 3 ⁇ m, more preferably 0.5 to 2 ⁇ m, and most preferably. is 0.7 to 1.5 ⁇ m. If the intermediate layer is too thin, the oxygen barrier properties may deteriorate.
• the inorganic layer may be formed of a metal and/or an inorganic compound, usually contains a metal or a metal compound, and is preferably composed of a metal or a metal compound capable of forming a thin film.
• Examples of the metal include periodic table 2A group elements (beryllium, magnesium, calcium, strontium, barium, etc.), transition elements (titanium, zirconium, ruthenium, hafnium, tantalum, copper, etc.), periodic table 2B group elements (zinc, etc.). ), periodic table 3B group elements (aluminum, gallium, indium, thallium, etc.), periodic table 4B group elements (germanium, tin, etc.).
• periodic table 2A group elements beryllium, magnesium, calcium, strontium, barium, etc.
• transition elements titanium, zirconium, ruthenium, hafnium, tantalum, copper, etc.
• periodic table 2B group elements zinc, etc.
• periodic table 3B group elements aluminum, gallium, indium, thallium, etc.
• periodic table 4B group elements germanium, tin, etc.
• the metal compound examples include oxides, nitrides, oxynitrides, halides, and carbides of the metals.
• metal oxides such as alumina and silica are preferable.
• metals or metal compounds can be used alone or in combination of two or more.
• a Group 3B element of the periodic table such as aluminum is preferable, and aluminum is particularly preferable, because it can improve not only the gas barrier properties but also the light shielding properties.
• metal oxides such as alumina and silica are also preferable from the viewpoint of highly improving gas barrier properties (especially water vapor barrier properties).
• the average thickness of the inorganic layer can be appropriately selected according to the film formation method, and is, for example, 10 to 300 nm, preferably 15 to 250 nm, more preferably 20 to 200 nm, and more preferably 30 to 100 nm.
• the average thickness of the inorganic layer is adjusted to 10 to 100 nm (especially 15 to 80 nm) from the viewpoint of preventing cracks from occurring and forming a uniform film to maintain gas barrier properties.
• the average thickness of the inorganic layer it is preferable to adjust the average thickness of the inorganic layer to 50 to 400 nm (especially 100 to 300 nm). If the thickness of the inorganic layer is too thin, the gas barrier properties may deteriorate, and if it is too thick, the flexibility may deteriorate.
• the inorganic layer is preferably a metal vapor deposition film, and particularly preferably an aluminum vapor deposition film.
• the inorganic layer is preferably a metal oxide deposited film such as alumina or silica.
• the laminated film of the present disclosure has excellent oxygen barrier properties.
• the oxygen permeability [unit: ml/(m 2 24 hours MPa)] of the laminated film of the present disclosure may be 150 or less (for example, about 0.1 to 150), preferably 100 or less, more preferably It is 10 or less, more preferably 5 or less, and most preferably 2 or less.
• the oxygen permeability can be measured by the MOCON method at a temperature of 20°C and a humidity of 0% RH, and more specifically by the method described in Examples below.
• the laminated film of the present disclosure also has excellent moisture resistance (water vapor barrier properties).
• the moisture permeability (water vapor permeability) [unit: g / (m 2 ⁇ 24 hours)] of the laminated film of the present disclosure may be 5 or less (for example, about 0.01 to 5), preferably 2 or less, and further It is preferably 1.5 or less, more preferably 1.2 or less, and most preferably 1 or less.
• the water vapor permeability can be measured by the MOCON method at a temperature of 40°C and a humidity of 90% RH, and more specifically by the method described in Examples below.
• the laminated film of the present disclosure also has excellent interlayer adhesion.
• the lamination strength between the substrate layer and the intermediate layer is, for example, 0.5 N/15 mm or more (for example, about 0.5 to 10 N/15 mm), preferably is 1 N/15 mm or more, more preferably 1.5 N/15 mm or more, more preferably 2 N/15 mm or more.
• the laminate strength can be measured with a tensile tester, and more specifically, by the method described in Examples below.
• the laminated film of the present disclosure has high light-shielding properties, and may have a total light transmittance of 30% or less, preferably 20% or less, more preferably 10% or less, and more preferably 5% or less. .
• the total light transmittance can be measured using a haze meter (NDH-7000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7361.
• the laminated film of the present disclosure may further have functional layers used in conventional gas barrier films.
• functional layers include organic barrier layers, moisture-proof layers, heat-seal layers, print layers, surface coat layers, etc., which are formed of vinylidene chloride resins.
• the method for producing a laminated film of the present disclosure includes an intermediate layer lamination step of laminating an intermediate layer on at least one surface of a substrate layer, and an inorganic layer lamination step of laminating an inorganic layer on the intermediate layer.
• the substrate layer may be coated with a liquid composition for forming the intermediate layer.
• the liquid composition may contain a solvent in addition to the solid content containing the water-soluble vinyl-based resin and the polyalkyleneimine-based resin.
• the solvent is not particularly limited as long as it can dissolve or disperse the water-soluble vinyl-based resin and the polyalkyleneimine-based resin, but water or a water-soluble solvent is preferable from the viewpoint of excellent solubility.
• water-soluble solvents examples include alkanols (e.g., C 1-3 alkanols such as methanol, ethanol and isopropanol), ketones (di-C 1-3 alkyl-ketones such as acetone and methyl ethyl ketone), ethers ( Examples include cyclic ethers such as tetrahydrofuran and dioxane).
• alkanols e.g., C 1-3 alkanols such as methanol, ethanol and isopropanol
• ketones di-C 1-3 alkyl-ketones such as acetone and methyl ethyl ketone
• ethers examples include cyclic ethers such as tetrahydrofuran and dioxane).
• water and water-soluble solvents can be used alone or in combination of two or more.
• it preferably contains at least water, more preferably water alone, a combination of water and a C 1-3 alkanol such as ethanol, and more preferably water alone.
• the total proportion of the water-soluble vinyl polymer and the polyalkyleneimine resin can be selected from the range of about 0.1 to 50% by mass in the liquid composition, preferably 0.5 to 30% by mass, more preferably 1 to 10% by mass. % by mass.
• Coating methods include conventional methods such as roll coaters, air knife coaters, blade coaters, rod coaters, reverse coaters, bar coaters, comma coaters, die coaters, gravure coaters and screen coaters, spray methods and spinner methods. etc.
• a blade coater method, a bar coater method, a gravure coater method and the like are widely used.
• Drying may be natural drying, but the solvent may be evaporated by drying by heating.
• the drying temperature is, for example, 50 to 110°C, preferably 80 to 105°C, more preferably 90 to 103°C.
• the drying time may be, for example, 10 seconds or longer, preferably 0.3 to 5 minutes, more preferably 0.5 to 3 minutes.
• any method may be used as long as it is a method of laminating a metal and/or an inorganic compound for forming an inorganic layer on the intermediate layer obtained in the above step, and a thin film containing a metal or a metal compound can be formed.
• a method of forming the inorganic layer using a conventional film forming method is preferred.
• PVD physical vapor deposition
• flash deposition electron beam deposition, ion beam deposition, ion plating (e.g., HCD, electron beam RF method, arc discharge method, etc.), sputtering method (e.g., direct current discharge method, radio frequency (RF) discharge method, magnetron method, etc.), molecular beam epitaxy method, laser ablation method, etc.
• sputtering method e.g., direct current discharge method, radio frequency (RF) discharge method, magnetron method, etc.
• molecular beam epitaxy method laser ablation method, etc.
• chemical vapor deposition method e.g. , thermal CVD, plasma CVD, MOCVD (metal organic chemical vapor deposition), optical CVD, etc.
• ion beam mixing ion implantation, and the like.
• a physical vapor phase method such as a vacuum vapor deposition method, an ion plating method, a sputtering method, and a chemical vapor phase method are widely used.
• a vacuum deposition method is particularly preferred.
• OPP Biaxially stretched polypropylene film
• PVA-a Polyvinyl alcohol, "3-98” manufactured by Kuraray Co., Ltd., degree of saponification 98 to 99 mol%, degree of polymerization 300, viscosity (4 mass% aqueous solution, 20°C)3. 2 to 3.8 mPa ⁇ s
• PVA-b Polyvinyl alcohol, manufactured by Kuraray Co., Ltd.
• An intermediate layer coating solution J was prepared so that the imine ratio was 100/1.2.
• Example 1 After coating the intermediate layer coating liquid A on a biaxially oriented polypropylene film (OPP) using a bar coater, the coating film was dried in an oven at 100° C. for 1 minute. The average thickness of the intermediate layer was 1 ⁇ m. After that, an aluminum deposition film was formed on the obtained intermediate layer by a vacuum deposition method to obtain a laminated film. The average thickness of the aluminum deposition film was 40 nm.
• OPP biaxially oriented polypropylene film
• Example 2 A laminate film was obtained in the same manner as in Example 1, except that the intermediate layer coating liquid B was used instead of the intermediate layer coating liquid A.
• Example 3 A laminate film was obtained in the same manner as in Example 1 except that the intermediate layer coating liquid C was used instead of the intermediate layer coating liquid A.
• Example 4 A laminate film was obtained in the same manner as in Example 1 except that the intermediate layer coating liquid D was used instead of the intermediate layer coating liquid A.
• Example 5 A laminate film was obtained in the same manner as in Example 1 except that the intermediate layer coating liquid E was used instead of the intermediate layer coating liquid A.
• Example 6 A laminate film was obtained in the same manner as in Example 1 except that intermediate layer coating liquid F was used instead of intermediate layer coating liquid A.
• Example 7 After coating the intermediate layer coating liquid A on the OPP using a bar coater, the coating film was dried in an oven at 100° C. for 1 minute. The average thickness of the intermediate layer was 1 ⁇ m. Thereafter, an alumina deposition film was formed on the obtained intermediate layer by a vacuum deposition method to obtain a laminated film. The average thickness of the alumina deposition film was 40 nm.
• Example 8 After coating the intermediate layer coating liquid A on the OPP using a bar coater, the coating film was dried in an oven at 100° C. for 1 minute. The average thickness of the intermediate layer was 1 ⁇ m. Thereafter, a silica deposited film was formed on the obtained intermediate layer by a vacuum deposition method to obtain a laminated film. The average thickness of the silica deposition film was 40 nm.
• Example 9 A laminate film was obtained in the same manner as in Example 1 except that the intermediate layer coating liquid G was used instead of the intermediate layer coating liquid A.
• Comparative Example 5 A laminate film was obtained in the same manner as in Comparative Example 1, except that the deposited layer was alumina.
• Comparative Example 7 A laminate film was obtained in the same manner as in Comparative Example 1, except that the deposited layer was silica.
• Table 1 shows the evaluation results of the laminated films obtained in Examples and Comparative Examples.
• the part by mass of the intermediate layer indicates the part by mass based on 100 parts by mass of the water-soluble vinyl polymer.
• the laminated films of Examples 1 to 9 were excellent in gas barrier properties, interlayer adhesion, and appearance.
• the laminated films of Comparative Examples 1, 5, and 7 had lower gas barrier properties.
• the laminated films of Comparative Examples 3, 6 and 8 had lower interlayer adhesion.
• the laminate films of Comparative Examples 2 and 4 had poor interlayer adhesion and appearance.
• the laminated film of the present disclosure can be used as a film that requires barrier properties against gases such as water vapor and oxygen in various fields such as foods, pharmaceuticals, sanitary products, agricultural products, electronic devices, and optical devices. It is particularly useful as a packaging material for pharmaceuticals, precision electronic parts, etc. where light shielding properties are required.

Landscapes

• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Laminated Bodies (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=86902659

Family Applications (1)

Country Status (2)

Cited By (2)

Citations (6)

• 2022
  • 2022-12-21 WO PCT/JP2022/047114 patent/WO2023120577A1/ja not_active Ceased
  • 2022-12-21 JP JP2023569490A patent/JPWO2023120577A1/ja active Pending

Patent Citations (6)

Also Published As

Similar Documents

Legal Events