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
  • 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
• • 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 is a gas barrier laminate in which a layer (A) containing ethyl cellulose and an inorganic compound in a non-aqueous solvent and a layer (B) containing a polyvalent carboxylic acid monomer are coated and laminated on a substrate. Regarding.
• Packaging materials used for packaging foods, chemicals, etc. are required to have barrier properties against oxygen and water vapor (hereinafter referred to as gas barrier properties) for the purpose of preventing denaturation of contents and flavor due to oxidation and deterioration of efficacy.
• gas barrier properties barrier properties against oxygen and water vapor
• an oxygen barrier resin a polymer having a highly hydrophilic hydrogen-bonding group represented by polyacrylic acid or polyvinyl alcohol in the molecule, or a polycarboxylic acid and an inorganic metal are coated on the film surface and ionized.
• Packaging materials that exhibit gas barrier properties by cross-linking have been used. Packaging materials made of these resins exhibit excellent oxygen barrier properties under dry conditions. On the other hand, under high humidity, there is a problem that the oxygen barrier property is significantly lowered due to the hydrophilicity of the resin.
• the present inventors have repeatedly studied gas barrier laminates in which the oxygen barrier property does not deteriorate even under high humidity.
• the present inventors have applied a coating solution containing ethyl cellulose and an inorganic compound to a non-aqueous solvent on the substrate (A) layer, a polyvalent carboxylic acid monomer.
• the present invention has been completed by finding that the above-mentioned problems can be solved by a gas-barrier laminated body in which the layer (B) containing the above is coated and laminated.
• the present invention comprises a layer (A) formed by applying a coating solution containing ethyl cellulose and an inorganic compound to a non-aqueous solvent on a substrate, and a layer (B) containing a polyvalent carboxylic acid monomer.
• A a coating solution containing ethyl cellulose and an inorganic compound to a non-aqueous solvent on a substrate
• B a layer containing a polyvalent carboxylic acid monomer.
• the base material used for the gas barrier laminate of the present invention is not particularly limited as long as the gas barrier effect of the present invention can be obtained, and a person skilled in the art can appropriately select it according to a desired application.
• the base material one or more base materials selected from resin films, paper, wood, metals, metal oxides, silicon, modified silicon and the like can be selected and used, and the gas barrier effect of the present invention is preferably used. Since it can be obtained, it is preferably a resin film or paper, and particularly preferably a resin film.
• the shape, hardness, thickness, etc. of the base material are not particularly limited, and various base materials such as a flat plate, a sheet shape, or a three-dimensional shape are selected according to the purpose, and the hardness, thickness, etc. of these are appropriately set. Can be used.
• the base material may contain additives, if necessary. For example, improve and modify workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, flame retardancy, antifungal properties, electrical properties, strength, etc.
• plastic compounding agents and additives such as lubricants, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing materials, antistatic agents and pigments can be added.
• the amount of the additive added can be appropriately used as long as the gas barrier effect of the present invention can be obtained.
• resin film preferably used in the gas barrier laminate of the present invention various resin films such as polyolefin resin, polyester resin, and polyamide resin, and a laminated film combining these can be used. Further, as the resin film, a stretched film or an unstretched film may be used.
• the base material may be a base material on which a metal or a metal oxide is vapor-deposited on one side or both sides thereof.
• This vapor deposition treatment may be carried out by a known and commonly used method, and may be carried out by using a material that can be appropriately selected by those skilled in the art according to the properties of the base material to be selected.
• the non-aqueous solvent used in the gas barrier laminate of the present invention is not particularly limited as long as the gas barrier effect of the present invention can be obtained, but is not particularly limited, but ethanol, methanol, 2-propanol, ethylene glycol, glycerin, and capryl alcohol. , Lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and other alcohols, and methyl acetate, ethyl acetate, pentyl acetate, octyl acetate, methyl butyrate, ethyl butyrate, pentyl butyrate, methyl salicylate, ethyl salicylate, pentyl salicylate.
• Esters such as methyl formate, ethyl formate, pentyl formate, and ketones such as acetone, methyl ethyl ketone, methyl propyl ketone and methyl isobutyl ketone can be used, and ethanol, methanol and 2-propanol can be used because ethyl cellulose can be dissolved well. , Ethyl acetate is preferred.
• ethyl cellulose used in the gas barrier laminate of the present invention those having various weight average molecular weights can be used as long as the gas barrier effect of the present invention can be obtained, and the weight average molecular weight is 20 but not limited. Those having a weight average molecular weight of 3,000 to 250,000 are preferable because they have excellent coatability, and those having a weight average molecular weight of 25,000 to 230,000 are particularly preferable, and those having a weight average molecular weight of 30,000 to 200,000 are particularly preferable. Is. As such ethyl cellulose, for example, Etocell (registered trademark) STD-4, 7, 10, 20, 45, 100, 200 of Dow Chemical Co., Ltd. can be used.
• Etocell registered trademark
• the inorganic compound used in the gas barrier laminate of the present invention is not particularly limited as long as the gas barrier effect of the present invention can be obtained, but is one or more selected from metal oxides, metal hydroxides, and metal salts. It is preferably an inorganic compound of the above, more preferably a metal oxide or a metal salt, and particularly preferably a metal oxide.
• the metal oxide preferably used as an inorganic compound in the gas barrier laminate of the present invention is not particularly limited as long as the gas barrier effect of the present invention can be obtained, but zinc oxide can be obtained because good gas barrier properties can be obtained.
• These metal compounds may be used alone or in combination of two or more.
• the layer (A) formed by applying a coating solution containing ethyl cellulose and an inorganic compound to a non-aqueous solvent in the present invention is prepared by dissolving ethyl cellulose in a non-aqueous solvent, and then adding and mixing the inorganic compound. ..
• the amount of the inorganic compound added is appropriately set based on the amount ratio with the polyvalent carboxylic acid monomer described later, but is preferably 1 to 15 parts by weight with respect to 100 parts by weight of the non-aqueous solvent. 3 to 10 parts by weight is more preferable, and 5 to 8 parts by weight is particularly preferable because good gas barrier properties and coatability can be obtained.
• the amount of the inorganic compound added to the layer (A) is not particularly limited as long as the gas barrier property of the present invention can be obtained, but it is preferably 50 wt% to 90 wt%, preferably 60 wt% in the solid content of the layer (A). -80 wt% is more preferable, and 70 wt% to 80 wt% is particularly preferable.
• the layer (A) coating liquid containing ethyl cellulose and an inorganic compound in the non-aqueous solvent of the present invention contains a solvent such as an aqueous solvent or a non-aqueous solvent, a resin, and a coupling agent for the purpose of improving the coatability.
• a solvent such as an aqueous solvent or a non-aqueous solvent, a resin, and a coupling agent for the purpose of improving the coatability.
• the solvent that can be added to the layer (A) coating liquid include water, ethanol, methanol, 2-propanol, ethylene glycol, glycerin, capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol.
• Alcohols such as oleyl alcohol, and esters such as methyl acetate, ethyl acetate, pentyl acetate, octyl acetate, methyl butyrate, ethyl butyrate, pentyl butyrate, methyl salicylate, ethyl salicylate, pentyl salicylate, methyl formate, ethyl formate, pentyl formate.
• Ethanol and ethyl acetate are preferable because they can be easily dried after coating.
• the polyvalent carboxylic acid monomer used in the gas barrier laminate of the present invention is not particularly limited as long as the effect of the present invention can be obtained, but citric acid, melitric acid, trimellitic acid, succinic acid, etc. Examples thereof include butanetetracarboxylic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid and salts thereof. It is preferable to use one or more polyvalent carboxylic acid monomers containing two or more carboxy groups in the molecule because good gas barrier properties can be obtained, from citric acid, butanetetracarboxylic acid, succinic acid, and trimellitic acid. It is more preferable to use one or more selected from the group.
• the amount of these polyvalent carboxylic acid monomers added is not particularly limited as long as the gas barrier property of the present invention can be obtained, but is preferably 30 wt% to 80 wt%, preferably 35 wt% in the solid content of the layer (B). % To 75 wt% is particularly preferable.
• the layer (B) containing the polyvalent carboxylic acid monomer used in the gas barrier laminate of the present invention includes a solvent such as an aqueous solvent or a non-aqueous solvent, a resin, or a resin for the purpose of improving the coatability.
• a solvent such as an aqueous solvent or a non-aqueous solvent, a resin, or a resin for the purpose of improving the coatability.
• Various additives such as a crystal nucleating agent, an oxygen trapping agent, and a tackifier may be added.
• the solvent that can be added to the layer (B) is preferably a solvent in which the polyhydric carboxylic acid monomer used is dissolved, and specifically, water, ethanol, methanol, 2-propanol, ethylene glycol, glycerin, and the like.
• Alcohols such as capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and methyl acetate, ethyl acetate, pentyl acetate, octyl acetate, methyl butyrate, ethyl butyrate, pentyl butyrate, methyl salicylate, ethyl salicylate, Ethanols and ethyl acetate are preferable because esters such as pentyl salicylate, methyl formate, ethyl formate, and pentyl formate can be used and drying after coating is easy.
• the additive that can be added to the layer (B) is not particularly limited as long as the effect of the present invention can be obtained, but various synthetic resins such as polyvinyl alcohol can be used and are excellent under dry conditions. Polyvinyl alcohol is particularly preferable because it exhibits a barrier property and is easy to apply and dry.
• the layer (A) formed by applying a coating liquid containing ethyl cellulose and an inorganic compound to a non-aqueous solvent and the layer (B) containing a polyvalent carboxylic acid monomer are provided.
• the order of coating the layers (A) and (B) when laminating on the substrate is not particularly limited as long as the gas barrier effect of the present invention can be obtained, but (B) is applied to the substrate. It is preferable to coat and laminate the layer (A) after coating the layer because a more suitable gas barrier effect can be obtained.
• the coating method of the (A) layer and the (B) layer is not particularly limited, and the roll coating method, the spray method, the spin coating method, the blade coating method, the dip method, the screen printing method, and the like.
• Known and conventional coating methods such as an inkjet method, a doctor roll method, a doctor blade method, a curtain coating method, a slit coating method, and a dispense method can be used.
• the gas barrier property can be improved by coating and laminating the (A) layer and the (B) layer and then drying them.
• the drying method after coating is not particularly limited as long as it can be dried, but a drying method such as room temperature drying, heating, decompression, and ventilation can be used.
• the gas barrier laminate of the present invention is excellent in transparency, and the haze value 24 hours after the layer (A) and the layer (B) are coated and laminated on the substrate is less than 6, which is more preferable. Is less than 4.
• the gas barrier laminate of the present invention may be a multilayer laminate in which a base material, a layer (A), a layer (B) and / or other coating layers are further laminated on one side or both sides of the laminate.
• the gas barrier laminate of the present invention has good gas barrier properties, it can be suitably used as various packages. In particular, it can be used for packaging applications that require gas barrier properties such as foods, daily necessities, electronic materials, and medical applications. Further, since it is excellent in heat resistance and moisture heat resistance, it can be suitably used as a packaging material for heat sterilization such as boiling and retort.
• ⁇ Preparation method of metal oxide dispersion liquid> (Metal Oxide Dispersion Liquid Adjustment Example 1) Regarding the ZnO dispersion, ZnO (FINEX-50, manufactured by Sakai Chemical Industry Co., Ltd., FINEX-50) with a primary particle diameter of 20 nm and IPA: 700 g are mixed and mixed in a bead mill (Ashizawa Finetech Co., Ltd .: Labstar Mini LMZ015). After dispersion treatment for 1 hour using zirconia beads having a diameter of 0.3 mm, the beads were sifted to obtain a ZnO solution having a solid content concentration of 30%. The particle size of ZnO in this dispersion was 88 nm.
• Example 1 The adjusting liquid 137g obtained in the resin solution adjusting example 1, 4.3 g of succinic acid and 59 g of water were mixed to obtain a coating liquid 1.
• the obtained coating agent is applied to the vapor-filmed surface of an AlOx-OPP film (manufactured by JINDAL: 16A0894, thickness: 16 ⁇ m) using a bar coater so that the coating thickness after drying becomes about 0.4 g / m 2. did.
• the laminate was heated in a dryer at 60 ° C. for 2 minutes to prepare a laminated body 1a.
• the adjusting liquid 227 g obtained in the resin solution adjusting example 2 and the ZnO dispersion liquid 28 g and the IPA 46 g obtained in the metal oxide dispersion adjusting example 1 were mixed to obtain a coating liquid 4.
• the obtained coating liquid is coated on the vapor-deposited surface of an AlOx-OPP film (manufactured by JINDAL: 16A0894, thickness: 16 ⁇ m) using a bar coater so that the coating thickness after drying becomes about 1.0 g / m 2. did.
• the laminate was heated in a dryer at 60 ° C. for 1 minute to prepare a laminated body 12.
• the obtained laminate 12 was aged in a dryer at 40 ° C. for 1 day, and then the gas barrier property of the laminate was evaluated and the haze was measured.
• the unit of oxygen permeability is cc / day ⁇ atm ⁇ m 2 .
• the haze of the film was measured using a haze meter NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.
• the laminate of the present invention exhibits excellent gas barrier properties as compared with conventional gas barrier laminates due to its composition. From this, the laminate of the present invention can be suitably used as a packaging material, particularly a packaging material that requires barrier properties such as food, daily necessities, electronic materials, and medical use.

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• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)
• Wrappers (AREA)

Priority Applications (1)

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Publications (1)

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Citations (4)

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• 2021
  • 2021-05-27 JP JP2022515519A patent/JP7136382B2/ja active Active
  • 2021-05-27 WO PCT/JP2021/020110 patent/WO2021246269A1/ja not_active Ceased
  • 2021-05-31 TW TW110119619A patent/TWI887425B/zh active

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