Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
  • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/048—Forming gas barrier coatings
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/08—Oxides
• • 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
  • B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D2565/38—Packaging materials of special type or form
  • B65D2565/381—Details of packaging materials of special type or form
  • B65D2565/387—Materials used as gas barriers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2400/00—Characterised by the use of unspecified polymers
  • C08J2400/14—Water soluble or water swellable polymers, e.g. aqueous gels
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
  • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
  • C08J2435/08—Copolymers with vinyl ethers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
  • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

• the present invention relates to a gas barrier laminated body in which a metal layer (A) formed by a physical vapor deposition method and a layer (B) formed of a compound having a carboxy group in the structure are laminated.
• Packaging materials used for packaging foods, pharmaceuticals, 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. ing.
• gas barrier properties barrier properties against oxygen and water vapor
• As the thin-film deposition process a process of depositing AlOx, SiOx, or the like is widely used. However, since these vapor-film deposition films are vulnerable to twisting, breaking, etc. and the coating film easily disintegrates, hydrogen having high hydrophilicity on the vapor-film deposition film.
• the resin having a highly hydrophilic hydrogen-bonding group used for coating exhibits excellent gas barrier properties under interference conditions, while the gas barrier property is lowered due to the presence of hydrogen-bonding groups under high humidity conditions. There was a problem.
• a polycarboxylic acid polyvalent metal salt is formed on the surface of the base material by coating an alcohol dispersion of a polycarboxylic acid-based polymer and a divalent metal salt on the base material which has been vapor-deposited.
• the present inventors have repeatedly studied a gas barrier laminate that can be manufactured by a simple process and can obtain a stable gas barrier even under high humidity.
• the present inventors have laminated a metal layer (A) formed by a vapor phase thin film forming method and a layer (B) formed of a compound having a carboxy group in the structure. It has been found that the above-mentioned problems can be solved by the gas barrier laminated body, and the present invention has been completed.
• the present invention it is possible to obtain a gas-barrier laminate that can be manufactured by a simple process and has a stable gas-barrier property even under high humidity.
• the present invention relates to a gas barrier laminated body in which a metal layer (A) formed by a vapor phase thin film forming method and a layer (B) formed of a compound having a carboxy group in the structure are laminated.
• the metal layer (A) may be a layer formed by one or more selected from the group consisting of metal oxides, metal hydroxides, and metal salts.
• the metal layer (A) may be a metal layer formed of one or more metal oxides selected from zinc oxide, magnesium oxide, and calcium oxide.
• the gas barrier laminate may be characterized in that the vapor phase thin film forming method is a physical deposition method.
• polyvalent carboxylic acid compound used in the gas barrier laminate a polyvalent carboxylic acid compound containing two or more carboxy groups in the molecule may be used.
• gas barrier laminate may be characterized by having a resin film base material layer.
• the present invention also relates to a package made of the gas barrier laminated body.
• the gas barrier laminate of the present invention has a metal layer (A) formed by a gas phase thin film forming method.
• the vapor phase thin film forming method used for forming the metal layer in the present invention includes a physical deposition method (hereinafter referred to as PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, and a chemical deposition method (hereinafter referred to as PVD method).
• PVD method physical deposition method
• PVD method chemical deposition method
• the method for producing a vapor phase thin film used in the present invention is not particularly limited, but it is produced by a PVD method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method because a stable thin film can be easily formed. It is most preferable to form a thin film by a vacuum vapor deposition method.
• the metal used to form the metal layer in the present invention is not particularly limited as long as the effect of the present invention can be obtained, and various metals, metal oxides, metal hydroxides, and metals that can impart gas barrier properties are not particularly limited.
• One or more selected from salts can be used. These metals are preferably one or more selected from zinc oxide, magnesium oxide, calcium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, and copper oxide because good gas barrier properties can be obtained. It is preferably one or more selected from zinc oxide, magnesium oxide and calcium oxide, and particularly preferably zinc oxide. These metal compounds may be used alone or in combination of two or more.
• the thickness of the metal layer (A) is not particularly limited as long as the effect of the present invention can be obtained, and may be any range as long as the effect of the present invention can be obtained.
• the thickness of the metal layer (A) is not particularly limited as described above, but is preferably 1 to 100 nm because sufficient gas barrier properties can be obtained, and 3 to 100 nm because the plasticity of the entire gas barrier laminated body can be ensured. 70 nm is more preferable, and 5 to 60 nm is particularly preferable.
• the vapor deposition process used as the PVD method evaporates by heating a target metal, metal oxide, metal hydroxide, resin (hereinafter, these vapor deposition raw materials may be collectively referred to as a target) by various heat sources.
• a target metal, metal oxide, metal hydroxide, resin
• a method is used in which the metal is deposited as droplets or crystals on the surface of the substrate kept at a lower temperature. Such a method is either a batch method in which the entire machined surface is treated at once, or a method in which the equipment is continuously treated or different machined surfaces are continuously treated by moving the base material or the reaction tank. You can use it even if you have it.
• the vapor deposition process in the present invention can be carried out in any of pressure, normal pressure, reduced pressure, vacuum state and its swing, atmosphere and atmosphere of an inert gas.
• By performing the treatment under reduced pressure or vacuum it is possible to improve the transpiration rate and lower the transpiration temperature, and pressurization can promote the precipitation of transpiration.
• the oxidation of the metal, the metal oxide, the metal hydroxide and the like and the carrier can be controlled by creating a vacuum or an inert atmosphere.
• oxidation in the vapor deposition process can be controlled and tolerated, it can be carried out in an atmospheric atmosphere in consideration of cost.
• a preferable thin film can be obtained according to the purpose by adjusting the vapor deposition conditions.
• the above conditions are the time during which the pressure in the chamber and the surface of the molecules and the substrate existing in the target vapor and the atmosphere come into contact with each other in order to control the chemical structure of the target vapor film, and the film is formed by controlling this time.
• the composition of the vapor-filmed thin film can be controlled.
• the structure of the thin film surface can be controlled by bringing the thin film into contact with oxygen or water vapor after the thin film is formed.
• Controlling the chemical structure of the target vapor deposition means for example, to obtain a compound in which a hydroxyl group or oxygen is added to the target metal as a vapor deposition layer by adding steam or oxygen at the time of vapor deposition.
• the vapor deposition conditions can be appropriately examined according to the desired vapor deposition film.
• the sputtering method in the present invention is not particularly limited as long as the effect of the present invention can be obtained, and can be selected from DC sputtering, RF sputtering, magnetron sputtering, ion beam sputtering, RF magnetron sputtering and the like. Since sputtering can be performed with high efficiency, a method using magnetron sputtering or RF magnetron sputtering is preferable. It is desirable that magnetron sputtering be performed in a processing space such as a chamber in which the pressure is reduced to 1 ⁇ 10 -4 Pa or less and an inert gas (for example, argon or the like) is introduced.
• an inert gas for example, argon or the like
• the target which is the raw material of the thin film, and the base material are arranged so as to face each other.
• a device such as a permanent magnet and a holder for holding the target, if necessary, is arranged on the back side of the target.
• the magnetic field of the permanent magnet can constrain the spiral orbit of electrons existing in the processing space, and generate a high-density plasma region.
• the presence of the high-density plasma region promotes ionization of the inert gas, and the ions collide with the target to generate target fine particles, and the generated fine particles adhere to the substrate to form a thin film. ..
• the high-frequency output when performing RF magnetron sputtering is not particularly limited, and may be adjusted from the viewpoint of achieving an appropriate film formation rate. Further, it is desirable to control the temperature of the substrate during film formation from room temperature to about 100 ° C.
• the compound having a carboxy group in the structure used for forming the layer (B) in the present invention is not particularly limited as long as the effect of the present invention can be obtained, but is a monovalent carboxylic acid compound or a polyvalent compound. It can be selected from a carboxylic acid compound, a resin having a carboxy substituent, and the like.
• a polyvalent carboxylic acid compound is preferable because it exhibits good barrier properties, and citric acid, melitonic acid, trimellitic acid, succinic acid, butanetetracarboxylic acid, benzenepentacarboxylic acid, and benzene are preferable. Hexacarboxylic acid and salts thereof can be used. It is preferable to use one or more polyvalent carboxylic acids containing two or more carboxy groups in the molecule because good gas barrier properties can be obtained. It is more preferable to use one or more selected.
• the layer (B) when the layer (B) is formed by using the monovalent carboxylic acid compound and the polyvalent carboxylic acid compound, the layer (B) is dissolved in a solvent, and a roll coating method, a spray method, a spin coating method, etc. are applied on the substrate.
• the coating may be performed by a known and commonly used coating method such as a blade coating method, a dip method, a screen printing method, an inkjet method, a doctor roll method, a doctor blade method, a curtain coating method, a slit coating method, and a dispensing method.
• solvents such as aqueous solvents and non-aqueous solvents, resins, coupling agents, silane compounds, phosphoric acid compounds, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.).
• solvents such as aqueous solvents and non-aqueous solvents, resins, coupling agents, silane compounds, phosphoric acid compounds, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.).
• Plasticizers, antistatic agents, solvents, antiblocking agents, colorants, crystal nucleating agents, oxygen trapping agents, tackifiers and the like may be added.
• the thickness of the (B) layer is not particularly limited as long as the effect of the present invention can be obtained. However, it is preferably in the range of 5 to 1000 nm because sufficient gas barrier properties can be obtained, and more preferably in the range of 10 to 500 nm because it can achieve both flexibility and robustness.
• the resin itself having a carboxy group may be used as a base material.
• the layer (B) has a solvent such as an aqueous solvent or a non-aqueous solvent, a resin, a coupling agent, a silane compound, a phosphoric acid compound, and an organic filler for the purpose of improving the coatability.
• a solvent such as an aqueous solvent or a non-aqueous solvent, a resin, a coupling agent, a silane compound, a phosphoric acid compound, and an organic filler for the purpose of improving the coatability.
• Inorganic fillers such as an aqueous solvent or a non-aqueous solvent, a resin, a coupling agent, a silane compound, a phosphoric acid compound, and an organic filler for the purpose of improving the coatability.
• Inorganic fillers such as an aqueous solvent or a non-aqueous solvent, a resin, a coupling agent, a silane compound, a phosphoric acid compound, and an organic filler for the purpose of improving the coatability.
• 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 capryl.
• Alcohols such as 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, salicylic acid.
• Ethanol and ethyl acetate are preferable because esters such as pentyl, methyl formate, ethyl formate, and pentyl formate can be used and drying after coating is easy.
• 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% and 80 wt%, preferably 35 wt% in the solid content of the layer (B). 75 wt% is particularly preferable.
• the gas barrier laminate of the present invention may be obtained by laminating the layer (A) and the layer (B) on various substrates such as a resin film, and when a resin having a carboxy group is used as the layer (B).
• the structure may be such that only the layer (A) and the layer (B) are laminated.
• the layers (A) and (B) when the layer (A) and the layer (B) are laminated on a base material layer such as a film to form a gas barrier laminated body, the layers (A) and (B) can be obtained within the range where the effect of the present invention can be obtained.
• the order of laminating is not particularly limited, but it is preferable that the (A) layer and the (B) layer are sequentially laminated on the base material layer in that the laminating process can be easily performed.
• the base material such as a film used in the present invention is not particularly limited as long as the gas barrier effect of the present invention can be obtained, and can be appropriately selected by those skilled in the art according to a desired application.
• the base material is one or more of various resin films such as polyolefin resin, polyester resin, polyamide resin, resin having a carboxy substituent, polystyrene resin, polyvinyl resin, etc., paper, wood, metal, metal oxide, silicon or modified silicon. Since one or more base materials selected from the above can be selected and used and the gas barrier effect of the present invention can be preferably obtained, resin films and papers are preferable, and resin films are particularly preferable. .. Those having an anchor coat layer on the surface of these base materials can also be used. Further, as the resin film, a stretched film or an unstretched film may be used.
• the shape, hardness, thickness, etc. of the base material are not particularly limited, and various base materials such as flat plates, sheet shapes, and three-dimensional shapes are selected according to the purpose, and the hardness, thickness, and the like thereof 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.
• the gas barrier property can be improved by 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, depressurization, and ventilation can be used.
• 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 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 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 products. 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.
• the packaging material of the present invention is obtained by using the laminate of the present invention, laminating the surfaces of the sealant films of the laminate facing each other, and then heat-sealing the peripheral ends thereof.
• the laminated body of the present invention is bent or overlapped so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral end thereof is, for example, a side seal type or a two-way seal type.
• the packaging material of the present invention can take various forms depending on the contents, the environment in which it is used, and the form in which it is used. Self-supporting packaging materials (standing pouches), etc. are also possible.
• As a heat sealing method a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.
• the opening After filling the packaging material of the present invention with the contents from the opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention.
• the contents to be filled include rice confectionery, bean confectionery, nuts, biscuits and cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snack confectionery and other confectionery, bread, snack noodles, instant noodles, dried noodles, pasta.
• the packaging material of the present invention can also be used as a packaging material for pharmaceuticals such as cigarettes, disposable body warmers, infusion packs, cosmetics, and vacuum heat insulating materials.
• a magnetron sputtering apparatus (manufactured by Cannon Anerva Co., Ltd .: model EB1100) was used.
• a zinc oxide target was used as the target, and a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Film Processing Co., Ltd.) was used as the base film.
• Argon was used as the process gas to form a zinc oxide vapor deposition layer.
• the sputtering power supply power was 5.0 W / cm 2 , and the film formation pressure was 0.4 Pa.
• the oxygen partial pressure was 10%.
• Example 1 137 g of the adjusting liquid obtained in Resin Solution Preparation Example 1, 1.85 g of citric acid and 59 g of water were mixed to obtain a coating liquid 1.
• the obtained coating agent was applied to a transparent vapor-deposited PET film vapor-deposited surface on which ZnO was vapor-deposited to a thickness of 100 nm using a bar coater so that the coating thickness after drying was about 0.4 g / m 2 .
• the laminate was heated in a dryer at 80 ° C. for 2 minutes to prepare a laminate.
• the obtained laminate was aged in a dryer at 40 ° C. for 1 day, and then the gas barrier property of the laminate was evaluated.
• a base material and a coating liquid in which ZnO was vapor-deposited to the thickness shown in Table 1 were prepared, and a laminate was produced and evaluated by the same method as in Example 1. These results are shown in Table 1.
• Examples 12 to 14 37 g of the adjusting liquid 1, 1.85 g of citric 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 a transparent thin-film PET film (Barrierox 1011HG, manufactured by Toray Film Processing Co., Ltd., thickness: 12 ⁇ m), and the coating thickness after drying with a bar coater is about 0.4 g / m. It was painted so that it became 2 .
• the film was heated in a dryer at 80 ° C. for 2 minutes to prepare a resin-coated film.
• Films having the film thicknesses shown in Table 1 (Examples 12 to 14) were obtained by controlling the vapor deposition time in the same manner as in Production Examples 1 to 3 except that a resin-coated film was used as the base material.
• the thickness of the adjusting liquid 2 obtained in the resin solution adjusting example 2 is about 0.4 g / m 2 after being dried by using a bar coater on the vapor-deposited surface of the transparent vapor-deposited PET film obtained by depositing ZnO to a thickness of 100 nm. It was painted like this. Immediately after coating, the laminate was heated in a dryer at 80 ° C. for 1 minute to prepare a laminate. The obtained laminate was aged in a dryer at 40 ° C. for 1 day, and then the gas barrier property of the laminate was evaluated.
• Example 1 A coating liquid 1 equivalent to that used in Example 1 was prepared, and a bar coater was placed on the vapor-deposited surface of a transparent vapor-deposited PET film (Barrierlocks 1011HG, manufactured by Toray Film Processing Co., Ltd., thickness: 12 ⁇ m) on which ZnO was not vapor-deposited. The coating was applied so that the coating thickness after drying was about 0.4 g / m 2 . Immediately after coating, the laminate was heated in a dryer at 80 ° C. for 2 minutes to prepare a laminate. The obtained laminate was aged in a dryer at 40 ° C. for 1 day, and then the gas barrier property of the laminate was evaluated.
• a transparent vapor-deposited PET film Barrierlocks 1011HG, manufactured by Toray Film Processing Co., Ltd., thickness: 12 ⁇ m
• the adjusting liquid 1 was applied to the vapor-deposited surface of the transparent vapor-deposited PET film in which ZnO was vapor-deposited to a thickness of 100 nm using a bar coater so that the coating thickness after drying was about 0.4 g / m 2 .
• the laminate was heated in a dryer at 80 ° C. for 2 minutes to prepare a laminate.
• the obtained laminate was aged in a dryer at 40 ° C. for 1 day, and then the gas barrier property of the laminate was evaluated.
• This ZnO dispersion is applied to a transparent thin-film PET film (Barrier Rocks 1011HG, manufactured by Toray Film Processing Co., Ltd., thickness: 12 ⁇ m) using a bar coater so that the coating thickness after drying is about 0.4 g / m 2 . Painted. Immediately after coating, the laminate was heated in a dryer at 80 ° C. for 1 minute to prepare a laminate. Next, a coating liquid 1 equivalent to that used in Example 1 was prepared, and a bar coater was used on the ZnO coated surface of the prepared film so that the coating thickness after drying was about 0.4 g / m 2 . Painted on. Immediately after coating, the laminate was heated in a dryer at 80 ° C. for 2 minutes to prepare a laminate. The obtained laminate was aged in a dryer at 40 ° C. for 1 day, and then the gas barrier property of the laminate was evaluated.
• the unit of oxygen permeability is cc / day ⁇ atm ⁇ m 2 .
• Water vapor permeability> The water vapor transmittance (MVTR) was measured according to JIS-K7129 in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH using a water vapor permeability measuring device 7001 manufactured by Illinois.
• the unit of oxygen permeability is g / m 2 ⁇ day.
• Tables 1 to 3 show the configurations of the laminated bodies and the results of barrier property evaluation in each Example and Comparative Example.
• the laminate of the present invention exhibits excellent gas barrier properties 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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• Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Laminated Bodies (AREA)
• Wrappers (AREA)

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• 2021
  • 2021-12-16 US US18/266,653 patent/US20240101325A1/en active Pending
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