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
  • B65D65/42—Applications of coated or impregnated materials
• • 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
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • 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
  • 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
  • C08J7/052—Forming heat-sealable coatings

Definitions

• the present invention is a transparent film having excellent gas barrier properties against water vapor, oxygen, etc., and a film for retort processing of food, a film for heating a microwave oven, a pharmaceutical product, a precision electronic component and the like.
• the present invention relates to a gas barrier film suitable for use and a method for producing the same. Background art
• Packaging films used for foods, pharmaceuticals, precision electronic parts, etc. require high transparency for the visibility and aesthetics of the contents, as well as deterioration of the contents due to moisture absorption and oxidation. In order to prevent such problems, gas barrier is required.
• cooked foods In recent years, with the spread of microwave ovens, cooked or semi-cooked foods (hereinafter collectively referred to as “cooked foods”) are heated in a microwave oven while being packaged and served before meals. In addition, the cooked food is often retorted after packaging. Such packaging materials must be able to withstand retorting and microwave heating. In addition, in order to prevent deterioration of food quality, it is required to have high gas barrier properties against water vapor, oxygen, etc., and high transparency for visual recognition of contents.
• Japanese Patent Application Laid-Open No. 559-19691 discloses that vinyl chloride dendetylene is applied to the surface of a base film such as a polyester film or a polypropylene film. There is disclosed a film coated or laminated with a polymer having excellent gas barrier properties such as a vinyl alcohol co-body. Further, as a packaging material, for example, a vinylidene chloride-based polymer film or a vinylidene chloride-based material having a gas barrier property is used. A multi-layer film in which a film coated with a polymer and the like and a non-stretched polypropylene film having a heat seal property are laminated is also proposed.
• a finolem laminated with a gas barrier polymer is excellent in transparency and allows the contents to be seen through, but the gas barrier properties against water vapor, oxygen, etc., are still insufficient. In particular, at high temperatures, the gas barrier properties against water vapor, oxygen gas, and the like are significantly reduced. Therefore, it is not suitable for long-term storage of cooked food.
• the thickness of vinylidene chloride-based polymer is increased to improve gas barrier properties, the loss of microwaves in the film increases when heating with an electronic range, and the heating time increases.
• film costs increase.
• the vinylidene chloride-based polymer when exposed to high temperatures (for example, at a temperature of 110 ° C or higher) due to retort treatment or microwave heating, the vinylidene chloride-based polymer has low heat resistance, and is therefore resistant to water vapor and oxygen gas. Gas barrier properties are significantly reduced. Therefore, it is not suitable for packaging retort foods or foods for microwave heating.
• whitening occurs at high temperatures and the transparency is reduced, so that the visibility of the contents is reduced.
• Japanese Patent Application Laid-Open No. Sho 62-15252764 discloses a film in which a metal deposition layer such as tin is formed on a base film such as polyethylene terephthalate, and an aluminum foil.
• a packaging film has been proposed which is laminated with a polypropylene film and the like. Films with laminated metal layers have excellent gas barrier properties and are used for packaging retort foods, but they are not transparent and have electrical conductivity, so they must be heated in a microwave oven. Can not.
• Japanese Patent Publication No. 53-12953 and Japanese Patent Application Laid-Open No. 4-173137 propose a film on which a silicon oxide is vapor-deposited.
• No. 237 proposes a film obtained by vacuum-depositing magnesium fluoride or the like. But like this In the composite film, when the thickness of the inorganic layer is increased in order to increase the gas barrier property against water vapor, oxygen, etc., the permeability is reduced, and the flexibility is reduced, and cracks and peeling are caused. On the other hand, if the film thickness is reduced to ensure transparency, sufficient gas barrier properties cannot be obtained.
• Japanese Patent Application Laid-Open No. 4-173137 also discloses a composite film in which a gay oxide is vapor-deposited on polyvinylidene chloride-coated polyethylene terephthalate.
• a mechanical external force acts on the surface inorganic thin film by bending, kneading, or the like, peeling or a defective portion is generated, and the gas barrier property is greatly reduced.
• Japanese Unexamined Patent Publication (Kokai) No. 63-237,940 discloses that a film obtained by sputtering an oxide of oxide or tin oxide is provided with a heat sink such as an ethylene-propylene copolymer base. There is disclosed a double-unit film having a metal layer formed thereon.
• Japanese Patent Application Laid-Open Nos. Hei 1 — 024365 and Hei 1 — Hei 0 24336 describe that, on the surface of a base film, a vapor-deposited layer of a gay oxide and a heat seal layer are provided.
• a packaging material for electronic range and packaging material for retort food having a protective layer formed thereon is disclosed, wherein the heat seal layer is formed of a heat-sealing resin film such as polypropylene.
• the protective layer is formed of a laminate of a film or a coating of a thermosetting resin.
• a film in which a heat seal layer or a protective layer is formed on an inorganic oxide layer still has low gas barrier properties, an oxygen transmission rate of lcc / m 2 ⁇ 24 hr, and a water vapor transmission rate of 1 g / m 2 * 24. It is only about hr. Therefore, it is not yet suitable for packaging food that requires long-term storage. In addition, since the resin film is laminated, the thickness of the film increases.
• Japanese Patent Application Laid-Open No. HEI 9-192636 discloses that two or more silicon oxide vapor-deposited layers are laminated on the surface of a substrate film, and the surface is further protected by the same protective layer or A packaging material coated with a heat seal layer has been proposed.
• the production of such packaging materials requires two or more depositions. Requires a process.
• it is necessary to return the apparatus to normal pressure and remove the film every time the deposition process is performed which not only complicates the production process but also increases the cost. Become.
• an object of the present invention is to provide a gas barrier film having excellent gas barrier properties and transparency even when the coating layer is thin, and a method for producing the same.
• Another object of the present invention is to have a high gas barrier property even at a high temperature, and to be excellent in flexibility, and to suppress a decrease in gas barrier property even when a mechanical external force such as bending or kneading acts.
• An object of the present invention is to provide a gas barrier film that can be produced and a method for producing the film.
• Still another object of the present invention is to provide a gas barrier capable of suppressing a decrease in transparency and gas barrier properties even when exposed to a high temperature and capable of preserving contents for a long period of time while suppressing deterioration and deterioration.
• An object of the present invention is to provide a neutral film and a method for producing the same.
• Another object of the present invention is to provide a gas barrier film and a gas barrier film that can suppress the loss of microwaves during electromagnetic wave heating and are useful for packaging foods and the like to be subjected to electromagnetic wave heating and retort treatment.
• the present inventors have conducted intensive studies in order to achieve the above object, and as a result, when the inorganic layer formed on the surface of the base film layer is coated with a resin having a high gas barrier property, transparency and flexibility are obtained. In addition to its properties, even if the coating layer is thin, it has excellent gas barrier properties. However, the present inventors have found that a film force that does not lower the gas barrier property can be obtained; and thus completed the present invention.
• the base film layer can be formed of various polymers, for example, an olefin-based polymer, polyester, or a polyamide.
• the inorganic layer having transparency can be composed of, for example, various metal simple substances such as a Group 2A element, a Group 2B element, a Group 3B element, a Group 4B element, and a Group 6B element, or an inorganic compound thereof.
• the barrier resin coating layer can be formed by applying a coating solution containing a gas barrier resin such as a vinylidene chloride copolymer or an ethylene-vinyl alcohol copolymer.
• the other surface of the base film or the barrier resin coating layer may be covered with a heat seal layer.
• the thickness of the inorganic layer may be about 100 to 500 ⁇ , and the thickness of the barrier resin coating layer may be about 0.05 to 15 ⁇ 1.
• the ratio n 2 Z n l of the thickness n 2 (m) of the barrier resin coating layer to the thickness n l (rn) of the inorganic layer is 0.1.
• carrier resin coating layer refers to an oxygen gas permeability of 20 cc / m at a temperature of 25 at a thickness of 2 m • 24 hours or less, a temperature of 4 CTC, 9 0?
• heat seal layer means a layer that can be thermally bonded by a method such as impulse sealing, high-frequency bonding, or ultrasonic bonding, as well as thermal bonding using a heat sealer.
• the polymer constituting the base film layer (1) can be formed into a film Various polymers, for example, polyethylene, ethylene monoethyl acrylate copolymer, ionomer, polypropylene,... Polyethylene propylene copolymerized copolymer, poly-olefin such as poly-4—methylpentene-1; polyethylene terephthalate evening rate, polyethylene 1-2, 6 —Polyesters such as naphthalate and polybutylene terephthalate; Nail opening 6, Nylon 11, Nylon 12, Nylon 66, Nylon 610 , Nylon 6Z66, Nylon 66Z610, etc .; Aromatic Polyamide; Polyvinyl Chloride; Vinylidene Polychloride, Vinylidene Chloride Vinylidene chloride resins such as vinyl monochloride copolymer, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride- (meth) acrylate copolymer; Polystyrene
• the light transmittance of the base film layer can be appropriately selected.
• the total light transmittance in white light is usually 40% or more, preferably. Should be at least 60%, more preferably at least 80%.
• the base film layer (1) may be made of a polymer such as an olefin polymer (especially a polypropylene polymer), a polyester (especially a polyethylene terephthalate), or the like. Polyalkyleneterefu evening rate), Polyamide, It is preferably composed of a polyethylene polymer, ethylene-vinyl alcohol copolymer, polyforce-bonate, polyacrylonitrile, and the like. Olefin-based polymers, polyesters, and polyamides are excellent in transparency, mechanical strength, and packaging suitability.
• a polymer such as an olefin polymer (especially a polypropylene polymer), a polyester (especially a polyethylene terephthalate), or the like. Polyalkyleneterefu evening rate), Polyamide, It is preferably composed of a polyethylene polymer, ethylene-vinyl alcohol copolymer, polyforce-bonate, polyacrylonitrile, and the like. Olefin-based polymers, polyesters, and polyamides
• Packaging materials for foods for retort processing and electromagnetic wave heating include highly heat-resistant polymers with excellent transparency, mechanical strength and packaging suitability, such as polypropylene, polyester, and polyamide.
• Preferred are ethylene, vinyl alcohol copolymer, polycarbonate, and polyacrylonitrile.
• Particularly preferred polymers constituting the base film layer (1) include polyesters and polyamides.
• the base film layer may be a single-layer film or a laminated film in which two or more polymer layers are laminated.
• the thickness of the base film layer is not particularly limited, and is appropriately selected in consideration of packaging suitability, mechanical strength, flexibility, and the like.
• the thickness of the substrate off I Lum layer is usually 3 to 2 0 0 ⁇ 0 1, is favored properly 5-1 0 0 ⁇ 01, is rather to favored by al 1 0-5 0 / about m.
• the Kimura film layer can be formed by a conventional film forming method, for example, a melt forming method such as an inflation method or a T-die method, or a casting method using a solution. . Further, the base film layer may be unstretched, or may be stretched for one or two times.
• a conventional stretching method such as roll stretching, rolling stretching, belt stretching, tensile stretching, tube stretching, or a combination thereof can be applied.
• the stretching ratio can be appropriately set according to the desired film properties, and is, for example, at least about 1.5 to 20 times, preferably about 2 to 15 times at least in one direction.
• At least one surface of the base film layer may be surface-treated.
• the surface treatment include corona discharge treatment, plasma treatment, glow discharge treatment, reverse sputter treatment, flame treatment, chromic acid treatment, solvent treatment, and surface roughening treatment.
• the surface By forming an inorganic layer and a barrier resin coating layer on the treated surface, the adhesion can be improved.
• An undercoat layer may be formed on the surface of the base film layer instead of or together with the surface treatment.
• the undercoat layer is composed of various resins, for example, a thermoplastic resin, a thermosetting resin, a light-curable resin (an electron-curable resin, an ultraviolet-curable resin, etc.), or a cupping. Can be.
• Specific examples of the components of the undercoat layer include, for example, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polycarbonate, nitrocellulose, and cellulose acetate.
• Thermoplastic resins such as cellulose-based polymers such as styrene, and rosin-modified maleic acid resins; urethane-based resins, urea-based resins, melamine-based resins, and urea-melamine-based resins; Thermosetting resins such as epoxy resins, alkyd resins, and amino alkyd resins; epoxy (meta) acrylate, urethane (meta) acrylate, and polyester ( (Meta) Photocurable resins such as acrylic acid; silane coupling agents; One or more of these can be used.
• the undercoat layer may contain a colorant such as a general-purpose dye or pigment.
• the content of the coloring agent is appropriately selected within a range not to impair the transparency of the film, and is usually about 1 to 30% by weight based on the resin constituting the undercoat layer.
• the thickness of the undercoat layer is not particularly limited, and is usually 0.
• the method of forming the undercoat layer is not particularly limited, and the organic or aqueous coating agent containing the components of the undercoat layer may be roll-coated, gravure-coated.
• a stage using a photocurable resin may be irradiated with an actinic ray.
• a main feature of the present invention is that a base material film is formed by combining a transparent inorganic layer (2) and a barrier resin coating layer (3). (1) is to cover the surface in a specific order. With this composite configuration, it is possible to suppress a decrease in transparency and gas barrier property under the action of a mechanical external force or at a high temperature, and to have high flexibility and excellent gas barrier even when the coating layer is thin. A film having properties can be obtained.
• the film having the above-described structure has higher performance than the film in which the barrier resin coating layer and the inorganic layer are formed on the base film layer in a different coating order. Show. This is considered for the base film layer as follows.
• the film of the present invention has a high affinity between the transparent inorganic layer (2) and the barrier resin coating layer (3). Therefore, even if the inorganic layer is a single layer and the coating layer is extremely thin, high gas barrier properties are obtained and transparency is excellent. In addition, there is no occurrence of peeling or defects that lower the flexibility or decrease the gas barrier property due to external force. Further, by combining the barrier resin coating layer and the inorganic layer, it is possible to suppress a decrease in transparency and gas barrier property even at a high temperature.
• the combination of the inorganic layer and the barrier resin coating layer allows it to be exposed to high temperatures due to retort treatment, electromagnetic wave heating, etc., for example, oxygen transmission rate of 1 cc / m 2 ⁇ 2
• High gas barrier properties of 4 hr or less preferably 0.5 ccm 2 ⁇ 24 hr or less
• water vapor permeability of 1.0 OgZm 2 ⁇ 24 hr or less can be maintained.
• the barrier resin coating layer can be easily formed by a simple operation of applying a coating solution.
• the loss of microwaves and microwaves during heating of an electromagnetic wave such as an electron range is small, and whitening does not occur even at high temperatures such as retorting.
• the film of the present invention can suppress the gas barrier property from being reduced even when a mechanical external force such as bending or kneading acts, for example, when processing or using the film, High gas barrier properties can be demonstrated even at high temperatures, and excellent gas barrier properties can be maintained over a long period of time.
• a transparent thin film can be formed. It is not particularly limited as long as it is an inorganic substance that can be used.
• an inorganic substance that can be used.
• Preferred inorganic substances include, for example, Periodic Table 2 Group elements such as magnesium, calcium, and barium; Periodic Table transition elements such as titanium, zirconium, tantalum, and ruthenium; Periodic Table 2B elements such as zinc A periodic table 3B element such as aluminum, indium, and thallium; a periodic table 4B element such as silicon and tin; a periodic group 6B element such as selenium, or Oxides containing these are included.
• the inorganic layer is formed by a simple substance of a Group 3B element or a Group 4B element of the periodic table or an oxide thereof.
• oxides containing the above elements have excellent transparency and gas barrier properties.
• the gay oxide can form a dense thin film, has a high affinity with the polymer constituting the barrier resin coating layer, and acts with mechanical external force.
• the silicon oxide includes not only silicon monoxide and silicon dioxide but also a gay oxide represented by a composition formula Siox (where 0 and x2).
• inorganic compounds having low conductivity for example, non-conductive inorganic substances such as oxides, halides, carbides, and nitrides can be used in the packaging material for electromagnetic wave heating.
• non-conductive inorganics include oxides, for example, gay oxide.
• the thickness of the inorganic layer is usually 1 ⁇ 0 to 500 ⁇ , Ngstrom (0.01 to 0.5 ⁇ m), preferably 200 to 3000 ⁇ ⁇ stroms (0. It can be selected from the range of about 2 to 0.3 ⁇ m), and more preferably about 300 to 1500 ⁇ ⁇ ngstrom (0.03 to 0.15 1m). If the thickness is less than 100 ⁇ , sufficient gas barrier properties cannot be obtained, and even if the thickness exceeds 5,000 ⁇ , the barrier properties will not be significantly improved, which is economically disadvantageous.
• the barrier resin coating layer is formed of a resin having a high gas barrier property as described above, for example, a vinylidene chloride copolymer, an ethylene-vinyl alcohol copolymer, a polyamide polymer, and a resin. Includes vinyl alcohol-based polymers, polyacrylonitrile-based polymers, and urethane-based superstructures.
• the barrier resin of the gas barrier resin coating layer does not include a resin that does not exhibit the gas barrier characteristics, for example, a general urethane polymer. These barrier resins can be used alone or in combination of two or more.
• Preferred barrier resins include, for example, vinylidene chloride-based copolymers and ethylene-vinyl alcohol copolymerized copolymers.
• the vinylidene chloride copolymer is a copolymer of vinylidene chloride and another polymerizable monomer.
• Examples of such a copolymerizable monomer include vinyl chloride, vinyl acetate, and Acid, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, isopropynoleate, butyl acrylate, isobutyl acrylate, tert —
• Various types of acrylates such as butyl acrylate, pentyl acrylate, hexyl acrylate, acrylonitrile, methacrylonitrile, and methacrylate Examples include lylic acid and methyl acrylate corresponding to the above acrylate.
• vinylidene chloride-based copolymers vinylidene chloride-acrylonitrile copolymers, vinylidene chloride-methacrylic acid copolymer, vinylidene chloride- Accelerate rate And vinylidene chloride-methacrylate mixture, and vinylidene chloride-vinyl acetate copolymer.
• the vinylidene chloride content in the dendritic co-base is usually 85 to 99% by weight, preferably about 90 to 97% by weight.
• the vinylidene copolymer has a high content of vinylidene chloride, so that it can maintain high transparency and gas barrier properties even after heat treatment.
• the ethylene-vinyl alcohol copolymer a solvent-soluble ethylene-vinyl alcohol copolymer is preferred.
• the ethylene content is usually from 5 to 50 mol%, preferably from 10 to 45 mol%, more preferably from 25 to 50 mol%. It is about to 3 5 mol%, the molecular weight, e.g., 1 X 1 0 4 ⁇ : 1 0 X 1 0 4, preferred and rather is 2 X 1 0 4 ⁇ 7 x 1 0 4, preferred and rather is 4 X 1 ⁇ 4-5 1 0 4 about.
• the degree of genification is 99.5% or more.
• Such a solvent-soluble ethylene-vinyl alcohol copolymer is soluble in water or a mixed solvent of water and alcohol, and can form a thin film by coating.
• the barrier resin coating layer is preferably made of the barrier resin (preferably a vinylidene chloride-based copolymer and ethylene-vinyl alcohol). At least one resin may be contained, or a plurality of resins may be contained. In addition, the barrier resin coating layer may be composed of a plurality of layers containing barrier resin. For example, the barrier resin coating layer may be composed of a plurality of layers including a layer containing a vinylidene chloride-based copolymer and a layer containing an ethylene-vinyl alcohol copolymer. The content of the barrier resin in the barrier resin coating layer is 50% by weight or more, preferably 75 to 100% by weight, and more preferably 90 to 10% by weight. It is about 0% by weight.
• the thickness of the barrier resin coating layer can be appropriately selected within a range that does not impair the properties of the film, and is, for example, 0.05 to 0.5 rri, preferably. Is about 0.1 to 10 m (for example, 0.2 to 7 m), and more preferably about 0.25 to 5 m (for example, 0.3 to 3 m). If the thickness of the coating layer is less than 0.05 m, it is difficult to impart high gas barrier properties, and if it exceeds 15 m, the gas barrier properties are not significantly improved, which is economically disadvantageous. In addition, the loss of micro-waves during electromagnetic heating tends to increase.
• the thickness of the inorganic layer (2) and the thickness of the barrier resin coating layer (3) can be set as appropriate; force; ', the ratio of the thickness affects gas barrier properties. .
• the ratio n 2 / n 1 of the thickness n 2 (m) of the barrier resin coating layer to the thickness n 1 ( ⁇ m) of the inorganic layer is For example, 0.1 to 150, preferably 0.5 to 5,000 (for example, about 1 to 200), and more preferably 1 to about L: 100. And about 2 to 50 (for example, about 5 to 50) in many cases.
• the thickness is out of the above range, it is difficult to provide high gas barrier properties. If the ratio is less than 0.1, defects are likely to occur in the inorganic layer due to external force, and the value exceeds 150. However, it is not economical because gas barrier properties are not improved much.
• the surface of the barrier resin coating layer may be subjected to a conventional surface treatment as exemplified in the base film layer.
• the barrier resin coating layer (3) may be covered with a heat seal layer (4).
• the heat seal layer (4) may be formed on the other surface of the base film layer (1).
• at least one surface of the base film (1) may be covered with at least the inorganic layer (2) and the barrier resin coating layer (3).
• the polymer constituting the heat seal layer includes a thermo-bonding polymer such as an olefin polymer, a vinyl acetate-vinyl chloride copolymer, a polymer, a polyamide, and the like.
• a thermo-bonding polymer such as an olefin polymer, a vinyl acetate-vinyl chloride copolymer, a polymer, a polyamide, and the like.
• examples include rubber polymers. This These polymers can be used alone or in combination of two or more.
• the heat-bonding olefin-based polymer include polyethylene, ethylene such as .. density polyethylene, and linear low-density polyethylene.
• Butene-1 copolymer ethylene-one (4—methylpentene-1) copolymer, ethylene-hexene-1 copolymer, ethylene-vinyl acetate copolymer, Ethylene- (meth) acrylic acid copolymer, Ethylene- (meth) acrylic acid copolymer, ionomer, polypropylene, propylene-butene 1 Copolymer, ethylene-propylene copolymer copolymer, ethylene-propylene-butene-11 copolymer, ethylene-propylene-gene copolymer copolymer, anhydrous maleic anhydride Modified polyolefins such as acid-modified polyethylene and maleic anhydride-modified polypropylene .
• Preferred oligomers include ethylene vinyl acetate copolymers, ethylene monoethyl acrylate copolymers, and amorphous polyolefins (e.g., amorphous polymers). Propylene).
• a preferable heat bonding film includes a non-stretched polypropylene film.
• the thermobonding polyester includes a polyester containing either an aliphatic diol or an aliphatic dicarboxylic acid as a constituent unit, particularly, an aliphatic diol and an aliphatic dicarboxylic acid.
• Aliphatic polyesters. Preferred heat-bonding polyesters often include units of saturated aliphatic carboxylic acids.
• Aliphatic diol components include, for example, ethylene glycol, diethyl glycol, triethylene glycol, propylene glycol, dipropylene glycol.
• aliphatic dicarboxylic acid component examples include unsaturated aliphatic dicarboxylic acids such as maleic acid and fumaric acid, succinic anhydride, adipic acid, azelic acid, and sebacic acid. Saturated aliphatic dicarboxylic acids such as siberic acid and dodecanoic acid And the like.
• thermal bonding polyimide examples include Nylon 6, Nylon 11, Nylon 12, Nylon 13, Nylon 6 10, and Nylon 6 1 2 And Nylon 616, and copolymerized Nylon (for example, Nylon 612 and the like) obtained by mixing these Nylon raw materials.
• Preferred polyamides include Nylon 11, Nylon 12, Nylon 6 Z 12, and the like.
• Rubber-based polymers include, for example, butyl rubber, isobutylene rubber, chloroprene rubber, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, and styrene copolymer. Includes chlorotrinolevene-gen copolymer.
• Preferred polymers for the heat seal layer include, for example, an olefin polymer, a vinyl acetate-vinyl chloride copolymer, a polyester, and a polyamide.
• the thickness of the heat seal layer can be appropriately selected, for example, in the range of about 3 to 100 m according to the use of the packaging material, etc., and the heat seal layer is formed by laminating the film. In such a case, for example, it is about 20 to 100 fi m., Preferably about 30 to 80 111.
• the heat seal layer is formed on a predetermined portion of the surface of the barrier resin coating layer, for example, on a portion provided for a heat seal.
• the heat seal layer is formed on the entire surface of the barrier resin coating layer.
• the heat seal layer may be formed on the heat seal portion on the other surface of the base film layer or on the entire surface.
• the base film layer may be formed of various additives, for example, stabilizers such as antioxidants, ultraviolet absorbers, and heat stabilizers; cation-based, anion-based, nonionic-based, amphoteric antistatic agents, and the like.
• Nucleating agent such as antioxidants, ultraviolet absorbers, and heat stabilizers
• Plastics fillers; synthesis of higher fatty acid amides, higher fatty acids and their salts, higher fatty acid esters, minerals, plant-based natural plastics, etc., polystyrene, etc.
• inorganic lubricants such as silica-based fine powder and alumina-based fine powder, and organic lubricants such as polyethylene-based fine powder and acryl-based fine powder Powdered lubricant of the formula (I);
• the barrier resin coating layer may be formed of another polymer, for example, an olefin-based polymer such as an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer; Acryl-based polymer; Styrene-based polymer; Polyester; Polyacetal; Polyvinyl acetate; Polyvinyl chloride; Vinyl chloride-g-vinyl acid copolymer; Polyamide; ⁇ It may contain resin-based polymer; acrylonitrile-based superstructure; polycarbonate; chlorinated polyolefin; cellulose-based polymer.
• an olefin-based polymer such as an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer
• Acryl-based polymer such as an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer
• Acryl-based polymer such as an ethylene-viny
• the barrier resin coating layer and the heat seal layer may contain the above-mentioned additives as necessary.
• the barrier resin coating layer may contain an anti-blocking agent; It may contain adhesiveness improvement such as litho silicate.
• the barrier film of the present invention is obtained by sequentially covering at least one side of the base film with a transparent inorganic layer and a barrier resin coating layer. be able to.
• At least one side of the base film is formed of a transparent inorganic layer, a barrier resin coating layer, and a heat seal.
• Layer, or one side of the base film is sequentially coated with a transparent inorganic layer and a barrier resin coating layer, and the other side of the base film is coated. It can be obtained by a method of coating with a heat seal layer.
• the inorganic layer may be formed by a conventional method, for example, a physical method (vacuum deposition, reactive deposition, sputtering, reactive sputtering, ionization, etc.).
• the surface of a substrate film is coated with the above-mentioned inorganic material by a plating method, a reactive ion plating method, etc., and a chemical method (CVD method, plasma CVD method, laser-CD method, etc.).
• CVD method plasma CVD method, laser-CD method, etc.
• the inorganic layer is often formed by a physical method such as vapor deposition, and the inorganic layer can be formed on one side or both sides of the base film layer.
• the barrier resin coating layer can be formed by applying a coating solution containing a barrier resin to the surface of the inorganic layer.
• the coating liquid can be prepared by selecting an appropriate solvent according to the type of the barrier resin, and may be in the form of either a solution or a dispersion.
• the solvent for the solution coating solution containing the vinylidene chloride-based copolymer can be appropriately selected according to the type of the vinylidene chloride-based copolymer, and examples thereof include acetate, methylethylketone, and cyclohexane.
• Ketones such as hexanone; ethers such as dioxane, getyl ether, and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene; ethyl acetate and butyl nitrate; Esters; amides such as dimethylformamide; mixed solvents of these.
• the dispersion is usually commercially available in the form of a 0 / W emulsion.
• the coating solution containing the ethylene vinyl alcohol copolymer can be usually prepared using a mixed solvent of water and alcohol.
• alcohols include methanol, ethanol, propanol, and isoprono. Examples include nor-hexanol.
• the coating liquid may contain the above-mentioned various additives, and may contain conventional additives such as an antifoaming agent and a viscosity adjusting agent in order to enhance the coating property.
• the coating method is not particularly limited, and a conventional method such as an air knife coating method, a roll coating method, a gravure coating method, a blade coating method, a dip coating method, and a spraying method can be employed.
• a barrier resin coating layer can be formed.
• the heat seal layer can be formed by a conventional method, for example, a dry laminating method, an extruding laminating method, a netting method, a coating method, or the like, depending on the type of the heat-bonding polymer.
• the gas barrier film of the present invention may have various types of coating layers and laminating layers, such as a lubricating layer and an antistatic layer, depending on the type and application of the film.
• a decorative printing film layer, a reinforcing layer of a nylon film or the like may be formed.
• the surface of the base film layer is sequentially coated with an inorganic layer having transparency and a barrier resin coating layer having high gas barrier properties. It has excellent transparency and high gas barrier properties even when the coating layer is thin. Further, even when a mechanical external force such as massaging acts, or even at a high temperature, a decrease in transparency and gas barrier properties can be suppressed, and excellent gas barrier properties can be exhibited over a long period of time.
• the bag can be easily formed using the heat seal layer, and the contents can be stored for a long time due to the high gas barrier property. Further, the loss of micro-waves during heating of electromagnetic waves is small, and foods and the like to be subjected to electromagnetic wave heating and retort treatment can be packaged while suppressing quality deterioration and deterioration.
• the gas barrier film of the present invention exhibits high gas barrier properties as described above even when exposed to high temperatures, and is characterized by high transparency.
• packaging materials include microwave foods, retort foods, and frozen foods. Microphones Mouth-wave sterilization, flavor barriers, pharmaceuticals, precision electronic components and other packaging materials, and balloons and balloons It can be suitably used as a forming material for use.
• packaging of foods and the like allows the contents to be stored for a long period of time while suppressing deterioration and deterioration.
• a package bag of a solid material such as hamburger, syumai, guilloza, etc. It can be used as a packaging bag for liquids such as curry, soup, coffee, and tea.
• the packaging bags containing these foods can be retorted or microwaved as they are.
• the contents When used as an inner bag of a paper container such as a sake pack, the contents can be heated by microwave heating or the like, for example, so-called canning can be performed.
• Packaging forms of the packaging material of the present invention include bags, cups, tubes, standing backs, trays and other containers, lids, sake, soy sauce, mirin, oil, milk, juice, etc. The strength of the inner material of the paper pack, etc .; Example
• one surface of a biaxially stretched polyethylene film of thickness 1 2 2 ⁇ 1 is used as an evaporation source.
• a 100-.ANG.-thick GaAs oxide vapor-deposited layer was formed as an inorganic layer by a vacuum vapor deposition method to obtain a multi-layer film.
• a vinylidene chloride copolymer manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Saran Resin F216
• mixed solvent of toluene and hydrofuran 12 (weight ratio)
• a coating solution for a barrier resin coating layer having a resin concentration of 15% by weight was prepared.
• This coating solution was applied to a vapor-deposited surface of the gay oxide vapor-deposited film obtained in Comparative Example 1 by using a bar coater after drying with a thickness of 0.5 m (Example 1) and a thickness of 2.5 mm. m (Example 2), and then dried in an oven at 105 ° C. for 30 seconds to form a barrier resin coating layer, thereby obtaining a composite film.
• This coating solution was applied to the vapor-deposited surface of the GaAs oxide vapor-deposited film obtained in Comparative Example 1 using a barco all-over-one so as to have a thickness of 4.0 m after drying. After drying in an oven at 115 ° C for 1 minute, a barrier resin coating layer was formed to obtain a composite film.
• a barrier resin coating layer having a thickness of 0.5 ⁇ m (Comparative Example 2) or a thickness of 2.5 urn (Comparative Example 3) was directly formed on a polyethylene latex film. Except for the formation, a composite film was obtained in the same manner as in Examples 1 and 2.
• Example 5 a coating solution containing a vinylidene chloride-based copolymer, a common urethane-based resin solution [Takeda Pharmaceutical Co., Ltd., trade name: Yu-Kerak A 6 15] was used to prepare an inorganic material.
• a composite film was obtained in the same manner as in Example 1, except that a coating layer having a thickness of 5.0 m was formed on the surface of the layer. Comparative Example 5
• a urethane-based adhesive [Toyo Morton Co., Ltd., trade name ADC ⁇ TE33E] is applied to the surface of the inorganic layer after drying.
• Example 2 except that an unstretched ethylene-propylene copolymer film having a thickness of 30 m was laminated by a dry lamination method using a dry laminating method. Similarly, a film was obtained.
• a vinyl chloride-vinyl acetate copolymer solution [Denka 100 C, manufactured by Denki Kagaku Kogyo Co., Ltd.] was used on the surface of the inorganic layer. 2 thick The composite film was reduced in size in the same manner as in Example 2 except that the coating layer was formed.
• Example 2 Using the barrier coating solution of Example 2 on the negative side of the 12 mm thick polystyrene polyethylene terephthalate, the thickness was 2 mm. A coating layer was formed. Next, a silicon oxide deposited layer was formed on the surface of the coating layer in the same manner as in Comparative Example 1 to obtain a composite film.
• the measurement was carried out by the same pressure method (measuring instrument: OXTRAN TV IN, Morcon) at 20 and a relative humidity of 65%.
• the unit is cc Zm 2 * 24 hr £ water vapor permeability:
• the unit is g / m 2 ⁇ 24 hr.
• the film was rubbed once by hand, and the oxygen gas permeability and water vapor permeability before and after that were measured, and the change in gas barrier properties due to the action of mechanical external force was evaluated.
• Table 1 shows the results. In the film of Example 3, the oxygen permeability before hand massage was below the measurement limit.
• the films of Comparative Examples 1 to 7 have insufficient gas barrier properties, and the films of Comparative Examples 1, 6, and 7 have gas barrier properties by hand massage. Is remarkably reduced.
• the films of Examples 1 to 3 not only have extremely high gas barrier properties, but also can maintain excellent gas barrier properties even when a mechanical external force such as hand massage acts.
• the combination of the inorganic layer and the barrier resin coating layer shows extremely high gas barrier properties even when the thickness of the coating layer is small. .
• Vinylidene chloride-based copolymer manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Saran Resin F2 16
• Saran Resin F2 16 Vinylidene chloride-based copolymer
• the resin was dissolved so that the resin concentration became 15% by weight to prepare a coating solution for a barrier resin coating layer.
• This coating solution was applied to the above-mentioned deposition surface so as to have a thickness of 1 m after drying, and then dried to form a barrier resin coating layer.
• a 3 m-thick polyester-based adhesive is applied to the surface of the barrier resin coating layer, dried at 80 ° C for 2 seconds, and then dried at 2 kg / cm ”. Under pressure, at 100 ° C. for 1 second, a non-stretched polypropylene film having a thickness of 40 ⁇ m was dry laminated to prepare a packaging film.
• a coating solution for a barrier resin coating layer having a resin concentration of 12% by weight was prepared
• the above-mentioned coating solution containing an ethylene-vinyl alcohol copolymer was used.
• a packaging film was produced in the same manner as in Example 4.
• a biaxially stretched nylon film having a thickness of 20 im was used as a base film, and one surface of this film was formed with 5 ⁇ 10 to A film for packaging was produced in the same manner as in Example 4 except that a silicon oxide vapor-deposited layer having a thickness of 600 angstroms was formed by a vacuum vapor deposition method under a vacuum of 5 Torr.
• Example 7
• Example 8 Except for applying the barrier resin coating layer coating solution to a thickness of 0.5 im after drying, on the surface to be oxidized with a gay oxide formed in the same manner as in Example 4. A packaging film was produced in the same manner as in Example 4 ( Example 8).
• a two-part urethane-based adhesive was applied to a thickness of 2 m on the surface of the barrier resin coating layer formed on one surface of the base film in the same manner as in Example 4, and applied to the substrate. After drying at 10 ° C for 10 seconds, the procedure was performed except that a 50 m thick linear low-density polyethylene film was dried under a pressure of 2.5 kg / cm2. In the same manner as in Example 4, a packaging film was produced.
• the non-stretched polypropylene having a thickness of 40 ⁇ m was formed on the surface of the inorganic layer by a polyester-based adhesive in the same manner as in Example 4. The film was dried and laminated to produce a packaging film.
• a coating solution containing the vinylidene chloride copolymer of Example 4 was applied to a 12-nm thick polyethylene terephthalate film without forming a gay oxide deposition layer. After forming a barrier resin coating layer having a thickness of 5 m after drying, a 40 m-thick non-stretched film was formed with a polyester-based adhesive in the same manner as in Example 4. The polypropylene film was dry-laminated to produce a packaging film.
• the unstretched polypropylene pipe with a thickness of 4 ⁇ ⁇ m was formed with a polyester-based adhesive in the same manner as in Example 4.
• the film was dried and dried to make a packaging film.
• the obtained packaging film was examined for gas barrier properties, transparency and electronic range suitability as follows. .
• Oxygen gas permeability was measured according to the M0C0N method, and water vapor permeability was measured according to JIS-Z-0208.
• Transparency Visually evaluated before and after retorting for 130 and 20 minutes.
• Microwave oven suitability The packaging films of Examples 4 and 5 and Comparative Examples 8 to 10 are packed in bags, and each bag is filled with 200 g of spaghetti ffl mint sauce and used in a household microwave oven. Heated. The time required for microwave oven heating was about 95 seconds for the film of Comparative Example 9, whereas it was about 75 seconds for the films of Examples 4, 5 and Comparative Example 8. In the film of Comparative Example 10, the conductive aluminum foil sparked, and could not be heated by an electron range.
• microwave oven suitability was comprehensively evaluated according to the following criteria.
• the film of the example has higher transparency and gas barrier properties than the film of the comparative example, and these properties are not significantly reduced by heating. Therefore, the example film has excellent overall suitability for retorting and microwave heating.
• Table 2 Example 4
• Example 5 Example 6 ⁇
• Example 7 Example 8 Comparative example 8 Comparative example Q Comparative example 1 ⁇ Thickness of resin coating layer 1 1 1 0.5 1 1 5 —-

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• 1994
  • 1994-09-14 TW TW083108463A patent/TW264494B/zh active
  • 1994-09-16 WO PCT/JP1994/001525 patent/WO1995007815A1/ja not_active Ceased

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