WO2017217546A1 - Procédé de fabrication d'une feuille multicouche, procédé de fabrication d'un récipient moulé et feuille multicouche - Google Patents

Procédé de fabrication d'une feuille multicouche, procédé de fabrication d'un récipient moulé et feuille multicouche Download PDF

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Publication number
WO2017217546A1
WO2017217546A1 PCT/JP2017/022396 JP2017022396W WO2017217546A1 WO 2017217546 A1 WO2017217546 A1 WO 2017217546A1 JP 2017022396 W JP2017022396 W JP 2017022396W WO 2017217546 A1 WO2017217546 A1 WO 2017217546A1
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Prior art keywords
resin composition
multilayer sheet
layer
adhesive resin
polyolefin
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PCT/JP2017/022396
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English (en)
Japanese (ja)
Inventor
茂樹 工藤
実 川▲崎▼
茂実 杉山
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凸版印刷株式会社
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Priority to JP2018524051A priority Critical patent/JP6954281B2/ja
Publication of WO2017217546A1 publication Critical patent/WO2017217546A1/fr

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    • 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
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
    • B65D85/72—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for edible or potable liquids, semiliquids, or plastic or pasty materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material

Definitions

  • the present invention relates to a method for producing a multilayer sheet, a method for producing a molded container, and a multilayer sheet, and particularly relates to a method for producing a multilayer sheet used for boil and retort applications, a method for producing a molded container, and a multilayer sheet.
  • Patent Document 1 proposes a thermoplastic barrier film in which a layer made of a mixture of a polycarboxylic acid polymer and a plasticizer and a layer made of a mixture of a divalent metal compound and a resin are laminated. According to the packaging container provided with the thermoplastic barrier film described in Patent Document 1, since the thermoplastic barrier film exhibits a barrier property by the hot water treatment, a retort shock seen in EVOH resin or the like does not occur.
  • Patent Document 1 a thermoplastic barrier film and a sheet made of a thermoplastic resin are produced separately, and after both are produced, the thermoplastic barrier film and the sheet are dry laminated through an adhesive to produce a multilayer sheet. is doing.
  • the multi-layer sheet described in Patent Document 1 has a problem that it takes time to manufacture and the productivity is low.
  • when dry lamination is performed there are restrictions on manufacturing conditions, and for example, it is difficult to process a sheet having a thickness of 1 mm or more (a limited processing machine is available), and thus a multilayer sheet having a predetermined thickness or more is manufactured. There is also a problem that it is difficult.
  • a squeeze container as one of the packaging containers using such a multilayer sheet.
  • a seasoning such as mayonnaise or mustard
  • a liquid food container such as pet food or baby food.
  • the present invention provides a method for producing a multilayer sheet, a method for producing a molded container, and a multilayer sheet, which can increase productivity more than before and can flexibly cope with many different product specifications.
  • the squeeze can be easily squeezed out, and the high barrier property that does not depend on the thickness of the container and does not cause deterioration of the barrier property due to the heat sterilization treatment. It aims at providing the squeeze container which has the property.
  • the present invention as one aspect thereof, relates to a method for producing a multilayer sheet.
  • a base material containing a thermoplastic resin, a first barrier layer containing a polycarboxylic acid polymer and a plasticizer, and a second barrier layer containing a polyvalent metal compound and a resin are laminated.
  • a method for producing a multilayer sheet having a thermoplastic barrier film the step of preparing a thermoplastic barrier film, the step of preparing a polyolefin resin composition and an adhesive resin composition, and supplying a thermoplastic barrier film And extruding the polyolefin resin composition and the adhesive resin composition from an extruder so that the adhesive resin composition is located between the layer formed of the polyolefin resin composition and the supplied thermoplastic barrier film.
  • the thermoplastic barrier film is adhered to a layer formed of the polyolefin resin composition serving as a sheet base material with the adhesive resin composition, and therefore, in the step of extruding, the thermoplastic barrier film is used.
  • the polyolefin resin composition and the adhesive resin composition are extruded from an extruder so that the adhesive resin composition is positioned between the layer formed by the polyolefin resin composition and the thermoplastic barrier film. I am doing so.
  • the polyolefin resin composition and the thermoplastic barrier film are also bonded together by thermal lamination.
  • the manufacturing time can be shortened and the productivity of the multilayer sheet can be increased.
  • the line speed when a thermoplastic barrier film and a 0.6 mm thick polypropylene sheet are bonded by dry lamination is 30 m / min, when producing 100,000 m per month, at least about 60 by only dry lamination processing. It takes time.
  • such a dry lamination process can be omitted, so that the time can be significantly reduced and the productivity of the multilayer sheet can be greatly increased.
  • a thermal laminate is used, so that it is possible to easily produce a polyolefin layer having a thickness of 1 mm or more, compared with a production method using a dry laminate. Therefore, it can flexibly respond to many different product specifications.
  • the adhesive resin composition preferably contains an acid-modified polyolefin.
  • the functional group imparted to the polyolefin is bonded by a hydrogen bond with the metal oxide contained in the surface layer of the thermoplastic barrier film, the thermoplastic barrier film and the layer made of the polyolefin resin composition serving as the sheet base material It becomes possible to increase the adhesive strength.
  • the adhesive resin composition used here preferably includes a graft-modified polyolefin obtained by graft-modifying or copolymerizing at least one polymerizable ethylenically unsaturated carboxylic acid or derivative thereof with a polyolefin resin before modification. .
  • the adhesive resin composition may have a melt flow rate (MFR) of 3 g / 10 min or more.
  • MFR melt flow rate
  • the adhesive resin composition preferably contains an acid-modified polypropylene resin or acid-modified polyethylene resin and a resin modifier made of an ⁇ -olefin copolymer.
  • flexibility can be imparted while maintaining a melting point that can withstand retort treatment and the like.
  • the adhesive resin composition in the step of extruding, may be extruded so that the thickness of the adhesive resin composition is 1 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the adhesive resin composition is 1 ⁇ m or more, peeling between the thermoplastic barrier film and the layer formed by the polyolefin resin composition can be suppressed, while the thickness of the adhesive resin composition is 50 ⁇ m or less. Thereby, the usage-amount of an expensive adhesive resin composition can be reduced, maintaining the adhesive force required.
  • the extruder is a multilayer extruder, and in the extruding step, the adhesive resin composition overlaps the surface on the thermoplastic barrier film side of the layer formed by the polyolefin resin composition. It is preferable to co-extrude the polyolefin resin composition and the adhesive resin composition from a multilayer extruder.
  • the adhesive resin composition is first extruded using a single layer extruder, and then the polyolefin resin composition is extruded to form the adhesive resin composition with the polyolefin resin composition.
  • the polyolefin resin composition and the adhesive resin composition may be extruded from an extruder so as to be positioned between the layer and the thermoplastic barrier film.
  • the polyolefin resin composition in the extruding step, may be extruded so that the layer made of the polyolefin resin composition has a thickness of 1 mm or more.
  • the layer portion formed by the polyolefin resin composition requires a thickness of 1 mm or more, but in dry lamination, it is difficult to process a sheet of 1 mm or more.
  • even a layer formed of a polyolefin resin composition having a thickness of 1 mm or more can be easily produced, so that a compatible product group can be widened.
  • the present invention relates to a method for manufacturing a molded container as another aspect.
  • This method for producing a molded container includes a step of producing a multilayer sheet by any one of the above-described methods for producing a multilayer sheet, and a step of producing a molded container by stretching the multilayer sheet. In this case as well, it is possible to achieve the same effects as the above-described multilayer sheet manufacturing method.
  • the present invention also relates to a multilayer sheet as another aspect.
  • This multilayer sheet is a multilayer sheet including a polyolefin resin layer and a thermoplastic barrier film attached to one surface of the polyolefin resin layer with an adhesive resin layer.
  • the thermoplastic barrier film includes a base material containing a thermoplastic resin, a first barrier layer containing a polycarboxylic acid polymer and a plasticizer, and a second barrier layer containing a polyvalent metal compound and a resin.
  • the thermoplastic barrier film is attached to one surface of the polyolefin resin layer with an adhesive resin layer, and the adhesive resin layer contains acid-modified polyolefin.
  • thermoplastic barrier film is a film in which a first barrier layer containing a polycarboxylic acid polymer and a plasticizer and a second barrier layer containing a polyvalent metal compound and a resin are laminated, heat and moisture resistance characteristics It can be set as the multilayer sheet excellent in.
  • the polyolefin resin layer and the thermoplastic barrier film are bonded together by the adhesive resin layer without using an adhesive, it is possible to produce a multilayer sheet without using an organic solvent generally contained in the adhesive, It can suppress that the odor of the remaining organic solvent transfers to the content arrange
  • FIG. 1 It is sectional drawing which shows the multilayer sheet which concerns on one Embodiment of this invention. It is a figure which shows typically the process for manufacturing the multilayer sheet
  • FIG. 1 is a cross-sectional view showing a multilayer sheet according to an embodiment of the present invention.
  • the multilayer sheet 10 includes a substrate 1, a barrier layer 2 provided on one surface of the substrate 1, and a polyolefin layer 3 provided on one surface of the barrier layer 2.
  • the barrier layer 2 and the polyolefin layer 3 are adhered to each other by an adhesive resin layer 4 made of an adhesive resin composition.
  • the barrier layer 2 includes a first barrier layer 5 containing a polycarboxylic acid polymer and a plasticizer, and a second barrier layer 6 containing a polyvalent metal compound and a resin.
  • a thermoplastic barrier film 7 is constituted by the base material 1 and the barrier layer 2 composed of the first barrier layer 5 and the second barrier layer 6.
  • the polyolefin layer 3 side (the upper side in the figure) of the multilayer sheet 10 is the side in contact with the package contents
  • the base material 1 side (the lower side) of the multilayer sheet 10 is the outer side of the container. It becomes.
  • the base material 1 is a base material of the thermoplastic barrier film 7 and includes a thermoplastic resin.
  • the type of the thermoplastic resin constituting the substrate 1 is not particularly limited.
  • polyolefin polymers such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, poly-4-methylpentene, and cyclic polyolefin are used.
  • thermoplastic resin which comprises the base material 1 a polyethylene terephthalate, a polypropylene, a polyamide-type polymer, a polystyrene, etc. are preferable from a viewpoint of stretch moldability.
  • the substrate 1 may be stretched or unstretched.
  • the thickness of the substrate 1 is, for example, 10 ⁇ m or more and 10 mm or less, and preferably 10 ⁇ m or more and 500 ⁇ m or less.
  • the substrate 1 may be composed of a plurality of layers.
  • the first barrier layer 5 is one of the layers constituting the barrier layer 2 and includes a polycarboxylic acid polymer and a plasticizer.
  • the polycarboxylic acid-based polymer generates a polyvalent metal compound and a salt contained in the second barrier layer 6 and exhibits a stable gas barrier property.
  • the plasticizer can be added in order to improve the stretchability of the polycarboxylic acid compound. Specifically, by replacing a part of the polycarboxylic acid polymer with a plasticizer, the glass transition temperature of the entire solid content can be lowered and the multilayer sheet 10 can be stretched under a lower temperature condition.
  • the polycarboxylic acid polymer is not particularly limited as long as it is an existing polycarboxylic acid polymer.
  • the existing polycarboxylic acid polymer is a general term for polymers having two or more carboxy groups in the molecule. Specifically, a homopolymer using ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid as the polymerizable monomer, and only ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid as the monomer component, At least two kinds of these copolymers, copolymers of ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid and other ethylenically unsaturated monomers, and intramolecular such as alginic acid, carboxymethylcellulose, pectin, etc. Examples thereof include acidic polysaccharides having a carboxy group.
  • These polycarboxylic acid polymers can be used alone or as a mixture of at least two kinds of polycarboxy
  • ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.
  • ethylenically unsaturated monomer copolymerizable with these include saturated carboxylic acid vinyl esters such as ethylene, propylene, and vinyl acetate, alkyl acrylate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, Styrene and the like are representative.
  • the polycarboxylic acid polymer is a copolymer of an ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid and a saturated carboxylic acid vinyl ester such as vinyl acetate, a saturated vinyl The ester moiety can be converted to vinyl alcohol for use.
  • the polycarboxylic acid polymer is a copolymer of an ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid and another ethylenically unsaturated monomer, and the multilayer sheet 10 is molded for retort.
  • the copolymer composition is such that the ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid monomer composition is 60 mol% or more.
  • the polycarboxylic acid polymer is an ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid.
  • a polymer composed only of an acid is preferred.
  • preferred specific examples thereof are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumar Examples thereof include polymers obtained by polymerization of at least one polymer monomer selected from the group consisting of acid and crotonic acid, and mixtures thereof.
  • a homopolymer, a copolymer, and / or a mixture thereof comprising at least one polymerizable monomer selected from acrylic acid, methacrylic acid, and maleic acid can be used.
  • polyacrylic acid, polymethacrylic acid, polymaleic acid, and mixtures thereof can be used.
  • the polycarboxylic acid polymer is, for example, an acidic polysaccharide other than the polymer of the ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid monomer, alginic acid can be preferably used.
  • the polycarboxylic acid polymer is partially mixed with a monovalent metal (alkali metal) or ammonia in advance as long as it does not impair gas barrier properties and resistance to high-temperature steam or hot water when used in a retort molding container. Can be neutralized.
  • a monovalent metal alkali metal
  • ammonia in advance as long as it does not impair gas barrier properties and resistance to high-temperature steam or hot water when used in a retort molding container. Can be neutralized.
  • the number average molecular weight of the polycarboxylic acid polymer is not particularly limited. From the viewpoint of film formability, it is preferably in the range of 2,000 to 10,000,000, more preferably 5,000 to 1,000,000.
  • the polycarboxylic acid-based polymer as a raw material has a dry condition (30 ° C., 0% relative humidity) when formed into a film alone from the viewpoint of gas barrier properties and stability to high-temperature steam and hot water.
  • a dry condition (30 ° C., 0% relative humidity) when formed into a film alone from the viewpoint of gas barrier properties and stability to high-temperature steam and hot water.
  • Yes and most preferably 100 cm 3 (STP) ⁇ ⁇ m / (m 2 ⁇ day ⁇ MPa) or less.
  • the oxygen permeability coefficient can be obtained by the following method, for example.
  • a 10% by mass solution is prepared by dissolving the polycarboxylic acid polymer in a solvent such as water.
  • the prepared solution is coated on a plastic substrate using a bar coater and dried to prepare a coating film on which a polycarboxylic acid polymer having a thickness of 1 ⁇ m is formed.
  • the oxygen permeability at 30 ° C. and 0% relative humidity when the obtained coating film is dried is measured.
  • the plastic substrate an arbitrary plastic film whose oxygen permeability is known is used.
  • the measured value of the oxygen permeability Can be regarded as the oxygen permeability of the polycarboxylic acid polymer layer alone.
  • the obtained value is the oxygen permeability of the polycarboxylic acid polymer (B) having a thickness of 1 ⁇ m, it can be converted to an oxygen permeability coefficient by multiplying the value by 1 ⁇ m.
  • the plasticizer can be appropriately selected from known plasticizers.
  • specific examples of the plasticizer include, for example, ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,3-butanediol, 2,3-butanediol, pentamethylene glycol, hexamethylene glycol, diethylene glycol, triethylene.
  • examples include glycols such as glycol, polyethylene glycol, and polyethylene oxide; sorbitol, mannitol, dulcitol, erythritol, glycerin, lactic acid, and fatty acid. These may be used in a mixture as required.
  • glycerin, ethylene glycol, polyethylene glycol and the like are preferable from the viewpoints of stretchability and gas barrier properties.
  • the mixing ratio of the polycarboxylic acid polymer and the plasticizer is preferably 70/30 to 99.9 / 0.1 in terms of mass ratio of the polycarboxylic acid polymer / plasticizer, and 80/20 to 99. / 1 is even more preferable. More preferably, the mass ratio of polycarboxylic acid polymer / plasticizer is 85/15 to 95/5. When the mass ratio of the polycarboxylic acid polymer / plasticizer is in the range of 70/30 to 99.9 / 0.1, both stretchability and gas barrier properties can be achieved.
  • the second barrier layer 6 is one of the layers constituting the barrier layer 2 and includes a polyvalent metal compound and a resin.
  • the polyvalent metal compound is used to ionically bond with the carboxyl group of the polycarboxylic acid polymer contained in the first barrier layer 5 to improve the gas barrier property.
  • the resin is used as a binder for improving the film formability of the second barrier layer 6.
  • the polyvalent metal compound is a single polyvalent metal atom having a metal ion valence of 2 or more, and a compound thereof.
  • a divalent metal compound is preferably used as the polyvalent metal compound from the viewpoints of gas barrier properties as a molded container for retort, resistance to high-temperature steam and hot water, and manufacturability.
  • the chemical equivalent of the polyvalent metal in the sum of the polyvalent metal compounds relative to the sum of the carboxy groups contained in those layers is 0.2 or more. Further, it is preferably 0.5 chemical equivalent or more and 10 chemical equivalents or less.
  • it is more preferably in a range of 0.8 chemical equivalents or more and 5 chemical equivalents or less.
  • polyvalent metal examples include alkaline earth metals such as beryllium, magnesium and calcium, transition metals such as titanium, zirconia, chromium, manganese, iron, cobalt, nickel, copper and zinc, and aluminum.
  • polyvalent metal compound examples include oxides, hydroxides, carbonates, organic acid salts, inorganic acid salts of the above polyvalent metals, ammonium complexes of polyvalent metals, and second to fourth grades of polyvalent metals. Examples include amine complexes and carbonates and organic acid salts of these complexes.
  • Organic salts include acetate, oxalate, citrate, lactate, phosphate, phosphite, hypophosphite, stearate, monoethylenically unsaturated carboxylate, etc. It is done.
  • inorganic acid salts include chlorides, sulfates and nitrates.
  • an alkyl alkoxide of a polyvalent metal can be used.
  • the form of the polyvalent metal compound is not particularly limited. However, from the viewpoint of transparency of the multilayer sheet 10, the polyvalent metal compound is preferably granular and has a smaller particle size. In addition, in preparing a coating mixture for producing a multilayer sheet constituting a retort molding container as described later, from the viewpoint of efficiency during preparation and obtaining a more uniform coating mixture, the polyvalent metal compound is It is preferable to be granular and have a small particle size.
  • the average particle size of the polyvalent metal compound is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the second barrier layer 6 contains a polyvalent metal compound
  • the odor generated from the contents after the retort treatment can be reduced.
  • the zinc oxide becomes zinc ions and reacts with sulfur of hydrogen sulfide (H 2 S) which causes odor generated from the contents. This is considered to adsorb hydrogen sulfide.
  • the resin is a thermoplastic resin, a thermosetting resin, or the like, and can be suitably used as long as it is a resin used for paints.
  • alkyd resin, amino alkyd resin, melamine resin, acrylic resin, nitrified cotton, urethane resin, polyester resin, phenol resin, amino resin, fluorine resin, silicone resin, epoxy resin, vinyl resin, cellulosic resin, natural Resins such as resins can be mentioned.
  • curing agent can be used as needed and well-known resin, such as a melamine resin, polyisocyanate, a polyamine, can be mentioned.
  • the mixing ratio of the polyvalent metal compound and the resin is preferably 1/100 to 10/1, more preferably 1/10 to 5/1, and even more preferably, by mass ratio. Is 1/5 to 2/1. It exists in this range from a viewpoint of making heat stretch moldability and oxygen gas barrier property compatible.
  • the barrier layer 2 is formed by laminating the first barrier layer 5 and the second barrier layer 6 on one surface of the substrate 1 via an adhesive layer or an anchor coat layer, or without an adhesive layer or an anchor coat layer. Is provided.
  • the arrangement of the first barrier layer 5 and the second barrier layer 6 is an ionic bond between the carboxy group of the polycarboxylic acid polymer contained in the first barrier layer 5 and the polyvalent metal compound contained in the second barrier layer 6.
  • the first barrier layer 5 and the second barrier layer 6 have a layer configuration including at least one unit of the first barrier layer 5 / second barrier layer 6 which are adjacent layer constituent units.
  • the layer constitutional unit in which the first barrier layer 5 and the second barrier layer 6 are adjacent may be a three-layer constitution of the second barrier layer 6 / the first barrier layer 5 / the second barrier layer 6, Conversely, a three-layer configuration of the first barrier layer 5 / second barrier layer 6 / first barrier layer 5 may be used, and a layer configuration including one or more of these is preferable.
  • the polyvalent metal compound contained in the second barrier layer 6 develops an adhesive resin layer containing an acid-modified polyolefin, which will be described later, by hydrogen bonding, the second barrier layer 6 is bonded to the adhesive resin layer 4. It is preferable that the layers are stacked in contact with each other.
  • the thickness of the first barrier layer 5 before stretch molding is such that the chemical equivalent of the polyvalent metal in the total of the polyvalent metal compound relative to the total of the carboxy groups of the polycarboxylic acid polymer is 0.2 or more.
  • the thickness of the first barrier layer 5 is not less than 0.05 ⁇ m and not more than 100 ⁇ m, more preferably not less than 0.1 ⁇ m and not more than 10 ⁇ m in order to ensure good oxygen gas barrier properties. More preferably, it is 0.2 ⁇ m or more and 5 ⁇ m or less.
  • the thickness of the second barrier layer 6 before being stretch-molded is 0.05 ⁇ m or more and 100 ⁇ m or less, more preferably 0.1 ⁇ m or more, in order to ensure good oxygen gas barrier properties and stretch moldability. It is 10 ⁇ m or less, more preferably 0.2 ⁇ m or more and 5 ⁇ m or less.
  • the polyolefin layer 3 is a layer provided on the surface of the barrier layer 2.
  • the polyolefin layer 3 imparts wear resistance, gloss, heat sealability, strength, moisture resistance, and the like to the multilayer sheet 10.
  • a polyolefin resin can be used as the resin used for the polyolefin layer 3, among the thermoplastic resins used for the substrate 1.
  • a polyolefin resin can be used as the resin used for the polyolefin layer 3, among the thermoplastic resins used for the substrate 1, a polyolefin resin can be used.
  • low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, poly Polyolefin polymers such as 4-methylpentene and cyclic polyolefin, copolymers thereof, and acid-modified products thereof can be used, and polyethylene, polypropylene, and the like are preferably used.
  • the thickness of the polyolefin layer 3 before being stretch-molded is appropriately determined depending on the thickness of the molded container to be stretch-molded.
  • the thickness is preferably 1 ⁇ m or more and 1000 ⁇ m or less, and more preferably 5 ⁇ m or more and 500 ⁇ m or less. More preferably, it is 5 ⁇ m or more and 300 ⁇ m or less.
  • the thickness of the polyolefin layer 3 is good also as 1 mm or more according to the specification of a product.
  • the polyolefin layer 3 is attached to the surface of the barrier layer 2 by an adhesive resin layer 4 described later.
  • the adhesive resin layer 4 is an adhesive resin layer for bonding the thermoplastic barrier film 7 to the polyolefin layer 3 without using an adhesive for dry lamination.
  • the adhesive resin layer 4 is formed, for example, by using an acid-modified polyolefin resin such as acid-modified polyethylene or polypropylene as a base resin and mixing a resin modifier such as an ⁇ -olefin copolymer. By mixing such a resin modifier, the adhesive resin layer 4 can impart flexibility while maintaining a melting point that can be tolerated even if retorting or the like is performed.
  • the adhesive resin layer 4 is preferably a graft-modified polyolefin obtained by graft-modifying or copolymerizing at least one polymerizable ethylenically unsaturated carboxylic acid or a derivative thereof with a polyolefin resin before modification.
  • the functional group imparted to the polyolefin can be bonded by hydrogen bonding with the metal compound contained in the surface layer of the thermoplastic barrier film 7.
  • Examples of the ethylenically unsaturated carboxylic acid or a derivative thereof that is graft-modified or copolymerized with the polyolefin resin before modification include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, and maleic anhydride. More preferably, maleic anhydride can be used, but these can be used alone or in combination of two or more.
  • the thickness of the adhesive resin layer 4 before being stretch-molded is not particularly limited as long as it satisfies the function as an adhesive layer, but is, for example, 1 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the adhesive resin layer 4 is 1 ⁇ m or more, the thermoplastic barrier film 7 can be sufficiently adhered to the polyolefin layer 3, and peeling of both can be suppressed.
  • the thickness of the adhesive resin layer 4 is 50 ⁇ m or less, the adhesive resin layer 4 can be prevented from being unnecessarily thick.
  • the melt flow rate (MFR) of the resin composition constituting the adhesive resin layer 4 is preferably 3 g / 10 min or more and 10 g / 10 min or less.
  • MFR melt flow rate
  • the adhesive resin layer 4 itself or the surface layer of the thermoplastic barrier film 7 is destroyed due to stress or the like, and as a result, the adhesive resin layer 4 and It can suppress that the adhesive strength between the thermoplastic barrier films 7 weakens.
  • the adhesive resin layer 4 is prevented from being deformed by stress during molding, and in particular, thermoplasticity due to the flow of the adhesive resin layer 4 by hot water treatment such as retort.
  • the base of the resin composition constituting the adhesive resin layer 4 is preferably polypropylene.
  • polypropylene is more flexible than polypropylene, but its melting point is as low as about 120 ° C., which limits the conditions for retorting. Therefore, as described above, as the adhesive resin composition, for example, it is preferable to use a mixture of polypropylene and a resin modifier such as an ⁇ -olefin copolymer. Thereby, a softness
  • the resin composition which comprises the adhesive resin layer 4 may consist of another material. Further, these MFRs are obtained by measuring the fluidity of the resin composition at 230 ° C. based on JIS K 7210-1999.
  • FIG. 2 is a diagram schematically showing a process for manufacturing the multilayer sheet shown in FIG.
  • a coating liquid containing a polycarboxylic acid polymer and a plasticizer is prepared.
  • PAA polyacrylic acid
  • PAA polyacrylic acid
  • PAA is diluted with distilled water to prepare a 5 mass% aqueous solution of PAA.
  • Aqueous solution is prepared.
  • the obtained PAA / glycerin mixture aqueous solution is applied to one side of the substrate 1 by a known coating method and dried, whereby the first barrier layer 5 is formed.
  • the drying temperature is between room temperature and 90 ° C., and the drying time is preferably between 10 seconds and 60 minutes.
  • a coating solution containing a polyvalent metal compound constituting the second barrier layer 6 and a resin is prepared.
  • a curing agent 0 to 15 parts by mass of a curing agent is added to 100 parts by mass of a mixed dispersion (mixed solvent: toluene / MEK) of zinc oxide fine particles as a polyvalent metal compound and a polyester resin as a resin.
  • a mixed solution containing a polyvalent metal compound mixed with is prepared. This mixed liquid is applied to the surface of the first barrier layer 5 by a known coating method and dried to form the second barrier layer 6. Conditions similar to the drying temperature and drying time when forming the first barrier layer 5 can be adopted as the drying temperature and drying time.
  • thermoplastic barrier film 7 is prepared.
  • a polyolefin resin composition that forms the polyolefin layer 3, such as polypropylene resin, and a resin composition that forms the adhesive resin layer 4, such as acid-modified polyethylene resin, are multilayered. It is put into an extruder (extruder) 20 and melted at a predetermined temperature so that the resin temperature during extrusion is 200 ° C. to 300 ° C. In order to sufficiently draw out the adhesive strength of the adhesive resin, it is preferable to melt at a predetermined temperature so that the resin temperature during extrusion is 280 ° C. to 300 ° C.
  • the prepared thermoplastic barrier film 7 is supplied to the lower side of the multilayer extruder 20 via the roll 21 and the polypropylene resin 23 and the acid-modified polyethylene resin 24 are shared from the T die of the multilayer extruder 20 or the like.
  • An acid-modified polyethylene resin 24, which is an adhesive resin, is extruded and positioned between the polypropylene resin 23 constituting the polyolefin layer 3 and the thermoplastic barrier film 7 to be supplied.
  • the polypropylene resin 23 and the thermoplastic barrier film 7 constituting the layer 3 are attached to each other. Thereafter, these films are laminated via the roller 22 to complete the multilayer sheet 10.
  • adhesive resin is more expensive than polyolefin resin, such as polypropylene resin which comprises the polyolefin layer 3, in order to adjust the thickness of the multilayer sheet 10, it is preferable to adjust thickness with polyolefin resin.
  • polyolefin resin such as polypropylene resin which comprises the polyolefin layer 3
  • an adhesive resin composition was supplied from one of the two, and the remaining two systems It is also possible to make the polyolefin layer 3 thicker by extruding a polyolefin resin composition.
  • FIG. 3 is a diagram schematically showing a process for producing a conventional multilayer sheet.
  • the thermoplastic barrier film 7 is produced by the process shown in FIG. 3A similar to FIG.
  • a polypropylene sheet (PP sheet) 33 is manufactured.
  • the thermoplastic barrier film 7 is bonded to the PP sheet 33 by dry lamination using an adhesive or the like.
  • thermoplastic resin film 7 when the polyolefin layer 3 is formed by co-extrusion of the resin 23 and the adhesive resin 24 constituting the polyolefin layer 3. In addition, bonding to the thermoplastic resin film 7 is performed. For this reason, it is possible to increase the processing speed by the amount of dry laminating compared to the conventional case. For example, in the case of dry laminating a thermoplastic barrier film and a PP sheet having a thickness of 0.6 mm, assuming that the line speed is 30 m / min, and if producing 100,000 m per month, the dry laminating time is 60 It takes a little time. If it is the method concerning this embodiment, since this time can be made unnecessary, it becomes possible to raise the productivity of the multilayer sheet 10 dramatically.
  • the polyolefin layer 3 may be required to have a thickness of 1 mm or more.
  • the polyolefin film 3 can be easily made to be 1 mm or more by a sheet film forming machine, so that it is possible to widen the applicable product group. .
  • the multilayer sheet 10 thus produced may be stretch-molded to produce a molded container, and an example of the molded container 40 thus produced is shown in FIG. 4 is a cross-sectional view showing an example of a molded container manufactured using the multilayer sheet shown in FIG.
  • a molded container 40 shown in FIG. 4 is used for storing retort food and the like, and includes a main body 41 and a lid 42. Since the molded container 40 is composed of the multilayer sheet 10 described above, even if a retort process such as pressure heating is applied, a high gas barrier property can be maintained.
  • FIGS. 5A and 5B are cross-sectional views showing an example of a squeeze container according to an embodiment of the present invention.
  • This squeeze container can be formed into a desired container shape by a melt forming method such as a vacuum forming method using the multilayer sheet 10 composed of the polyolefin layer 3 and the thermoplastic barrier film 7.
  • FIG. 5A shows a squeeze container when the formed multilayer sheets 10 face each other and are bonded together.
  • FIG. 5 (b) shows a squeeze container when a lid 41 produced by laminating a plastic film or the like on the molded multilayer sheet 10 is sealed.
  • the entire surface of the container has rigidity as a sheet forming container, and the contents can be protected.
  • FIG. 5B not only as a squeeze container, but also the container can be used like a tray by peeling off the lid 41 during use.
  • these squeeze containers according to an embodiment of the present invention by bonding the polyolefin resin layer and the thermoplastic barrier film with the adhesive resin layer, it is possible to give the container an appropriate rigidity,
  • the thermoplastic barrier film has a barrier property.
  • the thickness of the resin layer including the polyolefin layer 3 and the adhesive resin layer 4 before being stretch-molded can be appropriately determined depending on the thickness of the molded container to be stretch-molded. Is preferably 100 ⁇ m or more and 1000 ⁇ m or less, and more preferably 200 ⁇ m or more and 600 ⁇ m or less. By setting it to 600 ⁇ m or less, the squeeze property is improved.
  • the total thickness of the multilayer sheet including the thickness of the thermoplastic barrier film is also preferably 650 ⁇ m or less.
  • the present invention is not limited to the above embodiment, and various modifications can be applied.
  • the manufacturing method using the T die has been described.
  • the present invention is not limited to this, and a multilayer sheet may be manufactured using an inflation die or the like.
  • a multilayer extruder was shown as an extruder, it passed twice through a single-layer extruder. Specifically, first, an adhesive resin composition was extruded, and then a polyolefin layer 3 was formed. It is also possible to produce a multilayer sheet by extruding the polyolefin resin composition.
  • the multilayer sheet includes a multilayer sheet 10 a in which a polyolefin layer 3 and an adhesive resin layer 4 are provided on both sides of the multilayer sheet.
  • the multilayer sheet 10a employs a layer structure including a thermoplastic barrier film 7a having a barrier layer 2a in which the stacking order of the first barrier layer 5 and the second barrier layer 6 is further changed.
  • a multilayer sheet having Moreover, as shown in FIG.6 (b), the multilayer sheet 10b which has the layer structure which replaced the base material 1, and the barrier layer 2 which consists of the 1st barrier layer 5 and the 2nd barrier layer 6 may be sufficient.
  • Example 1 As the base material 1 of the thermoplastic barrier film, easy-formed tefflex (trade name, registered trademark, manufactured by Teijin DuPont Films Ltd.) 25 ⁇ m was selected, and a barrier layer was formed by the following method.
  • PAA was diluted with distilled water as a polycarboxylic acid polymer to prepare a 5% by mass aqueous solution of PAA.
  • a coating liquid (PAA / glycerin mixture aqueous solution) for forming the first barrier layer 5 by mixing and stirring 10 parts by mass of a glycerin 5 mass% aqueous solution as a plasticizer with respect to 90 parts by mass of the obtained PAA aqueous solution. was prepared.
  • the obtained PAA / glycerin mixture aqueous solution was applied to one side of the substrate 1 with a gravure roll coater and dried to form the first barrier layer 5.
  • an isocyanate system is used with respect to 100 parts by mass of a mixed dispersion (mixed solvent: toluene / MEK) of zinc oxide fine particles as a polyvalent metal compound and a polyester polyol resin as a resin.
  • a mixed solution containing a polyvalent metal compound mixed with 15 parts by mass of the curing agent was prepared. The liquid mixture was applied to the surface of the first barrier layer 5 by a gravure roll coater and dried to form the second barrier layer 6.
  • Homo PP “E111G (manufactured by Prime Polymer Co., Ltd., trade name), MFR 0.5 g / 10 min” is prepared as the PP resin constituting the polyolefin layer of the multilayer sheet, and modified PP “Admer QF551” is used as the adhesive resin. (Mitsui Chemicals, Inc., “Admer” is a registered trademark), MFR 5.7 g / 10 min ”was prepared.
  • the homo PP “E111G” and the modified PP “Admer QF551” were charged into an extruder (manufactured by Sumitomo Heavy Industries Modern Co., Ltd.) and melted so that the melting temperature during extrusion was 240 ° C.
  • thermoplastic barrier film is fed below the extruder, and the homo PP “E111G” and the modified PP “Admer QF551” are co-extruded with the extruder, and the modified PP “
  • the fed thermoplastic barrier film was heat laminated so that Admer QF551 ”was positioned between the thermoplastic barrier film and the homo PP.
  • the number of revolutions of the extruder screw was adjusted so that the film thickness of the homo PP resin was 600 ⁇ m and the film thickness of the adhesive resin was 25 ⁇ m.
  • the multilayer sheet 10 shown in FIG. 1 was obtained by the above method.
  • Example 2 The multilayer sheet 10 shown in FIG. 1 was used in the same manner as in Example 1 except that modified PP “Admer QB550 (Mitsui Chemicals,“ Admer ”is a registered trademark), MFR 2.8 g / 10 min” was used as the adhesive resin. Got.
  • Example 3 As an adhesive resin, modified PP “Admer QF551 (Mitsui Chemicals, Inc.,“ Admer ”is a registered trademark)” and “Toughmer XM-7070 (Mitsui Chemicals, Inc.,“ Tafmer ”are registered trademarks) MFR 7.0 g / 10 Using a material in which “min” was mixed at a weight ratio of 10%, and the other conditions were the same as in Example 1, the multilayer sheet 10 shown in FIG. 1 was obtained. The average MFR of the mixed adhesive resin composition was 3.2 g / 10 minutes.
  • thermoplastic barrier film was first produced by the same method as in Example 1.
  • thermoplastic barrier film and a general-purpose PP sheet having a thickness of 600 ⁇ m were bonded with a dry laminator (manufactured by Fuji Machine Industry Co., Ltd.) using an adhesive.
  • a dry laminator manufactured by Fuji Machine Industry Co., Ltd.
  • the adhesive “Takelac A626 (manufactured by Mitsui Chemicals)” and “Takenate A-50 (manufactured by Mitsui Chemicals)” were mixed at a weight ratio of 8: 1, and the coating amount after drying was 5 g / m 2 . Coated so that.
  • the multilayer sheet of Comparative Example 1 was obtained.
  • Comparative Example 2 As Comparative Example 2, a multilayer sheet having a layer structure in the order of PP resin / Admer / EVOH resin / Admer / PP resin was produced. Specifically, homo PP “E111G (manufactured by Prime Polymer Co., Ltd., trade name)” as PP resin, modified PP “Admer QF551 (manufactured by Mitsui Chemicals)” as adhesive resin, and Eval “F171B” as EVOH resin. (Manufactured by Kuraray Co., Ltd.) ".
  • the multilayer sheets of Examples 1 to 3 obtained as described above and the multilayer sheets of Comparative Examples 1 and 2 were heat-softened using a deep drawing type high-speed automatic vacuum packaging machine, vacuum-formed, and 120 mm long ⁇ 120 mm wide ⁇ A container with a height of 35 mm was obtained. Using the container thus formed, the following tests were conducted.
  • Test 1 The appearance after vacuum formation and after retorting was confirmed in five containers for each example and each comparative example.
  • the retort process was carried out as a single container, and two conditions of 121 ° C. ⁇ 30 minutes and 131 ° C. ⁇ 30 minutes were performed.
  • the case where wrinkles that can be visually confirmed and the floating of the laminate part occurred was determined to be “impossible”, and other cases were determined to be “good”.
  • Test 2 The oxygen barrier performance of the container before retort treatment and one day after the retort treatment was measured.
  • the retort process was carried out as a single container, and the conditions were 121 ° C. ⁇ 1/30.
  • Test 3 The taste sensory test was conducted according to the following procedure. First, the inside of the container was filled with ultrapure water, and a lid made of an aluminum foil and a sealant film was heat-sealed to the container and sealed, and the retort treatment was performed at 121 ° C. for 30 minutes. Next, water was taken out from the container without giving the type of container to five subjects, and the evaluation was requested in the form of comparison with the water filled in the container of Comparative Example 2. A case equal to or greater than that of Comparative Example 2 was determined as “good”, and a case where the taste / odor was inferior to that of Comparative Example 2 was determined as “impossible”.
  • Test 1 The results of Test 1 to Test 3 are shown in Table 1 below.
  • Comparative Example 1 the sensory test was inferior to the others due to the influence of the adhesive used for the laminate.
  • Comparative Example 2 the oxygen barrier after the retort treatment was greatly reduced by the retort shock.
  • both the sensory test and the oxygen barrier after the retort treatment gave good results. In particular, by adjusting the MFR of the adhesive resin, the initial appearance and the appearance after the retort treatment were improved.
  • the multilayer sheet according to the present invention is used, it is possible to provide an optimal container as a container for foods and the like that are required to be resistant to moist heat with respect to hot water treatment such as retort and to suppress odor transfer from the container. Was confirmed.
  • Example 4 Next, in Example 1, when the supplied thermoplastic barrier film was extrusion laminated, the screw speed of the extruder was adjusted so that the film thickness of the adhesive resin was 25 ⁇ m. In addition, the film thickness of homo PP was similarly adjusted by adjusting the number of rotations of the screw, and four levels were prepared in which the total thickness of the thermoplastic barrier film, adhesive resin, and polypropylene resin was 175 ⁇ m, 375 ⁇ m, 575 ⁇ m, and 757 ⁇ m.
  • Comparative Example 3 As Comparative Example 3, a multilayer sheet having a layer structure in the order of PP resin / adhesive resin / EVOH resin / adhesive resin / PP resin was produced. Specifically, homo PP “E111G (manufactured by Prime Polymer Co., Ltd., trade name)” as PP resin, modified PP “Admer QF551 (manufactured by Mitsui Chemicals)” as adhesive resin, and EVAL “F171B” as EVOH resin. (Kuraray Co., Ltd.) "was prepared.
  • each layer was designed so that the thickness of the adhesive resin was fixed at 10 ⁇ m with respect to the four levels of total film thickness of 200 ⁇ m, 400 ⁇ m, 600 ⁇ m and 800 ⁇ m, and the EVOH ratio was 8%. These resins were extruded using an extruder capable of coextrusion of 3 types and 5 layers to obtain a multilayer sheet using EVOH.
  • a container having a trapezoidal side surface shown in FIG. 7 was obtained by vacuum forming.
  • the opening has a length of the long side 51 of 50 mm, the length of the short side 52 of 30 mm, the bottom has a length of the long side 53 of 50 mm, a length of the short side 54 of 20 mm, and a depth of the container 55. It was 30 mm.
  • the following tests were conducted using the container thus molded.
  • Test 4 The container not filled with the contents was put into a retort process at 121 ° C. for 30 minutes. Next, the oxygen permeability of the container one day after the retort treatment was measured in an environment of 30 ° C. and 70% by the container mocon method.
  • Test 5 The contents were filled with ketchup sauce up to 90% of the full, and using a lid material in which PET 12 ⁇ m, aluminum foil 9 ⁇ m, and CPP 70 ⁇ m were bonded together in this order, they were bonded so as to close the opening of the container by heat sealing. Next, a 5 mm diameter hole was made in the center of the trapezoidal surface surrounded by the short side 52 and the short side 54 of the container to provide a pseudo squeeze mouth. If 5 subjects were able to squeeze out more than 90% of the contents without any difficulty, assuming that they were actually used, the test was passed. When it occurred, the squeeze property was evaluated as rejected.
  • Table 2 shows the results of Test 4 and Test 5.
  • the “resin thickness” in Table 2 is the combined thickness of the polypropylene resin and the adhesive resin in Example 4, and in Comparative Example 3, the combined thickness of the polypropylene resin, the adhesive resin, and the EVOH resin. is there.
  • Example 4 the value of oxygen permeability was constant without being affected by the resin thickness, and when the resin thickness was 600 ⁇ m or less, both squeeze property and barrier property could be achieved.
  • Comparative Example 3 the oxygen barrier changed depending on the resin thickness, and the barrier property was greatly inferior to the thickness of 800 ⁇ m when the thickness was 600 ⁇ m or less where the squeeze property was secured.
  • the use of the multilayer sheet according to one embodiment of the present invention makes it possible to obtain a squeeze container having both squeeze characteristics and high barrier characteristics without depending on the thickness of the container. .
  • the present invention can be applied to multilayer sheets and molded containers used for boil and retort applications, particularly squeeze containers, and methods for producing them.
  • SYMBOLS 1 Base material, 2 ... Barrier layer, 3 ... Polyolefin layer, 4 ... Adhesive resin layer, 5 ... 1st barrier layer, 6 ... 2nd barrier layer, 7 ... Thermoplastic barrier film, 10, 10a, 10b ... Multilayer Sheet, 20 ... multilayer extruder, 40 ... molded container.

Abstract

L'invention concerne un procédé de fabrication d'une feuille multicouche comportant un film barrière thermoplastique formé par empilement d'un matériau de base qui renferme une résine thermoplastique, d'une première couche barrière qui renferme un polymère à base d'acide polycarboxylique et un plastifiant, et d'une seconde couche barrière qui renferme un composé métallique polyvalent et une résine. Ce procédé de fabrication comprend : une étape de préparation du film barrière thermoplastique ; une étape de préparation d'une composition de résine de polyoléfine et d'une composition de résine adhésive ; et une étape d'extrusion de la composition de résine de polyoléfine et de la composition de résine adhésive à partir d'une extrudeuse afin d'introduire film barrière thermoplastique et de positionner la composition de résine adhésive entre le film barrière thermoplastique introduit et une couche formée par la composition de résine de polyoléfine.
PCT/JP2017/022396 2016-06-17 2017-06-16 Procédé de fabrication d'une feuille multicouche, procédé de fabrication d'un récipient moulé et feuille multicouche WO2017217546A1 (fr)

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WO2019142923A1 (fr) * 2018-01-19 2019-07-25 凸版印刷株式会社 Stratifié formant barrière contre les gaz et emballage pourvu de celui-ci
JP2020114637A (ja) * 2019-01-17 2020-07-30 凸版印刷株式会社 ガスバリア積層体及びそれを備える包装体
JP2020114631A (ja) * 2019-01-17 2020-07-30 凸版印刷株式会社 ガスバリア積層体及びそれを備える包装体
JP2020114636A (ja) * 2019-01-17 2020-07-30 凸版印刷株式会社 ガスバリア積層体及びそれを備える包装体
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WO2019142923A1 (fr) * 2018-01-19 2019-07-25 凸版印刷株式会社 Stratifié formant barrière contre les gaz et emballage pourvu de celui-ci
JP2020114637A (ja) * 2019-01-17 2020-07-30 凸版印刷株式会社 ガスバリア積層体及びそれを備える包装体
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