WO2021065887A1 - Stratifié barrière, stratifié thermosoudable comprenant ledit stratifié barrière et contenant d'emballage comprenant ledit stratifié thermosoudable - Google Patents

Stratifié barrière, stratifié thermosoudable comprenant ledit stratifié barrière et contenant d'emballage comprenant ledit stratifié thermosoudable Download PDF

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Publication number
WO2021065887A1
WO2021065887A1 PCT/JP2020/036838 JP2020036838W WO2021065887A1 WO 2021065887 A1 WO2021065887 A1 WO 2021065887A1 JP 2020036838 W JP2020036838 W JP 2020036838W WO 2021065887 A1 WO2021065887 A1 WO 2021065887A1
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Prior art keywords
barrier
laminate
film
resin layer
base material
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PCT/JP2020/036838
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English (en)
Japanese (ja)
Inventor
鈴木　剛
昌平 奥村
古谷　俊輔
高橋　秀明
行倫 金村
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大日本印刷株式会社
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Priority to JP2021508013A priority Critical patent/JP6962499B2/ja
Publication of WO2021065887A1 publication Critical patent/WO2021065887A1/fr
Priority to JP2021169182A priority patent/JP7351328B2/ja

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    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

  • the present invention relates to a barrier laminate, a heat-seal laminate having the barrier laminate, and a packaging container including the heat-seal laminate.
  • a film made of polyester such as polyethylene terephthalate (hereinafter, also referred to as polyester film) is excellent in mechanical properties, chemical stability, heat resistance and transparency, and is inexpensive. Therefore, conventionally, a polyester film has been used as a base material constituting a laminate used for producing a packaging container.
  • the packaging container is required to have high oxygen barrier properties and gas barrier properties such as water vapor barrier properties.
  • gas barrier properties such as water vapor barrier properties.
  • it is widely practiced to form a thin-film film containing alumina, silica, or the like on the surface of a polyester film in a packaging container (Patent Document 1).
  • the present inventors have considered using a polypropylene stretched film (hereinafter, also referred to as a stretched polypropylene film) instead of the conventional polyester film base material. As a result of the study, the present inventors have found a new problem that even if a vapor-deposited film is formed on the surface of the stretched polypropylene film, a satisfactory gas barrier property cannot be obtained.
  • a polypropylene stretched film hereinafter, also referred to as a stretched polypropylene film
  • the present inventors improve the adhesion of the vapor-deposited film formed on the surface resin layer by providing a surface resin layer containing a resin material having a melting point of 180 ° C. or higher on the surface of the stretched polypropylene film. At the same time, it was found that the gas barrier property is also improved.
  • the present invention has been made based on such findings, and an object to be solved thereof is to provide a barrier laminate having a multilayer base material having excellent adhesion between layers with a vapor-deposited film and having a high gas barrier property. ..
  • An object to be solved by the present invention is to provide a heat-sealing laminate provided with the barrier laminate.
  • An object to be solved by the present invention is to provide a packaging container provided with the heat-sealing laminate.
  • the barrier laminate of the present invention comprises a multilayer base material and a vapor-deposited film.
  • the multilayer base material has been stretched and has been stretched.
  • the multilayer base material includes at least a polypropylene resin layer and a surface resin layer.
  • the surface resin layer contains a resin material having a melting point of 180 ° C. or higher.
  • the vapor-deposited film is characterized by being composed of an inorganic oxide.
  • the barrier laminate may further include a barrier coat layer on the vapor-deposited film.
  • the melting point of the resin material may be 265 ° C. or lower.
  • the difference between the melting point of the resin material and the melting point of polypropylene contained in the polypropylene resin layer may be 20 to 80 ° C.
  • the resin material may have a polar group.
  • the resin material may be one or more resin materials selected from ethylene vinyl alcohol copolymer, polyvinyl alcohol, polyester, nylon 6, nylon 6,6, MXD nylon and amorphous nylon. ..
  • the resin material may be polyamide.
  • the resin material may be an ethylene vinyl alcohol copolymer.
  • the ratio of the thickness of the surface resin layer to the total thickness of the multilayer base material may be 1% or more and 10% or less.
  • the multilayer base material may be a co-press film.
  • the barrier laminate may be used for packaging containers.
  • the inorganic oxide may be silica, silicon carbide oxide, or alumina.
  • the heat-sealing laminate of the present invention is characterized by including the barrier laminate and a sealant layer.
  • the sealant layer may be made of the same material as the polypropylene resin layer, and the same material may be polypropylene.
  • the packaging container of the present invention is characterized by including the above heat-sealing laminate.
  • the present invention it is possible to produce a packaging container having excellent adhesion between layers of a polypropylene film and a vapor-deposited film and having high lamination strength, and to provide a barrier laminate having high gas barrier property. According to the present invention, it is possible to provide a heat-sealable laminate having the barrier laminate. According to the present invention, it is possible to provide a packaging container provided with the heat-sealing laminate.
  • the barrier laminate 10 of the present invention includes a multilayer base material 11 and a vapor-deposited film 12, and the multilayer base material 11 includes at least a polypropylene resin layer 13 and a surface resin layer 14. Be prepared.
  • the barrier laminate 10 of the present invention further includes a barrier coat layer 15 on the vapor-deposited film 12, as shown in FIG.
  • the multilayer base material 11 includes an adhesive resin layer 16 between the polypropylene resin layer 13 and the surface resin layer 14, as shown in FIG.
  • the barrier laminate 10 of the present invention includes a multilayer base material 11, a vapor-deposited film 12, and a barrier coat layer 15 provided on the vapor-deposited film 12, as shown in FIG.
  • the multilayer base material 11 includes a polypropylene resin layer 13, an adhesive resin layer 16, and a surface resin layer 14, and the adhesive resin layer 16 is provided between the polypropylene resin layer 13 and the surface resin layer 14. ing.
  • each layer included in the barrier laminate of the present invention will be described.
  • the haze value of the barrier laminate is preferably 20% or less, and more preferably 5% or less. Thereby, the transparency of the barrier laminate can be improved.
  • the haze value of the barrier laminate is measured by a haze meter (Murakami Color Technology Research Institute Co., Ltd.) in accordance with JIS K 7105: 1981.
  • the multilayer base material includes at least a polypropylene resin layer and a surface resin layer.
  • the multilayer base material may include an adhesive resin layer between the polypropylene resin layer and the surface resin layer.
  • the multilayer base material has been stretched.
  • the stretching treatment may be uniaxial stretching or biaxial stretching.
  • the draw ratio of the multilayer base material in the vertical direction (MD direction) and the horizontal direction (TD direction) is preferably 2 times or more and 15 times or less, and preferably 5 times or more and 13 times or less.
  • the draw ratio is preferably 15 times or less.
  • the surface resin layer included in the multilayer base material may be surface-treated. Thereby, the adhesion with the adjacent layer can be improved.
  • the surface treatment method is not particularly limited, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and / or nitrogen gas, physical treatment such as glow discharge treatment, and oxidation using chemicals. Examples include chemical treatment such as treatment.
  • the polypropylene resin layer is made of polypropylene.
  • the polypropylene resin layer may have a single-layer structure or a multi-layer structure.
  • the polypropylene contained in the polypropylene resin layer may be a homopolymer, a random copolymer or a block copolymer.
  • a polypropylene homopolymer is a polymer containing only propylene.
  • the polypropylene random copolymer is a random copolymer of propylene and other ⁇ -olefins other than propylene (for example, ethylene, butene-1, 4-methyl-1-pentene, etc.).
  • the polypropylene block copolymer is a copolymer having a polymer block made of propylene and a polymer block made of an ⁇ -olefin other than the above-mentioned propylene.
  • polypropylenes it is preferable to use a homopolymer or a random copolymer from the viewpoint of transparency. It is preferable to use a homopolymer when the rigidity and heat resistance of the packaging bag are important, and to use a random copolymer when the impact resistance and the like are important. Biomass-derived polypropylene and mechanically or chemically recycled polypropylene can also be used.
  • the polypropylene content in the polypropylene resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
  • the polypropylene resin layer may contain a resin material other than polypropylene as long as the characteristics of the present invention are not impaired.
  • the resin material include polyolefins such as polyethylene, (meth) acrylic resins, vinyl resins, cellulose resins, polyamide resins, polyesters and ionomer resins.
  • the polypropylene resin layer can contain additives as long as the characteristics of the present invention are not impaired. Additives include, for example, cross-linking agents, antioxidants, anti-blocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments and modifying resins. Can be mentioned.
  • the thickness of the polypropylene resin layer is preferably 10 ⁇ m or more and 50 ⁇ m or less, and more preferably 10 ⁇ m or more and 40 ⁇ m or less.
  • the thickness of the polypropylene resin layer is preferably 10 ⁇ m or more and 50 ⁇ m or less, and more preferably 10 ⁇ m or more and 40 ⁇ m or less.
  • the polypropylene resin layer may have a printing layer on its surface.
  • the image formed on the print layer is not particularly limited, and represents characters, patterns, symbols, and combinations thereof.
  • the print layer can be formed on the base material by using an ink derived from biomass. This can reduce the environmental load.
  • the method for forming the print layer is not particularly limited, and examples thereof include conventionally known printing methods such as a gravure printing method, an offset printing method, and a flexographic printing method.
  • the multilayer base material may include an adhesive resin layer between the polypropylene resin layer and the surface resin layer. Thereby, the adhesion between these layers can be improved.
  • the adhesive resin layer can be formed by using an adhesive resin such as a polyether, a polyester, a silicone resin, an epoxy resin, a polyurethane, a vinyl resin, a phenol resin, a polyolefin, and an acid-modified product of a polyolefin.
  • an adhesive resin such as a polyether, a polyester, a silicone resin, an epoxy resin, a polyurethane, a vinyl resin, a phenol resin, a polyolefin, and an acid-modified product of a polyolefin.
  • polyolefins and their acid-modified products are used from the viewpoint of recycling suitability of packaging containers produced by using the barrier laminate of the present invention and the laminate of the sealant layer made of polypropylene.
  • polypropylene and this acid-modified product are particularly preferred.
  • the adhesive polypropylene a commercially available product can be used, and for example, an Admer series manufactured by Mitsui Chemicals, Inc. can be used.
  • the thickness of the adhesive resin layer is not particularly limited, but can be, for example, 1 ⁇ m or more and 15 ⁇ m or less. By setting the thickness of the adhesive resin layer to 1 ⁇ m or more, the adhesion between the polypropylene resin layer and the surface resin layer can be further improved. By setting the thickness of the adhesive layer to 15 ⁇ m or less, the processability of the multilayer base material can be improved.
  • the multilayer base material is a co-pressed film, which can be produced by forming a film by using a T-die method, an inflation method, or the like, forming a laminated film, and then stretching the film.
  • a co-pressed film which can be produced by forming a film by using a T-die method, an inflation method, or the like, forming a laminated film, and then stretching the film.
  • the laminated film can be stretched at the same time.
  • the multilayer base material includes a surface resin layer containing a resin material having a melting point of 180 ° C. or higher (hereinafter, also referred to as a high melting point resin material) on the polypropylene resin layer, and has high adhesion on the surface resin layer.
  • a vapor-deposited film can be formed and the gas barrier property can be improved.
  • the packaging container produced by using the barrier laminate provided with the surface resin layer has high lamination strength.
  • the melting point of the high melting point resin material is more preferably 185 ° C. or higher, further preferably 190 ° C. or higher, and particularly preferably 205 ° C. or higher.
  • the melting point of the high melting point resin material is preferably 260 ° C. or lower, more preferably 260 ° C. or lower, and further preferably 250 ° C. or lower.
  • the melting point can be measured according to JIS K7121: 2012 (method for measuring the transition temperature of plastics). Specifically, a differential scanning calorimetry (DSC) device can be used to measure the DSC curve at a rate of temperature rise of 10 ° C./min to determine the melting point.
  • DSC differential scanning calorimetry
  • the difference between the melting point of the high melting point resin material contained in the surface resin layer and the melting point of polypropylene contained in the polypropylene resin layer is preferably 20 to 80 ° C, more preferably 20 to 60 ° C.
  • the difference between the melting point of the high melting point resin material contained in the surface resin layer and the melting point of polypropylene contained in the polypropylene resin layer is 20 ° C. or higher, the adhesion of the vapor-deposited film can be further improved and the gas barrier property is further improved. it can.
  • the lamination strength of the packaging container can be further improved.
  • the difference between the melting point of the high melting point resin material contained in the surface resin layer and the melting point of polypropylene contained in the polypropylene resin layer is 80 ° C. or less, the film forming property of the multilayer base material can be further improved.
  • the refractory resin material preferably has a polar group.
  • the polar group refers to a group containing one or more heteroatoms, for example, an ester group, an epoxy group, a hydroxyl group, an amino group, an amide group, a carboxyl group, a carbonyl group, a carboxylic acid anhydride group, and a sulfone group. , Thiol group and halogen group and the like.
  • a hydroxyl group, an ester group, an amino group, an amide group, a carboxyl group and a carbonyl group are preferable, and a hydroxyl group is more preferable.
  • the high melting point resin material can be used without particular limitation as long as the melting point is 180 ° C. or higher.
  • the refractory resin material include vinyl resin, polyamide, polyimide, polyester, (meth) acrylic resin, cellulose resin, polyolefin resin, and ionomer resin.
  • the high melting point resin material has a melting point of 180 ° C. or higher, and a resin material having a polar group is particularly preferable, and an ethylene vinyl alcohol copolymer, polyvinyl alcohol, polyester, nylon 6, nylon 6,6, MXD. Polyamides such as nylon and amorphous nylon are preferable, and ethylene vinyl alcohol copolymers and polyvinyl alcohol are more preferable.
  • the refractory resin material is more preferably an ethylene vinyl alcohol copolymer.
  • an ethylene vinyl alcohol copolymer as the refractory resin material, it is possible to suppress a decrease in gas barrier property even if the barrier laminate is bent.
  • the refractory resin material is preferably polyamide.
  • polyamide As the melting point resin material, it is possible to suppress a decrease in gas barrier property even if the barrier layer is bent, and it is possible to suppress a decrease in gas barrier property even if the barrier layer is heated.
  • Nylon 6 is more preferable as the refractory resin material.
  • the content of the refractory resin material in the surface resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
  • the surface resin layer may contain a resin material other than the refractory resin material as long as the characteristics of the present invention are not impaired.
  • the surface resin layer may contain additives as long as the characteristics of the present invention are not impaired. Additives include, for example, cross-linking agents, antioxidants, anti-blocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments and modifying resins. Can be mentioned.
  • the ratio of the thickness of the surface resin layer to the total thickness of the multilayer base material is preferably 1% or more and 10% or less, and more preferably 1% or more and 5% or less.
  • the thickness of the surface resin layer is preferably 0.1 ⁇ m or more and 5 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 4 ⁇ m or less.
  • the thickness of the surface resin layer is preferably 0.1 ⁇ m or more and 5 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 4 ⁇ m or less.
  • the barrier laminate of the present invention includes a vapor-deposited film composed of an inorganic oxide on a surface resin layer. Thereby, the gas barrier property of the barrier laminated body, specifically, the oxygen barrier property and the water vapor barrier property can be improved.
  • the packaging container produced by using the barrier laminate of the present invention can suppress the mass reduction of the contents filled in the packaging container.
  • the inorganic oxide examples include aluminum oxide (alumina), silicon oxide (silica), magsium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, and silicon carbide (carbon-containing silicon oxide). And so on.
  • silica, silicon carbide oxide and alumina are preferable.
  • silica is more preferable as the inorganic oxide because aging treatment after forming the vapor-deposited film is not required.
  • carbon-containing silicon oxide is more preferable as the inorganic oxide from the viewpoint that deterioration of gas barrier property can be suppressed even if the barrier laminate is bent.
  • the thickness of the vapor-deposited film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and further preferably 10 nm or more and 40 nm or less.
  • the thickness of the thin-film deposition film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and further preferably 10 nm or more and 40 nm or less.
  • the vapor deposition film can be formed by using a conventionally known method.
  • the method for forming the vapor deposition film includes, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method and an ion plating method, and a plasma chemical vapor deposition method and a thermochemical vapor deposition method. Examples thereof include a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a method and a photochemical vapor deposition method.
  • PVD method Physical Vapor Deposition method
  • CVD method chemical vapor deposition method
  • the thin-film deposition film may be a single layer formed by one vapor deposition step or a multilayer formed by a plurality of thin-film deposition steps. When there are multiple layers, each layer may be the same material or a different material. Each layer may be formed by the same method or by a different method.
  • the vacuum film forming apparatus includes a vacuum container A, an unwinding portion B, a film forming drum C, a winding portion D, a transport roll E, an evaporation source F, and a reaction gas.
  • a supply unit G, a protective box H, a vapor deposition material I, and a plasma gun J are provided.
  • FIG. 5 is a schematic cross-sectional view of the vacuum film forming apparatus in the XZ plane direction
  • FIG. 6 is a schematic cross-sectional view of the vacuum film forming apparatus in the XY plane direction.
  • a multilayer base material 11 wound by the film forming drum C method is arranged on the upper part of the vacuum container A with its surface resin layer surface facing downward, and the film is formed in the vacuum container A.
  • an electrically grounded protective box H is arranged below the use drum C.
  • the evaporation source F is arranged on the bottom surface of the protective box H.
  • the film forming drum is placed in the vacuum vessel A so that the surface resin layer surface of the multilayer base material 11 wound around the film forming drum C is located at a position facing the upper surface of the evaporation source F at a certain interval. C is placed.
  • the transport roll E is arranged between the unwinding portion B and the film forming drum C, and between the film forming drum C and the winding portion D.
  • the vacuum container is connected to the vacuum pump (not shown).
  • the evaporation source F is for holding the vaporized material I and includes a heating device (not shown).
  • the reaction gas supply unit G is a portion that supplies a reaction gas (oxygen, nitrogen, helium, argon, a mixed gas thereof, or the like) that reacts with the evaporated vaporized material.
  • the vaporized vaporized material I heated and evaporated from the evaporation source F is irradiated toward the surface resin layer of the multilayer base material 11, and at the same time, plasma is also irradiated from the plasma gun J toward the surface resin layer. A vaporized film is formed. Details of this forming method are disclosed in Japanese Patent Application Laid-Open No. 2011-214089.
  • the plasma generator used in the plasma chemical vapor deposition method a generator such as a high frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Further, an apparatus having two or more film forming chambers may be used. It is preferable that the device is provided with a vacuum pump and can hold each film forming chamber in a vacuum. The degree of vacuum in each film forming chamber is preferably 1 ⁇ 10 to 1 ⁇ 10 -6 Pa. An embodiment of a method for forming a vapor-deposited film using a plasma generator will be described below. First, the multilayer base material is sent out to the film forming chamber, and is conveyed onto the cooling / electrode drum at a predetermined speed via an auxiliary roll.
  • a mixed gas composition containing a film-forming monomer gas containing an inorganic oxide, an oxygen gas, an inert gas, etc. is supplied from the gas supply device into the film-forming chamber, and plasma is generated on the surface resin layer by glow discharge. Is generated and irradiated with this to form a vapor-deposited film containing an inorganic oxide on the surface resin layer. Details of this forming method are disclosed in Japanese Patent Application Laid-Open No. 2012-076292.
  • FIG. 7 is a schematic configuration diagram showing a plasma chemical vapor deposition apparatus used in the CVD method.
  • the plasma chemical vapor deposition apparatus unwinds the multilayer base material 11 from the unwinding portion B1 arranged in the vacuum vessel A1, and further conveys the multilayer base material 11. It is cooled at a predetermined speed via the roll E1 and conveyed onto the peripheral surface of the electrode drum C1. Oxygen, nitrogen, helium, argon and a mixed gas thereof are supplied from G1 to the reaction gas supply, and a monomer gas for film formation is supplied from the raw material gas supply unit I1 to prepare a mixed gas composition for vapor deposition composed of them.
  • the mixed gas composition for vapor deposition into the vacuum vessel A1 through the raw material supply nozzle H1, and on the surface resin layer of the multilayer base material 11 conveyed on the peripheral surface of the cooling / electrode drum C1 described above.
  • a plasma is generated by the glow discharge plasma F1 and irradiated with this to form a vapor deposition film.
  • a predetermined electric power is applied to the cooling / electrode drum C1 from the power supply K1 arranged outside the vacuum vessel A1, and a magnet J1 is arranged in the vicinity of the cooling / electrode drum C1 to generate plasma. Is promoting the outbreak of.
  • the multilayer base material 11 is wound around the winding portion D1 via the transport roll E1 at a predetermined winding speed after forming the thin-film deposition film.
  • L1 represents a vacuum pump.
  • a continuous vapor-deposited film deposition apparatus including a plasma pretreatment chamber and a film-forming chamber can be used.
  • An embodiment of a method for forming a vapor-deposited film using the apparatus is described below. First, in the plasma pretreatment chamber, plasma is irradiated from the plasma supply nozzle to the surface resin layer included in the multilayer base material. Next, a thin-film deposition film is formed on the plasma-treated surface resin layer in the film-forming chamber. Details of this forming method will be disclosed in the international publication WO2019 / 0879960 pamphlet.
  • the surface of the thin-film deposition film is preferably subjected to the above surface treatment. Thereby, the adhesion with the adjacent layer can be improved.
  • the vapor-deposited film is preferably a vapor-deposited film formed by the CVD method, and more preferably a carbon-containing silicon oxide vapor-deposited film formed by the CVD method.
  • the carbon-containing silicon oxide vapor deposition film contains silicon, oxygen, and carbon.
  • the ratio C of carbon is preferably 3% or more and 50% or less, preferably 5% or more and 40% or less, based on 100% of the total of the three elements of silicon, oxygen, and carbon. More preferably, it is more preferably 10% or more and 35% or less.
  • the ratio Si of silicon is preferably 1% or more and 45% or less, preferably 3% or more, based on 100% of the total of the three elements of silicon, oxygen, and carbon. It is more preferably 38% or less, and further preferably 8% or more and 33% or less.
  • the ratio O of oxygen is preferably 10% or more and 70% or less, more preferably 20% or more and 65% or less, and 25% with respect to 100% of the total of the three elements of silicon, oxygen, and carbon. It is more preferably 60% or more.
  • the oxygen ratio O is preferably higher than the carbon ratio C, and the silicon ratio Si is preferably lower than the carbon ratio C.
  • the ratio O of oxygen is preferably higher than the ratio Si of silicon, that is, each ratio is preferably lower in the order of ratio O, ratio C, and ratio Si.
  • the proportion C, proportion Si and proportion O in the carbon-containing silicon oxide vapor-deposited film can be measured by narrow scan analysis under the following measurement conditions by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • Ion sputtering conditions Ion species: Ar + Acceleration voltage: 0.2 (kV)
  • the barrier laminate of the present invention can further include a barrier coat layer on the vapor-deposited film. Thereby, the oxygen barrier property and the water vapor barrier property of the barrier laminated body can be improved.
  • the barrier coat layer is a polyamide such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyacrylonitrile, nylon 6, nylon 6,6 and polymethoxylylen adipamide (MXD6). , Polyester, polyurethane, and gas barrier resins such as (meth) acrylic resins.
  • polyvinyl alcohol is preferable from the viewpoint of oxygen barrier property and water vapor barrier property.
  • the content of the gas barrier resin in the barrier coat layer is preferably 50% by mass or more and 95% by mass or less, and more preferably 75% by mass or more and 90% by mass or less.
  • the barrier coat layer can contain the above additives as long as the characteristics of the present invention are not impaired.
  • the thickness of the barrier coat layer is preferably 0.01 ⁇ m or more and 10 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the thickness of the barrier coat layer is preferably 0.01 ⁇ m or more and 10 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the barrier coat layer can be formed by dissolving or dispersing the gas barrier resin in water or a suitable solvent, applying the resin, and drying the resin.
  • a barrier coat layer can also be formed by applying a commercially available barrier coat agent and drying it.
  • the barrier coat layer is a polycondensation of a metal alkoxide obtained by polycondensing a mixture of a metal alkoxide and a water-soluble polymer in the presence of a sol-gel method catalyst, water, an organic solvent, or the like by the sol-gel method.
  • a gas barrier coating film containing at least one resin composition such as a decomposition product or a hydrolyzed condensate of a metal alkoxide.
  • the metal alkoxide is represented by the following general formula.
  • R 1 n M (OR 2 ) m (However, in the formula, R 1 and R 2 each represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents an integer of 1 or more. , N + m represents the valence of M.)
  • metal atom M for example, silicon, zirconium, titanium, aluminum and the like can be used.
  • organic group represented by R 1 and R 2 include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group. ..
  • the metal alkoxide satisfying the above general formula for example, tetramethoxysilane (Si (OCH 3) 4) , tetraethoxysilane (Si (OC 2 H 5) 4), tetra propoxy silane (Si (OC 3 H 7) 4 ), Tetrabutoxysilane (Si (OC 4 H 9 ) 4 ) and the like.
  • a silane coupling agent it is preferable to use a silane coupling agent together with the above metal alkoxide.
  • the silane coupling agent known organic reactive group-containing organoalkoxysilanes can be used, but organoalkoxysilanes having an epoxy group are particularly preferable.
  • organoalkoxysilane having an epoxy group include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Be done.
  • silane coupling agent Two or more kinds of the above-mentioned silane coupling agent may be used, and the silane coupling agent is used within the range of about 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the above metal alkoxide. It is preferable to do so.
  • polyvinyl alcohol and ethylene-vinyl alcohol copolymer are preferable, and from the viewpoint of oxygen barrier property, water vapor barrier property, water resistance and weather resistance, it is preferable to use these in combination.
  • the content of the water-soluble polymer in the gas barrier coating film is preferably 5 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the metal alkoxide.
  • the content of the water-soluble polymer in the gas barrier coating film is preferably 5 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the metal alkoxide.
  • the ratio of the metal alkoxide to the water-soluble polymer is preferably 4.5 or less, preferably 1.0 or more and 4.5 or less, based on the mass. More preferably, it is more preferably 1.7 or more and 3.5 or less.
  • the ratio of silicon atoms to carbon atoms (Si / C) measured by X-ray photoelectron spectroscopy (XPS) is preferably 1.60 or less, and 0.50 or more. It is more preferably 60 or less, and further preferably 0.90 or more and 1.35 or less.
  • XPS X-ray photoelectron spectroscopy
  • XPS X-ray photoelectron spectroscopy
  • the thickness of the gas barrier coating film is preferably 0.01 ⁇ m or more and 100 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 50 ⁇ m or less. Thereby, the oxygen barrier property and the water vapor barrier property can be further improved while maintaining the recyclability.
  • the thickness of the gas barrier coating film By setting the thickness of the gas barrier coating film to 0.01 ⁇ m or more, the oxygen barrier property and the water vapor barrier property of the barrier laminate can be improved. In addition, it is possible to prevent the occurrence of cracks in the vapor deposition film.
  • the thickness of the gas barrier coating film By setting the thickness of the gas barrier coating film to 100 ⁇ m or less, the recyclability of the packaging container produced by using the laminate of the barrier laminate of the present invention and the sealant layer made of polypropylene can be improved.
  • the gas barrier coating film is prepared by applying a composition containing the above materials by a conventionally known means such as a roll coating such as a gravure roll coater, a spray coating, a spin coating, dipping, a brush, a bar code, and an applicator, and the composition thereof.
  • the product can be formed by polycondensing the product by the sol-gel method.
  • the sol-gel method catalyst an acid or amine compound is suitable.
  • the amine compound a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is preferable, and for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, and trypentyl are preferable. Amine and the like can be mentioned.
  • the sol-gel method catalyst is preferably used in the range of 0.01 parts by mass or more and 1.0 parts by mass or less, and 0.03 parts by mass or more and 0.3 parts by mass or less per 100 parts by mass of the metal alkoxide. Is more preferable.
  • the amount of the sol-gel method catalyst By setting the amount of the sol-gel method catalyst to be 0.01 part by mass or more per 100 parts by mass of the metal alkoxide, the catalytic effect can be improved.
  • the amount of the sol-gel method catalyst By setting the amount of the sol-gel method catalyst to be 1.0 part by mass or less per 100 parts by mass of the metal alkoxide, the thickness of the formed gas barrier coating film can be made uniform.
  • the composition may further contain an acid.
  • the acid is used as a catalyst for the sol-gel process, mainly as a catalyst for hydrolysis of metal alkoxides, silane coupling agents and the like.
  • the acid for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid are used.
  • the amount of the acid used is preferably 0.001 mol or more and 0.05 mol or less with respect to the total molar amount of the alkoxide content (for example, the silicate portion) of the metal alkoxide and the silane coupling agent.
  • the catalytic effect can be improved by setting the amount of the acid to be 0.001 mol or more with respect to the total molar amount of the alkoxide content (for example, the silicate portion) of the metal alkoxide and the silane coupling agent.
  • the amount of acid used can be 0.05 mol or less with respect to the total molar amount of the alkoxide content (for example, the silicate portion) of the metal alkoxide and the silane coupling agent.
  • the composition preferably contains water in a ratio of 0.1 mol or more and 100 mol or less, more preferably 0.8 mol or more and 2 mol or less, based on 1 mol of the total molar amount of the metal alkoxide. ..
  • water content By setting the water content to 0.1 mol or more with respect to 1 mol of the total molar amount of the metal alkoxide, the oxygen barrier property and the water vapor barrier property of the barrier laminate of the present invention can be improved.
  • the hydrolysis reaction can be carried out rapidly.
  • the above composition may contain an organic solvent.
  • the organic solvent for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.
  • a composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel method catalyst, water, an organic solvent and, if necessary, a silane coupling agent.
  • the polycondensation reaction gradually proceeds in the composition.
  • the composition is applied and dried on the thin-film deposition film by the above-mentioned conventionally known method. By this drying, the polycondensation reaction of the metal alkoxide and the water-soluble polymer (and the silane coupling agent if the composition contains a silane coupling agent) further proceeds to form a layer of the composite polymer.
  • the gas barrier coating film can be formed by heating the composition at a temperature of, for example, 20 to 250 ° C., preferably 50 to 220 ° C. for 1 second to 10 minutes.
  • the barrier coat layer may have a print layer formed on its surface.
  • the method of forming the print layer and the like are as described above.
  • the heat-sealable laminate 20 of the present invention is characterized by including the barrier laminate 10 and the sealant layer 21.
  • the barrier laminate 10 of the heat-sealable laminate 20 includes a multilayer base material 11 and a vapor-deposited film 12, and the multilayer base material 11 is a polypropylene resin layer 13. And at least the layer 14.
  • the barrier laminate 10 of the heat-sealable laminate 20 includes a multilayer base material 11, a vapor-deposited film 12, and a barrier coat layer 15 provided on the vapor-deposited film 12.
  • the multilayer base material 11 includes at least a polypropylene resin layer 13 and a surface resin layer 14.
  • the barrier laminate 10 of the heat-sealing laminate 20 includes a multilayer base material 11 and a vapor-deposited film 12.
  • the multilayer base material 11 includes a polypropylene resin layer 13, an adhesive resin layer 16, and a surface resin layer 14, and the adhesive resin layer 16 is provided between the polypropylene resin layer 13 and the surface resin layer 14.
  • the barrier laminate 10 of the heat-sealable laminate 20 includes a multilayer base material 11, a vapor-deposited film 12, and a barrier coat layer 15 provided on the vapor-deposited film 12. To be equipped.
  • the multilayer base material 11 includes a polypropylene resin layer 13, an adhesive resin layer 16, and a surface resin layer 14, and the adhesive resin layer 16 is provided between the polypropylene resin layer 13 and the surface resin layer 14. ing.
  • the lamination strength between the multilayer base material and the vapor-deposited film is preferably 3N or more, more preferably 4N or more, and further preferably 5.5N or more in a width of 15 mm.
  • the upper limit of the laminate strength of the heat-sealable laminate may be 20 N or less. A method for measuring the laminate strength of the heat-sealable laminate will be described in Examples described later.
  • the sealant layer can be formed of a resin material that can be fused to each other by heat.
  • Resin materials that can be fused to each other by heat include, for example, polyolefins such as polyethylene, polypropylene, polybutene, methylpentene polymer and cyclic olefin copolymer.
  • polyolefins such as polyethylene, polypropylene, polybutene, methylpentene polymer and cyclic olefin copolymer.
  • LDPE low-density polyethylene
  • MDPE medium-density polyethylene
  • HDPE high-density polyethylene
  • LLDPE linear low-density polyethylene
  • ethylene copolymerized using a metallocene catalyst ethylene copolymerized using a metallocene catalyst.
  • Examples thereof include ⁇ -olefin copolymers and polyethylene-propylene copolymers such as random or block copolymers of ethylene and propylene.
  • Examples of the resin material that can be fused to each other by heat include ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), and ethylene.
  • EMA ethylene-methyl methacrylate copolymer
  • EMMA ethylene-methyl methacrylate copolymer
  • ionomer resin heat-sealing ethylene-vinyl alcohol resin
  • polyolefin as acrylic acid, methacrylate, maleic acid, maleic anhydride, fumal
  • PAA ethylene-methyl methacrylate copolymer
  • EMMA ethylene-methyl methacrylate copolymer
  • ionomer resin heat-sealing ethylene-vinyl alcohol resin
  • polyolefin as acrylic acid, methacrylate, maleic acid, maleic anhydride, fumal
  • polyesters such as polyethylene terephthalate (PET), polyvinyl acetate resins, poly (meth) acrylic resins, and polyvinyl chloride resins.
  • the sealant layer is preferably made of polypropylene from the viewpoint of recyclability of the packaging container produced by using the heat-sealable laminate.
  • the sealant layer can contain the above additives as long as the characteristics of the present invention are not impaired.
  • the sealant layer may have a single-layer structure or a multi-layer structure.
  • the thickness of the sealant layer is preferably 20 ⁇ m or more and 100 ⁇ m or less, and more preferably 30 ⁇ m or more and 70 ⁇ m or less.
  • the thickness of the sealant layer is preferably 20 ⁇ m or more and 100 ⁇ m or less, and more preferably 30 ⁇ m or more and 70 ⁇ m or less.
  • the packaging container of the present invention is characterized by comprising the above-mentioned heat-sealing laminate.
  • the packaging container include a packaging product (packaging bag), a lid material, and a laminated tube.
  • a packaging bag for example, standing pouch type, side seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gassho-attached seal type (pillow-seal type), fold-attached seal type, flat-bottom seal type ,
  • Various types of packaging bags such as a square bottom seal type and a gusset type.
  • FIG. 12 is a diagram briefly showing an example of the configuration of a standing pouch, which is an example of a packaging container.
  • the packaged product 30 is composed of a body portion (side sheet) 31 and a bottom portion (bottom sheet) 32.
  • the side sheet 31 and the bottom sheet 32 included in the standing pouch 30 may be made of the same member or may be made of different members.
  • the body portion 31 included in the packaged product 30 can be formed by making a bag so that the heat-sealing layer included in the heat-sealing laminate of the present invention is the innermost layer.
  • two heat-sealable laminates of the present invention are prepared, these are laminated so that the heat-sealable layers face each other, and the heat-sealable laminates are overlapped from both ends of the heat-sealable laminate. It can be formed by inserting two V-shaped laminates and heat-sealing them so that the heat-sealing layer is on the outside. According to such a manufacturing method, the packaged product 30 having a body portion with a gusset 33 as shown in FIG. 13 can be obtained.
  • the bottom sheet 32 included in the packaged product 30 can be formed by inserting the laminate of the present invention between the bag-made side sheets and heat-sealing. More specifically, the heat-sealable laminate is folded in a V shape so that the heat seal layer is on the outside, and the V-shaped laminate is inserted between the bag-made side sheets.
  • the bottom sheet 32 can be formed by heat-sealing.
  • the packaged product 30 may be a flat packaging bag having no bottom, as shown in FIG.
  • a heat sealing method for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.
  • the contents to be filled in the packaging container are not particularly limited, and the contents may be liquid, powder or gel.
  • the contents may be food or non-food.
  • Example 1-1 Polyamide (manufactured by Ube Industries, Ltd., polyamide 6, melting point: 220 ° C.), adhesive resin (manufactured by Mitsui Chemicals, Inc., Admer QF500, maleic anhydride-modified polypropylene), and polypropylene (manufactured by Japan Polypropylene Corporation, After co-extruding with Novatec FL203D, melting point: 160 ° C.), a multilayer base material is prepared by stretching 5 times in the vertical direction (MD direction) and 10 times in the horizontal direction (TD direction) by a sequential biaxial stretching device. did.
  • MD direction vertical direction
  • TD direction horizontal direction
  • the multilayer base material produced as described above was provided with a surface resin layer made of polyamide, an adhesive resin layer made of an adhesive resin, and a polypropylene resin layer made of polypropylene, and had a total thickness of 20 ⁇ m.
  • the ratio of the thickness of the surface resin layer made of polyamide to the layer thickness of the multilayer base material was 2%.
  • the ratio C of carbon, the ratio Si of silicon, and the ratio O of oxygen are 32.7% and 29, respectively, with respect to 100% of the total of the three elements of silicon, oxygen, and carbon. It was 8.8% and 37.5%.
  • the proportion of each element was measured by X-ray photoelectron spectroscopy (XPS) by narrow scan analysis under the following measurement conditions.
  • a water-soluble polymer 14.7 g of polyvinyl alcohol having a degree of polymerization of 99% or more and a degree of polymerization of 2400 and 17 g of 324 g of water and 17 g of isopropyl alcohol were mixed to obtain a solution B.
  • Solution A and Solution B were mixed so that the ratio was 6.5: 3.5 on a mass basis to obtain a barrier coating agent.
  • a barrier coating agent is coated on a vapor-deposited film formed on a multilayer substrate by a spin coating method, and heat-treated in an oven at 80 ° C. for 60 seconds to form a barrier coating layer having a thickness of 300 nm.
  • a barrier laminate was obtained.
  • Example 1-2 The barrier was the same as in Example 1-1 except that the polyamide was changed to polyvinyl alcohol (manufactured by Japan Vam & Poval Co., Ltd., Bhopal JC-33, melting point: 200 ° C.) to form a surface resin layer. A sex laminate was prepared.
  • Example 1-3 A barrier laminate was produced in the same manner as in Example 1-1 except that the polyamide was changed to ethylene vinyl alcohol (manufactured by Kuraray Co., Ltd., EVAL F171B, melting point: 183 ° C.) to form a surface resin layer. did.
  • ethylene vinyl alcohol manufactured by Kuraray Co., Ltd., EVAL F171B, melting point: 183 ° C.
  • Example 1-4 Barrier lamination was carried out in the same manner as in Example 1-1 except that the polyamide was changed to a non-crystalline polyester (manufactured by Toyobo Co., Ltd., Byron RN-9300, melting point: 198 ° C.) to form a surface resin layer.
  • the body was made.
  • Comparative Example 1-1 After co-extruding polypropylene (manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160 ° C.), it is stretched 5 times in the vertical direction (MD direction) and 10 times in the horizontal direction (TD direction) by a sequential biaxial stretching device. Then, a base material having a thickness of 20 ⁇ m was prepared. A vapor-deposited film and a barrier coat layer were formed on the base material in the same manner as in Example 1-1 except that the multilayer base material was changed to the base material prepared as described above to obtain a laminated body.
  • polypropylene manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160 ° C.
  • Example 2-1 A barrier laminate was produced in the same manner as in Example 1-1 except that the formation of the thin-film deposition film was changed as follows.
  • the conditions for forming the vapor-deposited film were as follows.
  • Example 2-2 The barrier was the same as in Example 2-1 except that the polyamide was changed to polyvinyl alcohol (manufactured by Japan Vam & Poval Co., Ltd., Bhopal JC-33, melting point: 200 ° C.) to form a surface resin layer. A sex laminate was prepared.
  • Example 2-3 A barrier laminate was produced in the same manner as in Example 2-1 except that the polyamide was changed to ethylene vinyl alcohol (manufactured by Kuraray Co., Ltd., EVAL F171B, melting point: 183 ° C.) to form a surface resin layer. did.
  • ethylene vinyl alcohol manufactured by Kuraray Co., Ltd., EVAL F171B, melting point: 183 ° C.
  • Example 2-4 Barrier lamination was performed in the same manner as in Example 2-1 except that the polyamide was changed to a non-crystalline polyester (manufactured by Toyobo Co., Ltd., Byron RN-9300, melting point: 198 ° C.) to form a surface resin layer.
  • the body was made.
  • Comparative Example 2-1 After co-extruding polypropylene (manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160 ° C.), it is stretched 5 times in the vertical direction (MD direction) and 10 times in the horizontal direction (TD direction) by a sequential biaxial stretching device. Then, a base material having a thickness of 20 ⁇ m was prepared. A vapor-deposited film and a barrier coat layer were formed on the base material in the same manner as in Example 2-1 except that the multilayer base material was changed to the base material prepared as described above to obtain a laminated body.
  • polypropylene manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160 ° C.
  • Example 3-1 A barrier laminate was produced in the same manner as in Example 1-1 except that the formation of the thin-film deposition film was changed as follows.
  • the pretreatment section Roll to Roll using a continuous vapor deposition film deposition apparatus that separates the pretreatment section in which the oxygen plasma pretreatment device is arranged and the film formation section, which is an actual machine, on the surface resin layer. Therefore, while applying tension to the multilayer substrate, plasma is introduced from the plasma supply nozzle under the following conditions, oxygen plasma pretreatment is performed, and in the thin-film deposition section that is continuously conveyed, a vacuum is applied to the oxygen plasma treatment surface under the following conditions.
  • a reactive resistance heating method was used as the heating means of the vapor deposition method to form an aluminum oxide (alumina) vapor deposition film having a thickness of 12 nm (PVD method).
  • Example 3-2 The barrier was the same as in Example 3-1 except that the polyamide was changed to polyvinyl alcohol (manufactured by Japan Vam & Poval Co., Ltd., Bhopal JC-33, melting point: 200 ° C.) to form a surface resin layer.
  • a sex laminate was prepared.
  • Example 3-3 A barrier laminate was produced in the same manner as in Example 3-1 except that the polyamide was changed to ethylene vinyl alcohol (manufactured by Kuraray Co., Ltd., EVAL F171B, melting point: 183 ° C.) to form a surface resin layer. did.
  • ethylene vinyl alcohol manufactured by Kuraray Co., Ltd., EVAL F171B, melting point: 183 ° C.
  • Example 3-4 Barrier lamination was performed in the same manner as in Example 3-1 except that the polyamide was changed to a non-crystalline polyester (manufactured by Toyobo Co., Ltd., Byron RN-9300, melting point: 198 ° C.) to form a surface resin layer.
  • the body was made.
  • Comparative Example 3-1 After co-extruding polypropylene (manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160 ° C.), it is stretched 5 times in the vertical direction (MD direction) and 10 times in the horizontal direction (TD direction) by a sequential biaxial stretching device. Then, a base material having a thickness of 20 ⁇ m was prepared. A vapor-deposited film and a barrier coat layer were formed on the base material in the same manner as in Example 3-1 except that the multilayer base material was changed to the base material prepared as described above to obtain a laminated body.
  • polypropylene manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160 ° C.
  • [Oxygen permeability] Using an oxygen permeability measuring device (OX-TRAN2 / 20 manufactured by MOCON), set the test piece so that the multilayer base material side of the test piece is the oxygen supply side, and conform to JIS K 7126, 23 ° C., relative humidity. Oxygen permeability was measured in a 90% RH environment.
  • [Water vapor permeability] Using a water vapor permeability measuring device (MOCON, PERMATRAN-w 3/33), set the test piece so that the multilayer base material side of the test piece is the water vapor supply side, and set it at 40 ° C. in accordance with JIS K 7129. The water vapor permeability in a 90% relative humidity RH environment was measured.
  • Laminate strength test >> A sealant layer is formed by dry laminating an unstretched polypropylene film having a thickness of 40 ⁇ m on the barrier coat layer provided in the barrier laminates and the laminates obtained in the above Examples and Comparative Examples to prepare a heat-sealable laminate. did. This heat-sealable laminate was cut into strips with a width of 15 mm, and a test piece was used with a tensile tester (Orientec Co., Ltd., Tencilon universal material tester) in accordance with JIS K6854-2, and a vapor-deposited film.
  • a tensile tester Orientec Co., Ltd., Tencilon universal material tester
  • the lamination strength (N / 15 mm) between the surface resin layer and the vapor-deposited film and the polypropylene film was measured by 90 ° peeling (T-shaped peeling method) at a peeling speed of 50 mm / min.
  • T-shaped peeling method 90 ° peeling
  • a strip-shaped test piece 40 is obtained by cutting out a heat-sealable laminate and peeling the multilayer base material side 41 and the sealant layer side 42 by 15 mm in the long side direction as shown in FIG. Prepared.
  • the already peeled portions of the multilayer base material side 41 and the sealant layer side 42 were gripped by the gripping tool 43 of the measuring instrument, respectively.
  • Each of the gripping tools 43 is pulled in a direction orthogonal to the surface direction of the portion where the multilayer base material side 41 and the sealant layer side 42 are still laminated, in opposite directions at a speed of 50 mm / min, and a stable region (stable region).
  • the average value of the tensile stress in was measured.
  • the distance S between the gripping tools 43 at the start of pulling was set to 30 mm, and the distance S between the gripping tools 43 at the end of pulling was set to 60 mm.
  • FIG. 17 is a diagram showing changes in tensile stress with respect to the interval S between the gripping tools 43. As shown in FIG.
  • the change in tensile stress with respect to the interval S passes through the first region and enters the second region (stable region) where the rate of change is smaller than that of the first region.
  • the average value of the tensile stress in the stable region was measured, and the average value was taken as the lamination strength.
  • the environment at the time of measurement was a temperature of 23 ° C. and a relative humidity of 50%. The measurement results are summarized in Tables 1 to 3.
  • Example 4-1 Similar to Example 1-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 5.1 on a mass basis.
  • an unstretched polypropylene film having a thickness of 70 ⁇ m was dry-laminated with a two-component curable polyurethane adhesive on the barrier coat layer provided in the barrier laminate to form a sealant layer, thereby producing a heat-seal laminate. ..
  • Example 4-2 Similar to Example 4-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis. To prepare a barrier-type laminate and a heat-sealable laminate.
  • Example 4-3 Similar to Example 4-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 4-4 Similar to Example 4-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis. To prepare a barrier-type laminate and a heat-sealable laminate.
  • Example 4-5 Similar to Example 4-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 4-6 Similar to Example 4-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. To prepare a barrier-type laminate and a heat-sealable laminate.
  • Example 5-1 Similar to Example 3-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 5.1 on a mass basis.
  • an unstretched polypropylene film having a thickness of 70 ⁇ m was dry-laminated with a two-component curable polyurethane adhesive on the barrier coat layer provided in the barrier laminate to form a sealant layer, thereby producing a heat-seal laminate. ..
  • Example 5-2 Similar to Example 5-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 5-3 Similar to Example 5-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 5-4 Similar to Example 5-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 5-5 Similar to Example 5-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 5-6 Similar to Example 5-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. To prepare a barrier-type laminate and a heat-sealable laminate.
  • Example 6-1 Similar to Example 1-3, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 5.1 on a mass basis.
  • an unstretched polypropylene film having a thickness of 70 ⁇ m was dry-laminated with a two-component curable polyurethane adhesive on the barrier coat layer provided in the barrier laminate to form a sealant layer, thereby producing a heat-seal laminate. ..
  • Example 6-2 Same as Example 6-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis. To prepare a barrier-type laminate and a heat-sealable laminate.
  • Example 6-3 Same as Example 6-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis. To prepare a barrier-type laminate and a heat-sealable laminate.
  • Example 6-4 Similar to Example 6-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis. To prepare a barrier-type laminate and a heat-sealable laminate.
  • Example 6-5 Similar to Example 6-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 6-6 Similar to Example 6-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. To prepare a barrier-type laminate and a heat-sealable laminate.
  • Example 7-1 Similar to Example 3-3, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 5.1 on a mass basis.
  • an unstretched polypropylene film having a thickness of 70 ⁇ m was dry-laminated with a two-component curable polyurethane adhesive on the barrier coat layer provided in the barrier laminate to form a sealant layer, thereby producing a heat-seal laminate. ..
  • Example 7-2 Similar to Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 7-3 Similar to Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 7-4 Similar to Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 7-5 Similar to Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis.
  • metal alkoxide / water-soluble polymer metal alkoxide / water-soluble polymer
  • Example 7-6 Similar to Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. To prepare a barrier-type laminate and a heat-sealable laminate.
  • ⁇ Gas barrier property evaluation (after boiling) >> Using the barrier laminates obtained in Examples 4 and 5, a pouch-shaped packaging container as shown in FIG. 14 was prepared. The size of the pouch-shaped packaging container is B5 size (182 mm ⁇ 257 mm). The inside of the pouch-shaped packaging container is filled with 100 mL of water. The pouch-shaped packaging container was boiled at 95 ° C. for 30 minutes. A heat-sealable laminate was cut out from the pouch-shaped packaging container to obtain a test piece. Using this test piece, oxygen permeability (cc / m 2 ⁇ day ⁇ atm) and water vapor permeability (g / m 2 ⁇ day) were measured in the same manner as described above. The results are summarized in Tables 4 and 5. In Tables 4 and 5, the units of oxygen permeability and vapor permeability are omitted.
  • ⁇ Evaluation of gas barrier property (after retort) >> Using the barrier laminates obtained in Examples 4 and 5, a pouch-shaped packaging container as shown in FIG. 14 was prepared.
  • the size of the pouch-shaped packaging container is B5 size (182 mm ⁇ 257 mm).
  • the inside of the pouch-shaped packaging container is filled with 100 mL of water.
  • the pouch-shaped packaging container was retort-sterilized at 121 ° C. for 30 minutes. A heat-sealable laminate was cut out from the pouch-shaped packaging container to obtain a test piece.

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

Abstract

La présente invention vise à fournir un stratifié barrière qui : comprend un matériau de base multicouche ayant une excellente adhérence intercouche entre un film de dépôt en phase vapeur et le matériau de base multicouche ; et a des propriétés barrières aux gaz élevées. La solution selon l'invention porte sur un stratifié barrière qui comprend un matériau de base multicouche et un film de dépôt en phase vapeur. Le matériau de base multicouche a subi un traitement d'étirage et comprend au moins une couche de résine polypropylène et une couche de résine de surface. Le stratifié barrière est caractérisé par : la couche de résine de surface comprenant une matière de résine ayant un point de fusion d'au moins 180 °C ; et le film de dépôt en phase vapeur comprenant un oxyde inorganique.
PCT/JP2020/036838 2019-09-30 2020-09-29 Stratifié barrière, stratifié thermosoudable comprenant ledit stratifié barrière et contenant d'emballage comprenant ledit stratifié thermosoudable WO2021065887A1 (fr)

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JP2021508013A JP6962499B2 (ja) 2019-09-30 2020-09-29 バリア性積層体、該バリア性積層体を備えるヒートシール性積層体および該ヒートシール性積層体を備える包装容器
JP2021169182A JP7351328B2 (ja) 2019-09-30 2021-10-14 バリア性積層体、該バリア性積層体を備えるヒートシール性積層体および該ヒートシール性積層体を備える包装容器

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023157881A1 (fr) * 2022-02-15 2023-08-24 大日本印刷株式会社 Film barrière stratifié, film stratifié, corps stratifié et récipient d'emballage
DE102022120789A1 (de) 2022-08-17 2024-02-22 Huhtamaki Flexible Packaging Germany Gmbh & Co. Kg Retortensterilisierbares Lagenmaterial mit Barrierelage aus Metalloxid

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JP2001191462A (ja) * 1999-11-05 2001-07-17 Tohcello Co Ltd 積層体
JP2006256626A (ja) * 2005-03-15 2006-09-28 Toppan Printing Co Ltd 一方向引裂き性を有する包装袋
JP2014531341A (ja) * 2011-09-20 2014-11-27 テトラ・ラヴァル・ホールディングス・アンド・ファイナンス・ソシエテ・アノニムＴｅｔｒａ Ｌａｖａｌ Ｈｏｌｄｉｎｇｓ ＆ Ｆｉｎａｎｃｅ Ｓ．Ａ． 多層バリアフィルム、そのフィルムを含むパッケージングラミネート、そのパッケージングラミネートから形成されるパッケージング容器、及びそのフィルムの製造方法
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023157881A1 (fr) * 2022-02-15 2023-08-24 大日本印刷株式会社 Film barrière stratifié, film stratifié, corps stratifié et récipient d'emballage
DE102022120789A1 (de) 2022-08-17 2024-02-22 Huhtamaki Flexible Packaging Germany Gmbh & Co. Kg Retortensterilisierbares Lagenmaterial mit Barrierelage aus Metalloxid

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