WO2022102414A1 - Film ayant une perméabilité à l'alcool réduite, et matériau d'emballage et emballage comprenant ledit film ayant une perméabilité à l'alcool réduite - Google Patents

Film ayant une perméabilité à l'alcool réduite, et matériau d'emballage et emballage comprenant ledit film ayant une perméabilité à l'alcool réduite Download PDF

Info

Publication number
WO2022102414A1
WO2022102414A1 PCT/JP2021/039734 JP2021039734W WO2022102414A1 WO 2022102414 A1 WO2022102414 A1 WO 2022102414A1 JP 2021039734 W JP2021039734 W JP 2021039734W WO 2022102414 A1 WO2022102414 A1 WO 2022102414A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
alcohol
layer
intermediate layer
film
Prior art date
Application number
PCT/JP2021/039734
Other languages
English (en)
Japanese (ja)
Inventor
アウェルロース アウリア
康史 渡辺
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2022512358A priority Critical patent/JP7207604B2/ja
Publication of WO2022102414A1 publication Critical patent/WO2022102414A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—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
    • 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 an alcohol permeation suppressing film used for packaging materials such as foods and medical products. More specifically, the present invention can realize a packaging material having improved alcohol retention by suppressing alcohol permeation from the film. Regarding the suppression film.
  • foods such as bread, confectionery, noodles, and dried foods may contain an alcohol volatilizer inside a package such as a bag or container in order to maintain quality and freshness.
  • the alcohol volatilizer is a quality preservative that prevents the food from becoming moldy by volatilizing ethyl alcohol inside the package and the gasified ethyl alcohol covering the surface of the food.
  • an alcohol volatilizer By enclosing an alcohol volatilizer, it is thought that the softness of the food can be preserved, the texture of the food can be maintained, and the expiration date can be extended.
  • the alcohol volatilizer is enclosed in a package, it is necessary to fill the inside of the package with vaporized alcohol, so that a package having a low amount of alcohol gas permeation and a high sealing property is required.
  • a gas barrier laminated film in which a gas barrier vapor deposition layer containing an inorganic compound and a gas barrier coating layer containing a silicon compound are laminated on a plastic base material is disclosed (for example, a patent). See Document 1). Since the laminated film has transparency and is also excellent in alcohol blocking property, it can be used as a packaging member suitable for alcohol liquid containers, paper containers for alcoholic beverages, and the like.
  • a laminated film in which a polyolefin-based film having excellent flexibility is bonded is usually used.
  • a material having a lower alcohol gas permeation amount is required.
  • Patent Document 1 since the material described in Patent Document 1 needs to be provided with a gas barrier vapor deposition layer or a gas barrier coating layer containing an inorganic compound, the number of steps is large, the flexibility is inferior, and the cost is high. Therefore, there is a demand for a film having high alcohol retention and appropriate flexibility as a single film without providing a thin-film deposition layer or laminating and laminating with other films.
  • the problems to be solved by the present invention are low permeability of alcohol gas, flexibility and impact resistance, excellent alcohol retention even when used as a single film, and as a packaging material.
  • An object of the present invention is to provide an alcohol permeation inhibitory film that can be suitably used.
  • the present invention contains a polypropylene-based resin having no cyclic structure as a main component, and the polypropylene-based resin contains a propylene homopolymer (a1) and a base material containing propylene and another ⁇ -olefin copolymer (a2).
  • Layer (A) The first intermediate layer (B) containing a cyclic polyolefin resin as a main component,
  • the alcohol permeation suppressing film which is a multilayer film in which the sealing layer (D) containing a polyolefin resin as a main component is laminated in the order of (A) / (B) / (D), solves the above-mentioned problems. be.
  • the alcohol permeation suppressing film of the present invention has low permeability of alcohol gas, it is possible to have excellent alcohol retention even when the film is used alone. Further, since the alcohol permeation suppressing film of the present invention is excellent in flexibility and impact resistance, it is excellent in processability into various packaging forms such as sealing bags and containers, and further has good transparency. The visibility inside the package is also excellent. Therefore, it can be suitably applied to packaging applications for foods, medical products, and pharmaceuticals in which an alcohol volatilizer is encapsulated to maintain quality and freshness.
  • the alcohol permeation inhibitory film of the present invention has a base material layer (A) containing a polypropylene-based resin having no cyclic structure as a main component, a first intermediate layer (B) containing a cyclic polyolefin-based resin as a main component, and a polyolefin.
  • the seal layer (D) containing the based resin as a main component is a multilayer film in which (A) / (B) / (D) are laminated in this order.
  • the "main component" of each layer specifically means the component having the largest proportion among the components constituting the layer.
  • the base material layer (A) of the multilayer film of the present invention contains a polypropylene-based resin having no cyclic structure as a main component, and the polypropylene-based resin includes a propylene homopolymer (a1) and a propylene / other olefin copolymer. It is a layer containing (a2).
  • a2 propylene homopolymer
  • a2 propylene / other olefin copolymer
  • the base material layer (A) serves as the surface layer of the packaging material, so that the packaging material has a gloss.
  • propylene and other olefin copolymer (a2) examples include a propylene-olefin random copolymer, for example, a propylene-ethylene copolymer, a propylene-1-butene copolymer, a propylene-ethylene-1-butene copolymer, and the like. Examples thereof include a metallocene-catalyzed polypropylene. These may be used alone or in combination.
  • Examples of the other olefins include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1 and the like. Therefore, two or more of these may be copolymerized at the same time.
  • the copolymerization type either random copolymerization or block copolymerization can be used.
  • the content of other olefins in the copolymer is preferably 2 to 23 mol%, more preferably 2.5 to 15 mol%.
  • the propylene homopolymer (a1) in combination with the propylene-ethylene random copolymer as the propylene and another olefin copolymer (a2).
  • the propylene homopolymer can be expected to improve heat resistance and rigidity, and the propylene-ethylene random copolymer can be expected to improve glossiness.
  • these polypropylene-based resins preferably have an MFR (230 ° C.) of 0.5 to 30.0 g / 10 minutes and a melting point of 110 to 165 ° C., and more preferably MFR (230 ° C.) of 2. It is 0.0 to 15.0 g / 10 minutes and has a melting point of 115 to 162 ° C. When the MFR and the melting point are in this range, the film forming property of the film is improved.
  • the ratio of the propylene homopolymer (a1) and the propylene to the other olefin copolymer (a2) is the mass ratio of the propylene homopolymer (a1): propylene and the other.
  • the olefin copolymer (a2) is preferably in the range of 20:80 to 80:20, more preferably in the range of 30:70 to 70:30, and in the range of 40:60 to 60:40. Is even more preferable.
  • the base material layer (A) is mainly composed of the above polypropylene-based resin, and other coextrudable resins may be used in combination as long as the effects of the present invention are not impaired.
  • the proportion of the polypropylene-based resin in the total mass of the resin component used for the base material layer (A) is preferably 50% by mass or more, preferably 70% by mass or more, and 80% by mass or more. Is more preferable, and 90% by mass or more is further preferable.
  • the resin other than the polypropylene-based resin used for the base material layer (A) various resins used for packaging films can be used, and among them, olefin-based resins such as ethylene-based resins can be preferably used.
  • the ethylene resin include polyethylene resins such as ultra-low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), linear medium density polyethylene (LMDPE), and medium density polyethylene (MDPE).
  • VLDPE ultra-low density polyethylene
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear medium density polyethylene
  • MDPE medium density polyethylene
  • EVA Polyethylene-vinyl acetate copolymer
  • the content thereof is preferably 30% by mass or less of the resin component contained in the surface layer (A), preferably 10% by mass or less. More preferably, it is more preferably 5% by mass or less.
  • the content of the cyclic polyolefin resin in the resin component contained in the base material layer (A) is preferably 10% by mass or less. It is more preferably mass% or less, and it is also preferable not to use it substantially.
  • a resin other than the above may be used in combination with the base material layer (A) used in the present invention.
  • the other resin include thermoplastic elastomers such as ethylene-based elastomers, propylene-based elastomers, and butene-based elastomers; ethylene-methylmethacrylate copolymers (EMMA), ethylene-ethylacrylate copolymers (EEA), and ethylene.
  • EMA ethylene-ethyl acrylate-maleic anhydride copolymer
  • EAA ethylene-acrylic acid copolymer
  • EAA ethylene-methacrylic acid copolymer
  • Ethylene-based copolymers such as; further, an ionomer of an ethylene-acrylic acid copolymer, an ionomer of an ethylene-methacrylic acid copolymer, and the like can be exemplified.
  • the above other resin when used, it is preferable to use it in an amount of 30% by mass or less, and more preferably 20% by mass or less in the resin component contained in the base material layer (A). It is more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • various additives and the like may be appropriately used in the base material layer (A).
  • a lubricant, an anti-blocking agent, an ultraviolet absorber, a light stabilizer, an anti-static agent, an anti-fog agent, a colorant and the like can be appropriately used.
  • these additives are preferably used in an amount of preferably 2 parts by mass or less, more preferably about 0.01 to 1 part by mass, based on 100 parts by mass of the resin component used for the base material layer (A).
  • the friction coefficient of the base material layer (A) is preferably 0.9 or less, and more preferably 0.8 or less, so that the base material layer ( It is also preferable to appropriately add a lubricant or an antiblocking agent to A).
  • the thickness ratio of the base material layer (A) to the multilayer film is based on the total thickness (total thickness) of the multilayer film because it suppresses alcohol permeation and easily obtains suitable rigidity, heat resistance, packaging machine suitability, and the like.
  • the thickness ratio of the material layer (A) is preferably 15% or more, more preferably 20% or more.
  • the upper limit of the thickness ratio is preferably 75% or less, preferably 50% or less, preferably 30% or less, and 25% or less. Is preferable.
  • First middle layer (B) By containing the cyclic polyolefin resin in the first intermediate layer (B) of the multilayer film of the present invention, excellent easy tearing property and straight-line cutting property can be realized.
  • the cyclic polyolefin-based resin include norbornene-based polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Among these, norbornene-based polymers are preferable.
  • the norbornene-based polymer includes a ring-opening polymer of a norbornene-based monomer (hereinafter referred to as “COP”) and a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an olefin such as ethylene (hereinafter referred to as “COP”). , "COC”) and the like. Also, COP and COC hydrogenated additives are particularly preferred.
  • the weight average molecular weight of the cyclic polyolefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.
  • the norbornene-based polymer and the norbornene-based monomer used as a raw material are alicyclic-based monomers having a norbornene ring.
  • Examples of such norbornene-based monomers include norbornene, tetracyclododecene, etylidene norbornene, vinylnorbornene, etylidetetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenylnorbornene, methoxycarbonylnorbornene, and methoxy. Examples thereof include carbonyltetracyclododecene.
  • These norbornene-based monomers may be used alone or in combination of two or more.
  • the norbornene-based copolymer is a copolymer of the norbornene-based monomer and a copolymerizable olefin, and examples of such olefins include ethylene, propylene, and 1-butene. Examples thereof include olefins having 2 to 20 carbon atoms; cycloolefins such as cyclobutene, cyclopentene and cyclohexene; and non-conjugated diene such as 1,4-hexadiene.
  • the content ratio of the norbornene-based monomer in the norbornene-based copolymer (COC) is preferably 40 to 90 mol%, more preferably 50 to 80 mol%. When the content ratio is within this range, the alcohol permeation suppressing effect, the rigidity of the film, and the processing stability are improved.
  • the content of the cyclic polyolefin resin contained in the first intermediate layer (B) is preferably 70% by mass or more, preferably 80% by mass or more of the resin component contained in the first intermediate layer (B). Is more preferable, and 90% by mass or more is further preferable.
  • the cyclic polyolefin resin used in the first intermediate layer (B) preferably has a glass transition temperature of 140 ° C. or lower, more preferably 50 to 140 ° C., and 70 to 120 ° C. It is more preferable to have.
  • a cyclic polyolefin resin having a glass transition temperature it is easy to obtain good heat resistance and rigidity, and it is easy to improve bag breakage resistance against dropping and the like. In addition, it becomes easy to obtain good compatibility, and it becomes easy to suppress uneven appearance.
  • the glass transition temperature (Tg) is a value obtained by measuring with DSC.
  • a cyclic polyolefin resin having a different glass transition temperature may be used in combination, but 60% by mass or more thereof is a cyclic polyolefin resin having a glass transition point of 120 ° C. or less from the viewpoint of extrusion suitability, cost, easy tearability and the like. Is preferable.
  • the MFR of the cyclic polyolefin resin is 0.2 to 17 g / 10 minutes (230 ° C., 21.18N), preferably 3 to 15 g / 10 minutes (230 ° C., 21.18N), and more preferably 5 to 13 g / 10. Minutes (230 ° C., 21.18N).
  • MFR is in this range, it is preferable in that it has excellent compatibility with linear low-density polyethylene and good film forming property can be obtained in various multilayer film forming methods.
  • examples of the ring-opening polymer (COP) of the norbornene-based monomer include “ZEONOR” manufactured by Nippon Zeon Co., Ltd., and the norbornene-based monomer is used.
  • examples of the copolymer (COC) include "Appel” manufactured by Mitsui Kagaku Co., Ltd. and "TOPAS” manufactured by Polyplastics Co., Ltd.
  • the resin component in the first intermediate layer (B) it is preferable to contain only the cyclic polyolefin-based resin, but a resin other than these resin components may be used in combination as long as the effect of the present invention is not impaired. You may.
  • a resin other than these resin components may be used in combination as long as the effect of the present invention is not impaired. You may.
  • an olefin-based resin having no cyclic structure other than the cyclic polyolefin-based resin such as the polyethylene-based resin and the polypropylene-based resin exemplified in the base material layer (A) can be exemplified. ..
  • the content is preferably 30% by mass or less, preferably 20% by mass or less, in the resin component contained in the first intermediate layer (B). It is more preferably 10% by mass or less.
  • the lower limit is not particularly limited, but the content may be appropriately used in an amount of 1% by mass or more depending on the desired characteristics.
  • various additives and the like may be appropriately used in combination in the first intermediate layer (B).
  • a lubricant, an anti-blocking agent, an ultraviolet absorber, a light stabilizer, an anti-static agent, an anti-fog agent, a colorant and the like can be appropriately used.
  • these additives are preferably used in an amount of preferably 2 parts by mass or less, more preferably about 0.01 to 1 part by mass, based on 100 parts by mass of the resin component used for the first intermediate layer (B). do.
  • the thickness ratio of the first intermediate layer (B) to the multilayer film is preferably 25% or less, preferably 20% or less, from the viewpoint of cost, film forming property, and curling property of the film. It is preferably 15% or less, and preferably 10% or less. Further, the lower limit is preferably 3% or more, and preferably 5% or more in order to suppress alcohol permeation.
  • the seal layer (D) used for the multilayer film of the present invention for example, a heat seal layer used for various packaging films can be appropriately used.
  • the layer is mainly composed of a polyolefin resin, particularly a polyolefin resin having no cyclic structure. Is preferable.
  • the polyolefin-based resin the polyethylene-based resin or polypropylene-based resin exemplified in the base material layer (A) or the like can be preferably used.
  • a polypropylene- ⁇ -olefin random copolymer polymerized using a polyethylene resin having a density of 0.916 to 0.935 g / cm 3 or a metallocene catalyst from the viewpoints of strength, sealing property, and suitability for packaging machines. It is preferable to use a certain polypropylene resin. In particular, it is preferable to use linear low-density polyethylene because it is easy to obtain suitable sealing properties. Further, the above range of densities is preferable from the viewpoint of suppressing mutual adhesion of films in the boil sterilization step.
  • the content of the polyolefin-based resin in the resin component contained in the seal layer (D) is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. preferable. Further, 100% by mass of the resin component contained in the seal layer (D) may be linear low-density polyethylene.
  • a resin other than the above-mentioned polyolefin resin may be used in combination as long as the effect of the present invention is not impaired, and the other resin may be used in the base material layer (A) or the like.
  • the other resin examples thereof include thermoplastic elastomers, ethylene-based copolymers, ionomers, and the like.
  • the other resin it is preferable to use it in an amount of 30% by mass or less, and more preferably 20% by mass or less in the resin component contained in the seal layer (D). It is more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • the seal layer (D) various additives and the like may be appropriately used in the seal layer (D).
  • a lubricant, an anti-blocking agent, an ultraviolet absorber, a light stabilizer, an anti-static agent, an anti-fog agent, a colorant and the like can be appropriately used.
  • these additives are preferably used in an amount of 2 parts by mass or less, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the resin component used for the seal layer (D).
  • the coefficient of friction of the seal layer (D) is preferably 0.9 or less, and more preferably 0.8 or less in order to impart processing suitability at the time of film molding and packaging suitability of the filling machine. Therefore, the seal layer (D) It is also preferable to add a lubricant or an anti-blocking agent as appropriate.
  • the melting point of the base material layer (A) is 10 ° C. or more higher than the melting point of the sealing layer (D).
  • the thickness ratio of the seal layer (D) to the total thickness of the multilayer film is preferably 30% or less, and more preferably 10 to 25%, because it is easy to obtain suitable tearability and seal strength. preferable.
  • the alcohol permeation suppressing film of the present invention has a second intermediate layer (C) containing a polyethylene resin as a main component between the base material layer (A) and the first intermediate layer (B). May be good. That is, the base material layer (A), the second intermediate layer (C), the first intermediate layer (B), and the seal layer (D) containing a polyolefin resin as a main component are (A) / (C). It may be a multilayer film laminated in the order of / (B) / (D). As described above, the structure having the second intermediate layer (C) containing the polyethylene-based resin as the main component can enhance the flexibility, the impact resistance, and the alcohol permeation suppressing effect.
  • the second intermediate layer (C) is preferably a layer containing the polyethylene-based resin (c) as a main component.
  • polyethylene-based resin (c) examples include linear low-density polyethylene (LLDPE), linear medium-density polyethylene (LMDPE), linear high-density polyethylene (LHDPE), low-density polyethylene (LDPE), and medium-density.
  • LLDPE linear low-density polyethylene
  • LHDPE linear high-density polyethylene
  • LDPE low-density polyethylene
  • Polyethylene resins such as polyethylene (MDPE) and high density polyethylene (HDPE), ethylene-butene-rubber copolymer (EBR), ethylene-propylene-rubber copolymer (EPR), ethylene-vinyl acetate copolymer (EVA), ethylene- Methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH) , Ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), etc.; Ionomer and the like can be mentioned, and two or more types may be used alone or in admixture of two or more.
  • LDPE, LMDPE, LHDPE, LLDPE, MDPE, HDPE, and EBR are preferably used because
  • a high-density polyethylene (c1) having a density of 0.950 g / cm 2 or more and an ethylene resin (c2) having a density of 0.900 g / cm 2 or more and less than 0.945 g / cm 2 ) Is preferably contained.
  • High-density polyethylene (c1) is preferable because it tends to improve the alcohol permeation suppressing effect and rigidity.
  • the density of the high-density polyethylene (c1) is preferably 0.950 g / cm 2 or more, and more preferably 0.955 g / cm 2 or more as described above.
  • the ethylene resin (c2) is preferable because it improves impact resistance, and it is preferable to use an ethylene resin as a main component in the second intermediate layer.
  • the ethylene resin (c2) is preferably LLDPE or LMDPE, and as described above, the density is preferably in the range of 0.900 g / cm 2 or more and less than 0.945 g / cm 2 , but 0.930 g / cm.
  • the MFR of the ethylene resin (c2) is 0.1 to 20 g / 10 minutes (190 ° C., 21.18N), preferably 0.3 to 10 g / 10 minutes (190 ° C., 21.18N), more preferably. Is 0.5 to 5 g / 10 minutes (190 ° C., 21.18N). When the MFR is in this range, good film forming property can be obtained, which is preferable.
  • both high-density polyethylene (c1) and ethylene-based resin (c2) from the viewpoint of achieving both an alcohol permeation suppressing effect and flexibility and impact resistance.
  • the content of the polyethylene-based resin (c) in the second intermediate layer (C) is 65% by mass or more in the resin component contained in the second intermediate layer (C). Achieves excellent impact resistance and alcohol retention.
  • the content is preferably 68% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more in the resin component contained in the second intermediate layer (C). It is preferably 80% by mass or more, and particularly preferably 80% by mass or more. Further, 100% by mass of the resin component contained in the second intermediate layer (C) may be a polyethylene-based resin.
  • a resin other than the polyethylene-based resin (c) may be used in combination in the second intermediate layer (C) as long as the effect of the present invention is not impaired.
  • an olefin resin such as the polypropylene resin exemplified in the base material layer (A) can be exemplified.
  • an olefin resin such as a polypropylene resin
  • the content thereof is 35% by mass or less of the resin component contained in the second intermediate layer (C). It is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the content of the cyclic polyolefin resin in the resin component contained in the second intermediate layer (C) is preferably 10% by mass or less. It is more preferably 5% by mass or less, and it is also preferable not to use it substantially.
  • a resin other than the above may be used in combination in the second intermediate layer (C), and the other resin may be a thermoplastic elastomer or an ethylene-based resin exemplified in the base material layer (A). Examples thereof include copolymers and ionomers.
  • the other resin When the other resin is used, its content is preferably 35% by mass or less, and more preferably 30% by mass or less in the resin component contained in the second intermediate layer (C). It is more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • various additives and the like may be appropriately used in the second intermediate layer (C).
  • a lubricant, an anti-blocking agent, an ultraviolet absorber, a light stabilizer, an anti-static agent, an anti-fog agent, a colorant and the like can be appropriately used.
  • these additives are preferably used in an amount of preferably 5 parts by mass or less, more preferably about 0.01 to 3 parts by mass, based on 100 parts by mass of the resin component used for the second intermediate layer (C). do.
  • the thickness ratio of the second intermediate layer (C) containing the polyethylene resin (c) as a main component to the multilayer film is 30 from the viewpoint of the alcohol permeation suppressing effect and other performance balance, particularly low temperature impact resistance. % Or more, and particularly preferably in the range of 35 to 70%.
  • the substrate layer (A), the first intermediate layer (B), and the sealing layer (D) are laminated at least in the order of (A) / (B) / (D). It's a film.
  • the multilayer film of the present invention can suppress alcohol permeation, and can realize impact resistance and flexibility.
  • the base material layer (A), the second intermediate layer (C), and the first intermediate layer are used.
  • the layer (B) and the seal layer (D) are multilayer films in which at least (A) / (C) / (B) / (D) are laminated in this order.
  • the multilayer film of the present invention preferably has a total film thickness of 20 to 90 ⁇ m, more preferably 30 to 60 ⁇ m. When the thickness of the film is within this range, it becomes easy to achieve both stable sealing strength, packaging machine suitability, excellent pinhole resistance, and alcohol permeation suppressing effect.
  • each layer is not particularly limited, but for example, the thickness of the surface layer (A) is preferably 3 to 15 ⁇ m, more preferably 5 to 12 ⁇ m.
  • the thickness of the first intermediate layer (B) is preferably 1 to 20 ⁇ m, and preferably 2 to 15 ⁇ m.
  • the thickness of the first intermediate layer (B) is preferably 1 to 15 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the thickness of the second intermediate layer (C) is preferably 8 to 35 ⁇ m, more preferably 10 to 30 ⁇ m.
  • the thickness of the seal layer (D) is preferably 2 to 20 ⁇ m, more preferably 4 to 15 ⁇ m.
  • the multilayer film of the present invention preferably has a sealing strength of 5 N / 15 mm or more, and more preferably 10 N / 15 mm or more.
  • the degree of fogging of the multilayer film of the present invention is preferably 10% or less, more preferably 8% or less, still more preferably 5% or less, because the contents to be packaged are easily visible.
  • the multilayer film of the present invention has such high transparency, it is easy to realize suitable packaging suitability and suitable print adhesion.
  • the multilayer film of the present invention preferably has an alcohol concentration residual rate of 10 ppm or more, more preferably 20 ppm or more, after being held at a temperature of 25 ° C. for 6 days.
  • alcohol concentration residual rate 10 ppm or more, more preferably 20 ppm or more, after being held at a temperature of 25 ° C. for 6 days.
  • the impact strength of the laminated film of the present invention is preferably 0.60 J (0 ° C.) or higher, more preferably 0.70 J (0 ° C.) or higher, and 0.80 J (0 ° C.) or higher. It is more preferably present, and further preferably 0.90 J (0 ° C.) or higher.
  • the impact strength is determined by holding the sample in a constant temperature room adjusted to 0 ° C. for 4 hours and then measuring the impact strength by the film impact method using a spherical impact head having a diameter of 1.5 inches.
  • the method for producing the multilayer film of the present invention is not particularly limited, but is used for, for example, the base material layer (A), the second intermediate layer (C), the first intermediate layer (B), and the seal layer (D).
  • Each resin or resin mixture is heated and melted by a separate extruder, and the melted state is in the order of (A) / (C) / (B) / (D) by a method such as a coextrusion multi-layer die method or a feed block method. Examples thereof include a coextrusion method in which the film is formed into a film by inflation, a T-die chill roll method, or the like.
  • This coextrusion method is preferable because the thickness ratio of each layer can be adjusted relatively freely, and a multilayer film having excellent hygiene and cost performance can be obtained.
  • the polyethylene-based resin used in the second intermediate layer (C) has a difference in softening point (melting point) from the cyclic polyolefin-based resin used in the other layers. Due to its large size, phase separation and gel may occur. In order to suppress such phase separation and gel generation, the T-die chill roll method capable of melt extrusion at a relatively high temperature is preferable.
  • the multilayer film of the present invention can be obtained as a substantially unstretched multilayer film by the above manufacturing method, secondary molding such as deep drawing by vacuum forming is also possible.
  • a surface treatment to the base material layer (A).
  • examples of such surface treatments include corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, surface oxidation treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sandblasting. Corona treatment is preferable.
  • Examples of the packaging material made of the multilayer film of the present invention include packaging bags, packaging containers and the like used for foods, chemicals, industrial parts, miscellaneous goods, magazines and the like. Above all, since the multilayer film of the present invention can suppress alcohol permeation, it is preferable to use the multilayer film by enclosing the alcohol volatilizer inside the sealed package. Examples of such a package include a packaging bag in which an alcohol permeation inhibitor film is formed into a bag and sealed, a container lid, and the like. By encapsulating the alcohol volatilizer using the multilayer film of the present invention, the life of the food can be further extended.
  • the seal layer (D) of the multilayer film of the present invention is used as a heat seal layer, and the seal layers (D) are overlapped with each other for heat sealing, or the base material layer (A) and the seal layer (D) are overlapped with each other.
  • It is preferably a packaging bag formed by heat-sealing together.
  • the two multilayer films are cut into a desired size of a packaging bag, stacked on top of each other, heat-sealed on three sides to form a bag, and then the contents are filled from one side not heat-sealed.
  • It can be used as a packaging bag by heat-sealing and sealing.
  • a packaging bag / container by superimposing the sealing layer (D) and another film that can be heat-sealed and heat-sealing.
  • a film such as LDPE or EVA having a relatively weak mechanical strength can be used.
  • a laminated film obtained by laminating a film such as LDPE or EVA and a stretched film having relatively good tearability for example, a biaxially stretched polyethylene terephthalate film (OPET), a biaxially stretched polypropylene film (OPP), or the like is also used. Can be done.
  • OPET biaxially stretched polyethylene terephthalate film
  • OPP biaxially stretched polypropylene film
  • the multilayer film of the present invention can be used even if it is bonded to another base material.
  • the other base material that can be used at this time is not particularly limited, but from the viewpoint of easily exhibiting the effects of the present invention, a plastic base material having high rigidity and high gloss, particularly biaxial It is preferable to use a stretched resin film.
  • aluminum foil can be used alone or in combination.
  • stretched resin film examples include biaxially stretched polyester (PET), easily tearable biaxially stretched polyester (PET), biaxially stretched polypropylene (OPP), and biaxially stretched polyamide (PET), biaxially stretched polypropylene (OPP), and biaxially stretched polyamide (PET).
  • PA co-extruded biaxially stretched polypropylene with ethylene vinyl alcohol copolymer (EVOH) as the central layer, biaxially stretched ethylene vinyl alcohol copolymer (EVOH), co-extruded biaxially coated with polyvinylidene chloride (PVDC).
  • stretched polypropylene These may be used alone or in combination.
  • Examples of the laminating method in which the base material is laminated on the multilayer film obtained by the above manufacturing method to form a laminated film include dry lamination, wet lamination, non-solvent lamination, extrusion lamination and the like.
  • Examples of the adhesive used in the dry lamination include a polyether-polyurethane-based adhesive, a polyester-polyurethane-based adhesive, and the like. Although various pressure-sensitive adhesives can be used, it is preferable to use a pressure-sensitive pressure-sensitive adhesive.
  • Examples of the pressure-sensitive pressure-sensitive adhesive include polyisobutylene rubber, butyl rubber, a rubber-based pressure-sensitive adhesive obtained by dissolving a mixture thereof in an organic solvent such as benzene, toluene, xylene, and hexane, or rosin abiethylene acid in these rubber-based pressure-sensitive adhesives.
  • a tackifier such as an ester, a terpene / phenol copolymer, a terpene / inden copolymer, or a 2-ethylhexyl acrylate / n-butyl copolymer acrylate, a 2-ethylhexyl acrylate / ethyl acrylate.
  • examples thereof include an acrylic pressure-sensitive adhesive obtained by dissolving an acrylic copolymer having a glass transition point of ⁇ 20 ° C. or lower, such as a methyl methacrylate copolymer,
  • Example 1 The following resins were used as the resin components forming the base layer (A), the first intermediate layer (B), and the seal layer (D), respectively, to prepare a resin mixture forming each layer.
  • the resin mixture forming each layer is supplied to each of the three extruders, and the average thickness of each layer of the laminated film formed by the base material layer (A) / first intermediate layer (B) / sealing layer (D). It was co-extruded from the T-die at an extrusion temperature of 250 ° C. and cooled with a water-cooled metal cooling roll at 40 ° C. so that the thickness was 25 ⁇ m / 3 ⁇ m / 7 ⁇ m to form a laminated film having a total thickness of 35 ⁇ m.
  • Base material layer (A) 50 parts by mass of a propylene homopolymer (density 0.900 g / cm 3 , MFR 8.0 g / 10 min) (hereinafter referred to as HOPP (1)) and a propylene-ethylene random copolymer (hereinafter referred to as HOPP (1)). Density 0.900 g / cm 3 , MFR 7.0 g / 10 min) (hereinafter referred to as COPP (1)) 50 parts by mass.
  • Seal layer (D) Linear low-density polyethylene (density 0.935 / cm 3 , MFR 4.0 g / 10 min (hereinafter referred to as LLDPE (1)) 100 parts by mass.
  • LLDPE (1) Linear low-density polyethylene (density 0.935 / cm 3 , MFR 4.0 g / 10 min (hereinafter referred to as LLDPE (1)) 100 parts by mass.
  • LLDPE (1) Linear low-density polyethylene (density 0.935 / cm 3 , MFR 4.0 g / 10 min (hereinafter referred to as LLDPE (1)) 100 parts by mass.
  • the laminated film is co-extruded from a T-die at an extrusion temperature of 250 ° C. and cooled with a water-cooled metal cooling roll at 40 ° C. so that the average thickness of each layer of the laminated film is 8 ⁇ m / 17 ⁇ m / 3 ⁇ m / 7 ⁇ m, and the total thickness is 35 ⁇ m.
  • the laminated film of was molded.
  • Base material layer (A) Same as the base material layer (A) of Example 1.
  • Second intermediate layer (C) 65 parts by mass of LLDPE (1) and 35 parts by mass of high-density polyethylene (density 0.960 g / cm 3 , MFR 8.0 g / 10 min) (hereinafter referred to as HDPE (1)).
  • First intermediate layer (B) Same as the first intermediate layer (C) of Example 1.
  • Seal layer (D) Same as the first intermediate layer (C) of Example 1.
  • Base material layer (A) A mixture of 65 parts by mass of LLDPE (1) and 35 parts by mass of HDPE (1).
  • Base material layer (A) 100 parts by mass of HOPP (1).
  • Seal layer (D) 100 parts by mass of a propylene-ethylene random copolymer (density 0.900 g / cm 3 , MFR 8.0 g / 10 min) (hereinafter referred to as COPP (2)).
  • COPP (2) propylene-ethylene random copolymer
  • the resin components of the resin mixture used for the base material layer (A), the second intermediate layer (C), the first intermediate layer (B), and the seal layer (D) are as follows, and the base material layer (A) / Co-extruded so that the average thickness of each layer of the laminated film formed by the second intermediate layer (C) / first intermediate layer (B) / sealing layer (D) is 12 ⁇ m / 7 ⁇ m / 12 ⁇ m / 4 ⁇ m.
  • a laminated film was obtained in the same manner as in Example 2 except for the above.
  • Second intermediate layer (C) 100 parts by mass of LLDPE (1).
  • First intermediate layer (B) Same as the base material layer (A) of Comparative Example 3.
  • Seal layer (D) 30 parts by mass of LLDPE (1) and 70 parts by mass of LLDPE (2).
  • the multilayer films of the present invention of Examples 1 and 2 include Comparative Example 1 in which the base material layer (A) does not contain a polypropylene-based resin as a main component, or a generally used olefin-based resin.
  • the alcohol permeation could be suppressed while maintaining the performance of impact resistance, rigidity, and transparency without any problem in practicality.
  • Example 2 provided with the second intermediate layer containing a polyethylene resin as a main component, alcohol permeation can be suppressed in the same manner as in Example 1, and the impact resistance is excellent, and the rigidity and transparency are further increased. The result was also excellent in balance.
  • Comparative Example 3 although the alcohol permeation suppressing effect was high, the impact resistance was inferior.

Landscapes

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

Abstract

La présente invention concerne un film ayant une perméabilité à l'alcool réduite qui est un film multicouche comprenant une couche de base (A) qui comprend, en tant que composant principal, une résine à base de polypropylène n'ayant pas de structure cyclique et comprenant un homopolymère de propylène (a1) et un copolymère (a2) de propylène avec une autre oléfine, une première couche intermédiaire (B), qui comprend une résine à base de polyoléfine cyclique en tant que composant principal, et une couche d'étanchéité (D) comprenant une résine à base de polyoléfine en tant que composant principal, les couches ayant été superposées dans l'ordre (A)/(B)/(D).
PCT/JP2021/039734 2020-11-10 2021-10-28 Film ayant une perméabilité à l'alcool réduite, et matériau d'emballage et emballage comprenant ledit film ayant une perméabilité à l'alcool réduite WO2022102414A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022512358A JP7207604B2 (ja) 2020-11-10 2021-10-28 アルコール透過抑制フィルム、及びアルコール透過抑制フィルムを用いた包装材並びに包装体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020187117 2020-11-10
JP2020-187117 2020-11-10

Publications (1)

Publication Number Publication Date
WO2022102414A1 true WO2022102414A1 (fr) 2022-05-19

Family

ID=81601073

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/039734 WO2022102414A1 (fr) 2020-11-10 2021-10-28 Film ayant une perméabilité à l'alcool réduite, et matériau d'emballage et emballage comprenant ledit film ayant une perméabilité à l'alcool réduite

Country Status (3)

Country Link
JP (1) JP7207604B2 (fr)
TW (1) TW202222586A (fr)
WO (1) WO2022102414A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115402628B (zh) * 2022-09-30 2024-05-28 湖南义龙包装股份有限公司 一种果蔬用保鲜包装结构

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002275327A (ja) * 2001-03-22 2002-09-25 Grand Polymer Co Ltd ポリプロピレン樹脂組成物および二軸延伸フィルム
JP2004107417A (ja) * 2002-09-17 2004-04-08 Tohcello Co Ltd 二軸延伸防湿ポリプロピレンフィルム
JP2004315582A (ja) * 2003-04-11 2004-11-11 Mitsui Chemicals Inc ポリプロピレン樹脂組成物および二軸延伸フィルム
WO2015064653A1 (fr) * 2013-10-31 2015-05-07 出光興産株式会社 Composition de polyoléfine, film de polyoléfine orienté et procédé de production associé
JP2016117227A (ja) * 2014-12-22 2016-06-30 Dic株式会社 保香性フィルム及び包装材

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007111982A (ja) 2005-10-20 2007-05-10 Toppan Printing Co Ltd 多層フィルムおよび多層包装用材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002275327A (ja) * 2001-03-22 2002-09-25 Grand Polymer Co Ltd ポリプロピレン樹脂組成物および二軸延伸フィルム
JP2004107417A (ja) * 2002-09-17 2004-04-08 Tohcello Co Ltd 二軸延伸防湿ポリプロピレンフィルム
JP2004315582A (ja) * 2003-04-11 2004-11-11 Mitsui Chemicals Inc ポリプロピレン樹脂組成物および二軸延伸フィルム
WO2015064653A1 (fr) * 2013-10-31 2015-05-07 出光興産株式会社 Composition de polyoléfine, film de polyoléfine orienté et procédé de production associé
JP2016117227A (ja) * 2014-12-22 2016-06-30 Dic株式会社 保香性フィルム及び包装材

Also Published As

Publication number Publication date
TW202222586A (zh) 2022-06-16
JPWO2022102414A1 (fr) 2022-05-19
JP7207604B2 (ja) 2023-01-18

Similar Documents

Publication Publication Date Title
JP6863483B2 (ja) 積層フィルム及び食品包装袋
JP5713190B2 (ja) 易開封性多層フィルム及び該フィルムを用いた包装材
JP5459535B2 (ja) 共押出多層フィルム及び該フィルムからなる包装材
JP5741935B2 (ja) 多層フィルム及び該フィルムからなる包装材
JP5787157B2 (ja) 易引裂き性多層フィルム、その製造方法及び該フィルムを用いた包装材
JPWO2018163836A1 (ja) 積層フィルム及び食品包装袋
JP6172398B2 (ja) 多層フィルム、包装材用積層フィルム、包装袋及びスタンディングパウチ
JP5779866B2 (ja) 多層フィルム及び該フィルムを用いた包装材
KR102131124B1 (ko) 저흡착성 라미네이트용 다층 필름, 이를 사용한 복합 필름 및 포장재
JP5716286B2 (ja) 共押出多層フィルム及び該フィルムからなる包装材
JP6797353B2 (ja) 多層フィルム及び包装材
JP7207604B2 (ja) アルコール透過抑制フィルム、及びアルコール透過抑制フィルムを用いた包装材並びに包装体
WO2014207950A1 (fr) Corps stratifié et emballage dans lequel il est utilisé
JP6465343B2 (ja) 保香性フィルム及び包装材
KR20180089394A (ko) 첩부제의 포장 구조
JP5569659B1 (ja) 積層体及びこれを用いた包装材
JP6839924B2 (ja) 蓋材
JP7257777B2 (ja) 積層フィルム及び包装材
JP7276394B2 (ja) 積層フィルム及び包装材
US20230234346A1 (en) Sealant film, laminate film, and packaging material
JP2021102277A (ja) 積層フィルム及び包装袋
JP2021102300A (ja) 積層フィルム及び包装材
JP2020049670A (ja) 罫線加工性に優れた包装用の低吸着性積層体

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2022512358

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21891661

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21891661

Country of ref document: EP

Kind code of ref document: A1