WO2022102414A1 - Film with reduced alcohol permeability, and packaging material and package including said film with reduced alcohol permeability - Google Patents

Film with reduced alcohol permeability, and packaging material and package including said film with reduced alcohol permeability Download PDF

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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
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Prior art keywords
resin
alcohol
layer
intermediate layer
film
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PCT/JP2021/039734
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French (fr)
Japanese (ja)
Inventor
アウェルロース アウリア
康史 渡辺
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Dic株式会社
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Priority to JP2022512358A priority Critical patent/JP7207604B2/en
Publication of WO2022102414A1 publication Critical patent/WO2022102414A1/en

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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.

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Abstract

The present invention relates to a film with reduced alcohol permeability which is a multilayer film comprising a base layer (A) that comprises, as a main component, a polypropylene-based resin having no cyclic structure and comprising a propylene homopolymer (a1) and a copolymer (a2) of propylene with another olefin, a first interlayer (B), which comprises a cyclic-polyolefin-based resin as a main component, and a sealing layer (D) comprising a polyolefin-based resin as a main component, the layers having been superposed in the order of (A)/(B)/(D).

Description

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Alcohol permeation suppression film, packaging materials and packaging materials using alcohol permeation suppression film
　本発明は、食品や医療品等の包装材に使用するアルコール透過抑制フィルムに関し、より詳細には、フィルムからのアルコール透過を抑制することによりアルコール保持性を高めた包装材を実現可能なアルコール透過抑制フィルムに関する。 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.
　食品、医薬及び医療品等の包装材として、プラスチック素材を使用したフレキシブルパッケージングが世界的に使用されている。近年は、消費者の嗜好性の向上やＣＯＶＩＤ１９による生活様式の変化に伴い、包装材には、内容物の変質を抑制して安全性を確保すること、更に食品用においては作り立てのおいしさを維持した状態で品質保持期間を１日でも長く確保することへの要求が高まっている。 Flexible packaging using plastic materials is used worldwide as packaging materials for foods, medicines, medical products, etc. In recent years, with the improvement of consumer taste and the change of lifestyle due to COVID 19, the packaging material has been improved to ensure safety by suppressing the deterioration of the contents, and the taste of freshly made food has been improved. There is an increasing demand for ensuring a long quality retention period as long as one day while maintaining the condition.
　例えばパン、菓子類、麺類、乾物等の食品は、品質や鮮度を保持するために、袋・容器等の包装体内部にアルコール揮散剤が封入される場合がある。アルコール揮散剤は包装体の内部でエチルアルコールを揮散させ、ガス化したエチルアルコールが食品の表面を覆うことにより、食品のカビを防ぐ品質保持剤である。アルコール揮散剤を封入することにより、食品の柔らかさを守り作りたての食感を保ち、賞味期限延長に貢献できると考えられる。アルコール揮散剤を包装体に封入する場合、包装体の内部に気化したアルコールを充満させる必要があることから、アルコールガスの透過量が低く、また、シール性が高い包装体が求められる。 For example, 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. 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. When 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.
　アルコール透過量が低い包装体の材料としては、例えば、プラスチック基材上に無機化合物を含むガスバリア蒸着層と、ケイ素化合物を含むガスバリア被覆層を積層したガスバリア積層フィルムが開示されている（例えば、特許文献１参照）。当該積層フィルムは、透明性を有し、アルコール遮断性にも優れていることから、アルコール液体容器や酒類の紙容器などに適した包装部材として利用可能である。 As a material for a package having a low alcohol permeation amount, for example, 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.
特開２０１６－４６４号公報Japanese Unexamined Patent Publication No. 2016-464
　アルコール揮散剤を封入した食品用包装材には、通常、柔軟性に優れたポリオレフィン系のフィルムを貼り合わせたラミネートフィルムが用いられている。しかし、上述のように品質保持期間を１日でも長く確保するためには、よりアルコールガスの透過量が低い材料が求められる。 As a food packaging material containing an alcohol volatilizer, a laminated film in which a polyolefin-based film having excellent flexibility is bonded is usually used. However, as described above, in order to secure the quality retention period as long as one day, a material having a lower alcohol gas permeation amount is required.
　一方、特許文献１に記載の材料は無機化合物を含むガスバリア蒸着層やガスバリア被覆層を設ける必要があることから、工程数が多く、柔軟性が劣り、また、コストが高くなってしまう。そのため、蒸着層を設けたり、他のフィルムと積層してラミネートしたりすることなく、単体のフィルムで高いアルコール保持性と適度な柔軟性を有するフィルムが望まれている。 On the other hand, 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.
　本発明が解決しようとする課題は、アルコールガスの透過性が低く、また、柔軟性と耐衝撃性を有し、フィルム単体で用いた場合においても優れたアルコール保持性を有し、包装材として好適に利用することが可能なアルコール透過抑制フィルムを提供することにある。 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.
　本発明は、環状構造を有さないポリプロピレン系樹脂を主成分とし、該ポリプロピレン系樹脂として、プロピレン単独重合体（ａ１）及びプロピレンと他のα－オレフィン共重合体（ａ２）を含有する基材層（Ａ）、
　環状ポリオレフィン系樹脂を主成分とする第一の中間層（Ｂ）、
及びポリオレフィン系樹脂を主成分とするシール層（Ｄ）が、（Ａ）／（Ｂ）／（Ｄ）の順に積層された多層フィルムである、アルコール透過抑制フィルム
により、上記課題を解決するものである。 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 α-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.
　本発明のアルコール透過抑制フィルムは、アルコールガスの透過性が低いことから、フィルム単体で用いた場合においても優れたアルコール保持性を有することが可能である。また、本発明のアルコール透過抑制フィルムは柔軟性と耐衝撃性に優れていることから、密封用の袋や容器等の様々な包装形態への加工性に優れており、更に、良好な透明性を有することから包装体内部の視認性も優れている。そのため、アルコール揮散剤を封入して品質や鮮度を維持したい食品や医療・医薬品の包装用途に好適に適用できる。 Since 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.
本発明のアルコール透過抑制フィルムは、環状構造を有さないポリプロピレン系樹脂を主成分とする基材層（Ａ）、環状ポリオレフィン系樹脂を主成分とする第一の中間層（Ｂ）、及びポリオレフィン系樹脂を主成分とするシール層（Ｄ）が、（Ａ）／（Ｂ）／（Ｄ）の順に積層された多層フィルムである。
なお、本明細書において各層の「主成分」とは、具体的には、層を構成する各成分のうち最も割合が多い成分をいうものとする。 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.
In the present specification, the "main component" of each layer specifically means the component having the largest proportion among the components constituting the layer.
［基材層（Ａ）］
　本発明の多層フィルムの基材層（Ａ）は、環状構造を有さないポリプロピレン系樹脂を主成分とし、該ポリプロピレン系樹脂として、プロピレン単独重合体（ａ１）及びプロピレンと他のオレフィン共重合体（ａ２）を含有する層である。ポリプロピレン系樹脂としてこれらの２成分を含有することにより、安価及び工業的入手容易な材料を用いてアルコール透過を抑制することができ、また、耐熱性や適度な剛性を付与できる。更に、単体で使用する場合には、この基材層（Ａ）が包装材の表層となることから、光沢を有した包装材とすることができる。 [Base material layer (A)]
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). By containing these two components as a polypropylene-based resin, alcohol permeation can be suppressed by using an inexpensive and industrially easily available material, and heat resistance and appropriate rigidity can be imparted. Further, when used alone, the base material layer (A) serves as the surface layer of the packaging material, so that the packaging material has a gloss.
　プロピレンと他のオレフィン共重合体（ａ２）としては、プロピレン－オレフィンランダム共重合体、たとえばプロピレン－エチレン共重合体、プロピレン－１－ブテン共重合体、プロピレン－エチレン－１－ブテン共重合体、メタロセン触媒系ポリプロピレンなどが挙げられる。これらはそれぞれ単独で使用してもよいし、併用してもよい。 Examples of the propylene and other olefin copolymer (a2) 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.
　前記その他のオレフィンとしては、例えば、エチレン、１－ブテン、1－ペンテン、１－へキセン、１－オクテン、１－ヘプテン、４－メチル－ペンテン－１、４－メチル－ヘキセン－１等が挙げられ、これらの２種以上を同時に共重合したものであっても良い。共重合形式としてはランダム共重合、ブロック共重合のいずれもでも使用できる。 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. As the copolymerization type, either random copolymerization or block copolymerization can be used.
　これらの中でも、エチレンとの共重合体であることが好ましい。また、共重合体におけるその他のオレフィンの含有率としては、２～２３モル％が好ましく、より好ましくは２．５～１５モル％である。 Among these, it is preferable that it is a copolymer with ethylene. The content of other olefins in the copolymer is preferably 2 to 23 mol%, more preferably 2.5 to 15 mol%.
　中でも、プロピレン単独重合体（ａ１）と、プロピレンと他のオレフィン共重合体（ａ２）としてプロピレン－エチレンランダム共重合体を併用することが好ましい。プロピレン単独重合体は、耐熱性や剛性の向上が期待でき、プロピレン－エチレンランダム共重合体は、光沢性の向上が期待できる。そして、これらポリプロピレン系樹脂を併用する事で、アルコール透過抑制・耐熱性・光沢性を有した包装材を得やすくなる。 Above all, it is preferable to use 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. By using these polypropylene-based resins together, it becomes easy to obtain a packaging material having alcohol permeation suppression, heat resistance, and gloss.
　また、これらのポリプロピレン系樹脂は、ＭＦＲ（２３０℃）が０．５～３０．０ｇ／１０分で、融点が１１０～１６５℃であるものが好ましく、より好ましくは、ＭＦＲ（２３０℃）が２．０～１５．０ｇ／１０分で、融点が１１５～１６２℃のものである。ＭＦＲ及び融点がこの範囲であれば、フィルムの成膜性が向上する。 Further, 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.
環状構造を有さないポリプロピレン系樹脂において、プロピレン単独重合体（ａ１）及びプロピレンと他のオレフィン共重合体（ａ２）の割合は、質量比で、プロピレン単独重合体（ａ１）：プロピレンと他のオレフィン共重合体（ａ２）＝２０：８０～８０：２０の範囲であることが好ましく、３０：７０～７０：３０の範囲であることがより好ましく、４０：６０～６０：４０の範囲であることが更に好ましい。 In the polypropylene-based resin having no cyclic structure, 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.
　基材層（Ａ）は、上記ポリプロピレン系樹脂を主成分とするものであり、本発明の効果を損なわない範囲で共押出可能なその他の樹脂を併用しても良い。基材層（Ａ）に用いる樹脂成分の総質量うち、上記ポリプロピレン系樹脂の割合は、５０質量％以上であることが好ましく、７０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることが更に好ましい。 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.
　基材層（Ａ）に使用する、上記ポリプロピレン系樹脂以外の樹脂としては、包装用フィルムに使用される各種樹脂を使用でき、なかでも、エチレン系樹脂等のオレフィン系樹脂を好ましく使用できる。エチレン系樹脂としては超低密度ポリエチレン（ＶＬＤＰＥ）、線状低密度ポリエチレン（ＬＬＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、線状中密度ポリエチレン（ＬＭＤＰＥ），中密度ポリエチレン（ＭＤＰＥ）等のポリエチレン樹脂や、エチレン－酢酸ビニル共重合体（ＥＶＡ）等を使用できる。 As 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. Examples of 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). Polyethylene-vinyl acetate copolymer (EVA) or the like can be used.
　上記プロピレン系樹脂以外の樹脂としてオレフィン系樹脂を使用する場合には、その含有量が表面層（Ａ）に含まれる樹脂成分中の３０質量％以下であることが好ましく、１０質量％以下であることがより好ましく、５質量％以下であることがさらに好ましい。 When an olefin resin is used as a resin other than the propylene resin, 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.
　また、オレフィン系樹脂として環状ポリオレフィン系樹脂を使用してもよいが、基材層（Ａ）に含まれる樹脂成分中の環状ポリオレフィン系樹脂の含有量は１０質量％以下とすることが好ましく、５質量％以下とすることがより好ましく、実質的に使用しないことも好ましい。 Although a cyclic polyolefin resin may be used as the olefin resin, 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.
　本発明で使用する基材層（Ａ）中には、上記以外の他の樹脂を併用してもよい。当該他の樹脂としては、例えば、エチレン系エラストマー、プロピレン系エラストマー、ブテン系エラストマー等の熱可塑性エラストマー；エチレン－メチルメタアクリレート共重合体（ＥＭＭＡ）、エチレン－エチルアクリレート共重合体（ＥＥＡ）、エチレン－メチルアクリレート（ＥＭＡ）共重合体、エチレン－エチルアクリレート－無水マレイン酸共重合体（Ｅ－ＥＡ－ＭＡＨ）、エチレン－アクリル酸共重合体（ＥＡＡ）、エチレン－メタクリル酸共重合体（ＥＭＡＡ）等のエチレン系共重合体；更にはエチレン－アクリル酸共重合体のアイオノマー、エチレン－メタクリル酸共重合体のアイオノマー等を例示できる。 A resin other than the above may be used in combination with the base material layer (A) used in the present invention. Examples of 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. -Methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA) 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.
　上記他の樹脂を使用する場合には、その含有量が基材層（Ａ）に含まれる樹脂成分中の３０質量％以下で使用することが好ましく、２０質量％以下で使用することがより好ましく、１０質量％以下であることがより好ましく、５質量％以下であることがさらに好ましい。 When the above other resin is 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.
　基材層（Ａ）中には、上記樹脂成分以外に各種添加剤等を適宜併用してもよい。添加剤としては、例えば、滑剤、ブロッキング防止剤、紫外線吸収剤、光安定剤、耐電防止剤、防曇剤等、着色剤等を適宜使用できる。これら添加剤を使用する場合には、基材層（Ａ）に使用する樹脂成分１００質量部に対して、好ましくは２質量部以下、より好ましくは０．０１～１質量部程度で使用する。 In addition to the above resin components, various additives and the like may be appropriately used in the base material layer (A). As the additive, for example, 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. When these additives are used, they 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).
　特に、フィルム成形時の加工適性、充填機の包装適性を付与するため、基材層（Ａ）の摩擦係数は０．９以下、中でも０．８以下である事が好ましいので、基材層（Ａ）には、滑剤やブロッキング防止剤を適宜添加する事も好ましい。 In particular, in order to impart processing suitability at the time of film molding and packaging suitability of the filling machine, 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).
　基材層（Ａ）の多層フィルムに対する厚み比率は、アルコール透過を抑制し、且つ、好適な剛性や耐熱性、包装機械適性等を得やすいことから、多層フィルムの総厚み（全厚）に対する基材層（Ａ）の厚み比率としては、１５％以上であることが好ましく、２０％以上であることがより好ましい。一方、柔軟性と光沢性の観点から、厚み比率の上限は、７５％以下であることが好ましく、５０％以下であることが好ましく、３０％以下であることが好ましく、２５％以下であることが好ましい。 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. On the other hand, from the viewpoint of flexibility and glossiness, 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.
［第一の中間層（Ｂ）］
　本発明の多層フィルムの第一の中間層（Ｂ）には環状ポリオレフィン系樹脂を含有することで、優れた易引き裂き性や直進カット性を実現できる。当該環状ポリオレフィン系樹脂としては、例えば、ノルボルネン系重合体、ビニル脂環式炭化水素重合体、環状共役ジエン重合体等が挙げられる。これらの中でも、ノルボルネン系重合体が好ましい。また、ノルボルネン系重合体としては、ノルボルネン系単量体の開環重合体（以下、「ＣＯＰ」という。）、ノルボルネン系単量体とエチレン等のオレフィンを共重合したノルボルネン系共重合体（以下、「ＣＯＣ」という。）等が挙げられる。また、ＣＯＰ及びＣＯＣの水素添加物も、特に好ましい。また、環状ポリオレフィン系樹脂の重量平均分子量は、５，０００～５００，０００が好ましく、より好ましくは７，０００～３００，０００である。 [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. Examples of 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.
　前記ノルボルネン系重合体と原料となるノルボルネン系単量体は、ノルボルネン環を有する脂環族系単量体である。このようなノルボルネン系単量体としては、例えば、ノルボルネン、テトラシクロドデセン、エチリデンノルボルネン、ビニルノルボルネン、エチリデテトラシクロドデセン、ジシクロペンタジエン、ジメタノテトラヒドロフルオレン、フェニルノルボルネン、メトキシカルボニルノルボルネン、メトキシカルボニルテトラシクロドデセン等が挙げられる。これらのノルボルネン系単量体は、単独で用いても、２種以上を併用しても良い。 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.
　前記ノルボルネン系共重合体（ＣＯＣ）は、前記ノルボルネン系単量体と共重合可能なオレフィンとを共重合したものであり、このようなオレフィンとしては、例えば、エチレン、プロピレン、１－ブテン等の炭素原子数２～２０個を有するオレフィン；シクロブテン、シクロペンテン、シクロヘキセン等のシクロオレフィン；１，４－ヘキサジエン等の非共役ジエンなどが挙げられる。 The norbornene-based copolymer (COC) 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.
　また、前記ノルボルネン系共重合体（ＣＯＣ）中のノルボルネン系単量体の含有比率は、４０～９０モル％が好ましく、より好ましくは５０～８０モル％である。含有比率がこの範囲にあれば、アルコール透過抑制効果、フィルムの剛性、加工安定性が向上する。 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.
　第一の中間層（Ｂ）中に含まれる環状ポリオレフィン系樹脂の含有量は、第一の中間層（Ｂ）に含まれる樹脂成分中の７０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。環状ポリオレフィン系樹脂の含有量を当該範囲とすることで、耐衝撃性を損なうことなく、好適な易引き裂き性や直進カット性を実現しやすくなる。 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. By setting the content of the cyclic polyolefin resin in the above range, it becomes easy to realize suitable easy tearing property and straight-line cutting property without impairing the impact resistance.
　また、第一の中間層（Ｂ）中に使用する環状ポリオレフィン系樹脂は、そのガラス転移温度が１４０℃以下であることが好ましく、５０～１４０℃であることがより好ましく、７０～１２０℃であることがさらに好ましい。環状ポリオレフィン系樹脂として当該ガラス転移温度のものを使用することで、良好な耐熱性や剛性を得やすく、また、落下等に対する耐破袋性を向上させやすくなる。また、良好な相溶性を得やすくなり、外観ムラを抑制しやすくなる。ガラス転移温度（Ｔｇ）は、ＤＳＣにより測定して得られる値である。 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. By using 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.
　また、異なるガラス転移温度の環状ポリオレフィン系樹脂を併用してもよいが、その６０質量％以上は、押出適性、コスト、易裂け性等の観点からガラス転移点が１２０℃以下の環状ポリオレフィン系樹脂であることが好ましい。 Further, 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.
　環状ポリオレフィン系樹脂のＭＦＲは、０．２～１７ｇ／１０分（２３０℃、２１．１８Ｎ）、好ましくは３～１５ｇ／１０分（２３０℃、２１．１８Ｎ）、より好ましくは５～１３ｇ／１０分（２３０℃、２１．１８Ｎ）である。ＭＦＲがこの範囲であると、直鎖状低密度ポリエチレンとの相溶性に優れ、なおかつ各種の多層成膜法において良好な成膜性が得られる点で好ましい。 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). When the 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.
　本発明に使用する環状ポリオレフィン系樹脂として使用できる市販品として、ノルボルネン系モノマーの開環重合体（ＣＯＰ）としては、例えば、日本ゼオン株式会社製「ゼオノア（ＺＥＯＮＯＲ）」等が挙げられ、ノルボルネン系共重合体（ＣＯＣ）としては、例えば、三井化学株式会社製「アペル」、ポリプラスチックス社製「トパス（ＴＯＰＡＳ）」等が挙げられる。 As a commercially available product that can be used as the cyclic polyolefin resin used in the present invention, 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.
　第一の中間層（Ｂ）中の樹脂成分としては、上記環状ポリオレフィン系樹脂のみを含有することも好ましいが、本発明の効果を損なわない範囲で、これら樹脂成分以外の他の樹脂を併用してもよい。その他の併用できる樹脂種としては、例えば、上記基材層（Ａ）にて、例示したポリエチレン系樹脂やポリプロピレン系樹脂等の環状ポリオレフィン系樹脂以外の環状構造を有さないオレフィン系樹脂を例示できる。これら環状構造を有さないオレフィン系樹脂を使用する場合には、第一の中間層（Ｂ）に含まれる樹脂成分中の３０質量％以下とすることが好ましく、２０質量％以下とすることがより好ましく、１０質量％以下とすることがさらに好ましい。また下限は特に制限されるものではないが、所望する特性に応じて１質量％以上の含有量にて適宜使用すればよい。 As 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. As other resin types that can be used in combination, for example, 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. .. When these olefinic resins having no cyclic structure are used, 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.
　第一の中間層（Ｂ）中には、上記樹脂成分以外に各種添加剤等を適宜併用してもよい。添加剤としては、例えば、滑剤、ブロッキング防止剤、紫外線吸収剤、光安定剤、耐電防止剤、防曇剤等、着色剤等を適宜使用できる。これら添加剤を使用する場合には、第一の中間層（Ｂ）に使用する樹脂成分１００質量部に対して、好ましくは２質量部以下、より好ましくは０．０１～１質量部程度で使用する。 In addition to the above resin components, various additives and the like may be appropriately used in combination in the first intermediate layer (B). As the additive, for example, 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. When these additives are used, they 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.
　また、第一の中間層（Ｂ）の多層フィルムに対する厚み比率としては、コスト面と成膜性やフィルムのカール性の観点より、２５％以下であることが好ましく、２０％以下であることが好ましく、１５％以下であることが好ましく、１０％以下であることが好ましい。また、下限は、アルコール透過を抑制するために、３％以上であることが好ましく、５％以上であることが好ましい。 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.
［シール層（Ｄ）］
　本発明の多層フィルム使用するシール層（Ｄ）は、例えば、各種包装用フィルムに使用されるヒートシール層を適宜使用できる。なかでも、前記基材層（Ａ）、第一の中間層（Ｂ）等と積層しやすいことから、ポリオレフィン系樹脂、特に環状構造を有さないポリオレフィン系樹脂を主成分とする層であることが好ましい。当該ポリオレフィン系樹脂としては、上記基材層（Ａ）等にて例示したポリエチレン系樹脂やポリプロピレン系樹脂を好ましく使用できる。 [Seal layer (D)]
As 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. Among them, since it is easy to be laminated with the base material layer (A), the first intermediate layer (B), etc., the layer is mainly composed of a polyolefin resin, particularly a polyolefin resin having no cyclic structure. Is preferable. As 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.
　なかでも、強度や密封性、包装機械適性の観点から、密度が０．９１６～０．９３５ｇ／ｃｍ３のポリエチレン系樹脂あるいはメタロセン触媒を用いて重合されたプロピレン－α－オレフィンランダム共重合体であるポリプロピレン樹脂を用いることが好ましい。特に、好適なシール性を得やすいことから直鎖低密度ポリエチレンを使用することが好ましい。また、ボイル殺菌工程でのフィルムの互着の抑制からも上記密度の範囲が好ましい。 Among them, a polypropylene-α-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.
　シール層（Ｄ）に含まれる樹脂成分中の上記ポリオレフィン系樹脂の含有量は７０質量％以上とすることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。また、シール層（Ｄ）に含まれる樹脂成分中の１００質量％が、直鎖低密度ポリエチレンであってもよい。 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.
　シール層（Ｄ）中には、本発明の効果を損なわない範囲で、上記ポリオレフィン系樹脂以外の他の樹脂を併用してもよく、当該他の樹脂としては、基材層（Ａ）等にて例示した熱可塑性エラストマーやエチレン系共重合体、アイオノマー等を例示できる。当該他の樹脂を使用する場合には、その含有量がシール層（Ｄ）に含まれる樹脂成分中の３０質量％以下で使用することが好ましく、２０質量％以下で使用することがより好ましく、１０質量％以下であることがより好ましく、５質量％以下であることがさらに好ましい。 In the seal layer (D), 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. Examples thereof include thermoplastic elastomers, ethylene-based copolymers, ionomers, and the like. When the other resin is 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 seal layer (D). It is more preferably 10% by mass or less, and further preferably 5% by mass or less.
　シール層（Ｄ）中には、上記樹脂成分以外に各種添加剤等を適宜併用してもよい。添加剤としては、例えば、滑剤、ブロッキング防止剤、紫外線吸収剤、光安定剤、耐電防止剤、防曇剤等、着色剤等を適宜使用できる。これら添加剤を使用する場合には、シール層（Ｄ）に使用する樹脂成分１００質量部に対して、好ましくは２質量部以下、より好ましくは０．０１～１質量部程度で使用する。特に、フィルム成形時の加工適性、充填機の包装適性を付与するため、シール層（Ｄ）の摩擦係数は０．９以下、中でも０．８以下である事が好ましいので、シール層（Ｄ）には、滑剤やアンチブロッキング剤を適宜添加する事も好ましい。 In addition to the above resin components, various additives and the like may be appropriately used in the seal layer (D). As the additive, for example, 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. When these additives are used, they 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). In particular, 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.
　また、特に単体で包装機械を使用して包装する場合には、多層フィルムの基材層（Ａ）と、シール層（Ｄ）とで、融点に差がある樹脂を用いることが、シールバーの温度を高くすることができ、シール強度を向上できる観点より好ましく、具体的には、基材層（Ａ）の融点が、シール層（Ｄ）の融点より１０℃以上高くすることが好ましい。 Further, especially when packaging by itself using a packaging machine, it is recommended to use a resin having a different melting point between the base material layer (A) and the seal layer (D) of the multilayer film. It is preferable from the viewpoint that the temperature can be raised and the sealing strength can be improved. Specifically, it is preferable that the melting point of the base material layer (A) is 10 ° C. or more higher than the melting point of the sealing layer (D).
　シール層（Ｄ）の多層フィルムの総厚みに対する厚み比率は、好適な裂け性とシール強度とを得やすいことから、３０％以下であることが好ましく、１０～２５％の範囲であることがより好ましい。 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.
本発明のアルコール透過抑制フィルムは、基材層（Ａ）と第一の中間層（Ｂ）との間に、ポリエチレン系樹脂を主成分とする第二の中間層（Ｃ）を有していてもよい。つまり、基材層（Ａ）、第二の中間層（Ｃ）、第一の中間層（Ｂ）、及びポリオレフィン系樹脂を主成分とするシール層（Ｄ）が、（Ａ）／（Ｃ）／（Ｂ）／（Ｄ）の順に積層された多層フィルムであってもよい。このように、ポリエチレン系樹脂を主成分とする第二の中間層（Ｃ）を有する構成により、柔軟性、耐衝撃性及びアルコール透過抑制効果を高めることができる。 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.
［第二の中間層（Ｃ）］
　第二の中間層（Ｃ）は、ポリエチレン系樹脂（ｃ）を主成分とする層であることが好ましい。 [Second middle layer (C)]
The second intermediate layer (C) is preferably a layer containing the polyethylene-based resin (c) as a main component.
　ポリエチレン系樹脂（ｃ）としては、具体的には、線状低密度ポリエチレン（ＬＬＤＰＥ）、線状中密度ポリエチレン（ＬＭＤＰＥ）、線状高密度ポリエチレン（ＬＨＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等のポリエチレン樹脂や、エチレン－ブテンーゴム共重合体（ＥＢＲ）、エチレン－プロピレンーゴム共重合体（ＥＰＲ）、エチレン－酢酸ビニル共重合体（ＥＶＡ）、エチレン－メチルメタアクリレート共重合体（ＥＭＭＡ）、エチレン－エチルアクリレート共重合体（ＥＥＡ）、エチレン－メチルアクリレート（ＥＭＡ）共重合体、エチレン－エチルアクリレート－無水マレイン酸共重合体（Ｅ－ＥＡ－ＭＡＨ）、エチレン－アクリル酸共重合体（ＥＡＡ）、エチレン－メタクリル酸共重合体（ＥＭＡＡ）、等のエチレン系共重合体；更にはエチレン－アクリル酸共重合体のアイオノマー、エチレン－メタクリル酸共重合体のアイオノマー等が挙げられ、単独でも、２種類以上を混合して使用して良い。これらの中でもアルコール透過抑制、耐熱性、落下衝撃性等とのバランスが良好なことからＬＤＰＥ、ＬＭＤＰＥ、ＬＨＤＰＥ、ＬＬＤＰＥ、ＭＤＰＥ、ＨＤＰＥ、ＥＢＲを用いることが好ましい。 Specific examples of the polyethylene-based resin (c) include linear low-density polyethylene (LLDPE), linear medium-density polyethylene (LMDPE), linear high-density polyethylene (LHDPE), low-density polyethylene (LDPE), and medium-density. 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. Among these, LDPE, LMDPE, LHDPE, LLDPE, MDPE, HDPE, and EBR are preferably used because they have a good balance with alcohol permeation suppression, heat resistance, drop impact resistance, and the like.
　中でも、ポリエチレン系樹脂（ｃ）として、密度が０．９５０ｇ／ｃｍ２以上の高密度ポリエチレン（ｃ１）、及び密度が０．９００ｇ／ｃｍ２以上０．９４５ｇ／ｃｍ２未満のエチレン系樹脂（ｃ２）の少なくともいずれかを含有することが好ましい。 Among them, as the polyethylene-based resin (c), 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.
　高密度ポリエチレン（ｃ１）は、アルコール透過抑制効果及び剛性を向上させやすいため好ましい。高密度ポリエチレン（ｃ１）の密度は、前述のように０．９５０ｇ／ｃｍ２以上であることが好ましく、０．９５５ｇ／ｃｍ２以上であることがより好ましい。
エチレン系樹脂（ｃ２）は、耐衝撃性を向上させるため好ましく、第二の中間層においてエチレン系樹脂を主成分として用いることが好ましい。エチレン系樹脂（ｃ２）はＬＬＤＰＥあるいはＬＭＤＰＥであることが好ましく、前述のように密度は０．９００ｇ／ｃｍ２以上０．９４５ｇ／ｃｍ２未満の範囲であることが好ましいが、０．９３０ｇ／ｃｍ３以下であることがより好ましく、は０．９２５ｇ／ｃｍ３以下であることがより好ましく、０．９１０～０．９２０ｇ／ｃｍ３であることが更に好ましい。また、エチレン系樹脂（ｃ２）のＭＦＲは、０．１～２０ｇ／１０分（１９０℃、２１．１８Ｎ）、好ましくは０．３～１０ｇ／１０分（１９０℃、２１．１８Ｎ）、より好ましくは０．５～５ｇ／１０分（１９０℃、２１．１８Ｎ）である。ＭＦＲがこの範囲であると、良好な成膜性が得られる点で好ましい。 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. It is more preferably 3 or less, more preferably 0.925 g / cm 3 or less, and further preferably 0.910 to 0.920 g / cm 3 . 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.
　アルコール透過抑制効果と、柔軟性及び耐衝撃性とを両立させる観点から、高密度ポリエチレン（ｃ１）及びエチレン系樹脂（ｃ２）を共に用いることが好ましい。高密度ポリエチレン（ｃ１）及びエチレン系樹脂（ｃ２）の割合は、質量比で高密度ポリエチレン（ｃ１）：エチレン系樹脂（ｃ２）＝１０：９０～５０：５０であることが好ましく、２０：８０～４０：６０であることがより好ましい。 It is preferable to use 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 ratio of the high-density polyethylene (c1) and the ethylene-based resin (c2) is preferably high-density polyethylene (c1): ethylene-based resin (c2) = 10: 90 to 50:50 in terms of mass ratio, and is 20:80. It is more preferably to 40:60.
　本発明においては、第二の中間層（Ｃ）中のポリエチレン系樹脂（ｃ）の含有量を第二の中間層（Ｃ）に含まれる樹脂成分中の６５質量％以上とすることで、好適な耐衝撃性やアルコール保持性を実現できる。当該含有量は、第二の中間層（Ｃ）に含まれる樹脂成分中の６８質量％以上であることが好ましく、７０質量％以上であることがより好ましく、７５質量％以上であることがさらに好ましく、８０質量％以上であることが特に好ましい。また、第二の中間層（Ｃ）に含まれる樹脂成分中の１００質量％が、ポリエチレン系樹脂であってもよい。 In the present invention, it is preferable that 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.
　第二の中間層（Ｃ）中には、本発明の効果を損なわない範囲で、上記ポリエチレン系樹脂（ｃ）以外の他の樹脂を併用してもよい。その他の併用できる樹脂種としては、例えば、上記基材層（Ａ）にて例示したポリプロピレン系樹脂等のオレフィン系樹脂等を例示できる。上記ポリエチレン系樹脂（ｃ）以外の樹脂としてポリプロピレン系樹脂等のオレフィン系樹脂を使用する場合には、その含有量が第二の中間層（Ｃ）に含まれる樹脂成分中の３５質量％以下であることが好ましく、３０質量％以下であることがより好ましく、２０質量％以下であることがさらに好ましく、１０質量％以下であることが特に好ましい。 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. As other resin types that can be used in combination, for example, an olefin resin such as the polypropylene resin exemplified in the base material layer (A) can be exemplified. When an olefin resin such as a polypropylene resin is used as a resin other than the polyethylene resin (c), 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.
　また、オレフィン系樹脂として環状ポリオレフィン系樹脂を使用してもよいが、第二の中間層（Ｃ）に含まれる樹脂成分中の環状ポリオレフィン系樹脂の含有量は１０質量％以下とすることが好ましく、５質量％以下とすることがより好ましく、実質的に使用しないことも好ましい。 Although a cyclic polyolefin resin may be used as the olefin resin, 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.
　また、第二の中間層（Ｃ）中には、上記以外の他の樹脂を併用してもよく、当該他の樹脂としては、基材層（Ａ）にて例示した熱可塑性エラストマーやエチレン系共重合体、アイオノマー等を例示できる。当該他の樹脂を使用する場合には、その含有量が第二の中間層（Ｃ）に含まれる樹脂成分中の３５質量％以下で使用することが好ましく、３０質量％以下であることがより好ましく、２０質量％以下であることがさらに好ましく、１０質量％以下であることが特に好ましい。 Further, 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. 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.
　第二の中間層（Ｃ）中には、上記樹脂成分以外に各種添加剤等を適宜併用してもよい。添加剤としては、例えば、滑剤、ブロッキング防止剤、紫外線吸収剤、光安定剤、耐電防止剤、防曇剤等、着色剤等を適宜使用できる。これら添加剤を使用する場合には、第二の中間層（Ｃ）に使用する樹脂成分１００質量部に対して、好ましくは５質量部以下、より好ましくは０．０１～３質量部程度で使用する。 In addition to the above resin components, various additives and the like may be appropriately used in the second intermediate layer (C). As the additive, for example, 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. When these additives are used, they 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.
　前記ポリエチレン系樹脂（ｃ）を主成分とする第二の中間層（Ｃ）の多層フィルムに対する厚み比率としては、アルコール透過抑制効果と、その他の性能バランス、特に耐低温衝撃性の観点より、３０％以上であることが好ましく、特に３５～７０％の範囲であることが好ましい。 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%.
［多層フィルム］
　本発明の多層フィルムは、上記基材層（Ａ）、第一の中間層（Ｂ）、及びシール層（Ｄ）が、（Ａ）／（Ｂ）／（Ｄ）の順に少なくとも積層された多層フィルムである。本発明の多層フィルムは当該構成により、アルコール透過を抑制でき、また、耐衝撃性、柔軟性を実現できる。また、本発明の多層フィルムは、アルコール透過をより抑制し、且つ柔軟性及び耐衝撃性をより向上させるために、基材層（Ａ）、第二の中間層（Ｃ）、第一の中間層（Ｂ）及びシール層（Ｄ）が、（Ａ）／（Ｃ）／（Ｂ）／（Ｄ）の順に少なくとも積層された多層フィルムであることが好ましい。 [Multilayer film]
In the multilayer film of the present invention, 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. With this structure, the multilayer film of the present invention can suppress alcohol permeation, and can realize impact resistance and flexibility. Further, in the multilayer film of the present invention, in order to further suppress alcohol permeation and further improve flexibility and impact resistance, the base material layer (A), the second intermediate layer (C), and the first intermediate layer are used. It is preferable that the layer (B) and the seal layer (D) are multilayer films in which at least (A) / (C) / (B) / (D) are laminated in this order.
　本発明の多層フィルムは、フィルムの総厚みが２０～９０μｍのものが好ましく、より好ましくは３０～６０μｍである。フィルムの厚さがこの範囲であれば、安定したシール強度、包装機械適性、優れた耐ピンホール性能と、アルコール透過抑制効果を両立しやすくなる。 The multilayer film of the present invention preferably has a total film thickness of 20 to 90 μm, more preferably 30 to 60 μm. 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.
　また、各層の厚みは、特に制限されるものではないが、例えば、表面層（Ａ）の厚みとしては、３～１５μｍであることが好ましく、５～１２μｍであることがより好ましい。第一の中間層（Ｂ）の厚みは１～２０μｍであることが好ましく、２～１５μｍであることが好ましい。第二の中間層（Ｃ）を有する場合には第一の中間層（Ｂ）の厚みは１～１５μｍであることが好ましく、２～１０μｍであることがより好ましい。第二の中間層（Ｃ）の厚みは８～３５μｍであることが好ましく、１０～３０μｍであることがより好ましい。シール層（Ｄ）の厚みは２～２０μｍであることが好ましく、４～１５μｍであることがより好ましい。 The thickness of each layer is not particularly limited, but for example, the thickness of the surface layer (A) is preferably 3 to 15 μm, more preferably 5 to 12 μm. The thickness of the first intermediate layer (B) is preferably 1 to 20 μm, and preferably 2 to 15 μm. When the second intermediate layer (C) is provided, the thickness of the first intermediate layer (B) is preferably 1 to 15 μm, more preferably 2 to 10 μm. The thickness of the second intermediate layer (C) is preferably 8 to 35 μm, more preferably 10 to 30 μm. The thickness of the seal layer (D) is preferably 2 to 20 μm, more preferably 4 to 15 μm.
　本発明の多層フィルムは、内容物保護の観点から、そのシール強度が５Ｎ／１５ｍｍ以上である事が好ましく、１０Ｎ／１５ｍｍ以上であることがより好ましい。 From the viewpoint of content protection, 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.
　本発明の多層フィルムの曇り度は、包装する内容物を視認しやすいことから、１０％以下である事が好ましく、８％以下であることがより好ましく、５％以下であることが更に好ましい。本発明の多層フィルムは、このような高い透明性を有する場合には、好適な包装適性や好適な印刷密着性を実現しやすい。 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. When the multilayer film of the present invention has such high transparency, it is easy to realize suitable packaging suitability and suitable print adhesion.
　本発明の多層フィルムは、温度２５℃の条件下で６日間保持した後のアルコール濃度の残存率が１０ｐｐｍ以上であることが好ましく、２０ｐｐｍ以上であることがより好ましい。このように、本発明の多層フィルムはアルコール保持性に優れていることから、単層で用いてもアルコール透過を効果的に抑制することができ、フィルムを貼り合わせたラミネート構成のフィルムに比べて低コスト化を図れる。 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. As described above, since the multilayer film of the present invention has excellent alcohol retention, alcohol permeation can be effectively suppressed even when used as a single layer, as compared with a film having a laminated structure in which films are laminated. Cost can be reduced.
また、本発明の積層フィルムの衝撃強度は、０．６０Ｊ（０℃）以上であることが好ましく、０．７０Ｊ（０℃）以上であることがより好ましく、０．８０Ｊ（０℃）以上であることがよりより好ましく、０．９０Ｊ（０℃）以上であることが更に好ましい。衝撃強度は、積層フィルムを０℃に状態調整された恒温室内で、サンプルを４時間保持した後、直径１．５インチの球状の衝撃頭を用いてフィルムインパクト法で測定することにより求められる。 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.
　本発明の多層フィルムの製造方法としては、特に限定されないが、例えば、基材層（Ａ）、第二の中間層（Ｃ）、第一の中間層（Ｂ）、シール層（Ｄ）に用いる各樹脂又は樹脂混合物を、それぞれ別々の押出機で加熱溶融させ、共押出多層ダイス法やフィードブロック法等の方法により溶融状態で（Ａ）／（Ｃ）／（Ｂ）／（Ｄ）の順で積層した後、インフレーションやＴダイ・チルロール法等によりフィルム状に成形する共押出法が挙げられる。この共押出法は、各層の厚さの比率を比較的自由に調整することが可能で、衛生性に優れ、コストパフォーマンスにも優れた多層フィルムが得られるので好ましい。特に、第二の中間層（Ｃ）を設ける場合は、第二の中間層（Ｃ）で用いるポリエチレン系樹脂は、その他の層で使用する環状ポリオレフィン系樹脂との軟化点（融点）の差が大きいため、相分離やゲルを生じることがある。このような相分離やゲルの発生を抑制するためには、比較的高温で溶融押出を行うことができるＴダイ・チルロール法が好ましい。 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. In particular, when the second intermediate layer (C) is provided, 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.
　本発明の多層フィルムは、上記の製造方法によって、実質的に無延伸の多層フィルムとして得られるため、真空成形による深絞り成形等の二次成形も可能となる。 Since 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.
　さらに、印刷インキとの接着性や、ラミネート用シーラントフィルムとして使用する場合のラミネート適性を向上させるため、前記基材層（Ａ）に表面処理を施すことが好ましい。このような表面処理としては、例えば、コロナ処理、プラズマ処理、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線処理等の表面酸化処理、あるいはサンドブラスト等の表面凹凸処理を挙げることができるが、好ましくはコロナ処理である。 Further, in order to improve the adhesiveness with the printing ink and the laminating suitability when used as a sealant film for laminating, it is preferable to apply 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.
　本発明の多層フィルムからなる包装材としては、食品、薬品、工業部品、雑貨、雑誌等の用途に用いる包装袋、包装容器等が挙げられる。中でも、本発明の多層フィルムはアルコール透過を抑制できることから、多層フィルムを用いて密閉した包装体の内部にアルコール揮散剤封入して使用することが好ましい。このような包装体としては、アルコール透過抑制フィルムを袋状にして密閉した包装袋や、容器の蓋等が挙げられる。本発明の多層フィルムを用いてアルコール揮散剤を封入することにより、食品寿命をより延長することができる。 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.
　前記包装袋は、本発明の多層フィルムのシール層（Ｄ）をヒートシール層として、シール層（Ｄ）同士を重ねてヒートシール、あるいは基材層（Ａ）とシール層（Ｄ）とを重ね合わせてヒートシールすることにより形成した包装袋であることが好ましい。例えば当該多層フィルム２枚を所望とする包装袋の大きさに切り出して、それらを重ねて３辺をヒートシールして袋状にした後、ヒートシールをしていない１辺から内容物を充填しヒートシールして密封することで包装袋として用いることができる。さらには自動包装機によりロール状のフィルムを円筒形に端部をシールした後、上下をシールすることにより包装袋を形成することも可能である In the packaging bag, 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. For example, 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. Furthermore, it is also possible to form a packaging bag by sealing the end of a roll-shaped film in a cylindrical shape with an automatic packaging machine and then sealing the top and bottom.
　また、シール層（Ｄ）とヒートシール可能な別のフィルムを重ねてヒートシールすることにより包装袋・容器を形成することも可能である。その際、使用する別のフィルムとしては、比較的機械強度の弱いＬＤＰＥ、ＥＶＡ等のフィルムを用いることができる。また、ＬＤＰＥ、ＥＶＡ等のフィルムと、比較的引き裂き性の良い延伸フィルム、例えば、二軸延伸ポリエチレンテレフタレートフィルム（ＯＰＥＴ）、二軸延伸ポリプロピレンフィルム（ＯＰＰ）等とを貼り合わせたラミネートフィルムも用いることができる。 It is also possible to form a packaging bag / container by superimposing the sealing layer (D) and another film that can be heat-sealed and heat-sealing. At that time, as another film to be used, a film such as LDPE or EVA having a relatively weak mechanical strength can be used. Further, 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.
　本発明の多層フィルムは、他の基材と貼りあわせても使用できる。この時使用することができる他の基材としては、特に限定されるものではないが、本発明の効果を容易に発現させる観点から、高剛性、高光沢を有するプラスチック基材、特には二軸延伸された樹脂フィルムを用いることが好ましい。また透明性を必要としない用途の場合はアルミ箔を単独あるいは組み合わせて使用することもできる。 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. For applications that do not require transparency, aluminum foil can be used alone or in combination.
　延伸された樹脂フィルムとしては、易引裂き性等の観点から、例えば、二軸延伸ポリエステル（ＰＥＴ）、易裂け性二軸延伸ポリエステル（ＰＥＴ）、二軸延伸ポリプロピレン（ＯＰＰ）、二軸延伸ポリアミド（ＰＡ）、エチレンビニルアルコール共重合体（ＥＶＯＨ）を中心層とした共押出二軸延伸ポリプロピレン、二軸延伸エチレンビニルアルコール共重合体（ＥＶＯＨ）、ポリ塩化ビニリデン（ＰＶＤＣ）をコートした共押出二軸延伸ポリプロピレン等が挙げられる。これらは、単独あるいは複合化して使用しても良い。 Examples of the stretched resin film 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). Examples thereof include stretched polypropylene. These may be used alone or in combination.
　上記の製造方法によって得られた多層フィルムに前記基材を積層し、ラミネートフィルムとする場合の積層方法としては、例えば、ドライラミネーション、ウェットラミネーション、ノンソルベントラミネーション、押出ラミネーション等の方法が挙げられる。 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.
　前記ドライラミネーションで用いる接着剤としては、例えば、ポリエーテル－ポリウレタン系接着剤、ポリエステル－ポリウレタン系接着剤等が挙げられる。また各種の粘着剤を使用することもできるが、感圧性粘着剤を用いることが好ましい。感圧性粘着剤としては、例えば、ポリイソブチレンゴム、ブチルゴム、これらの混合物をベンゼン、トルエン、キシレン、ヘキサンのような有機溶剤に溶解したゴム系粘着剤、或いは、これらゴム系粘着剤にアビエチレン酸ロジンエステル、テルペン・フェノール共重合体、テルペン・インデン共重合体などの粘着付与剤を配合したもの、或いは、２－エチルヘキシルアクリレート・アクリル酸ｎ－ブチル共重合体、２－エチルヘキシルアクリレート・アクリル酸エチル・メタクリル酸メチル共重合体などのガラス転移点が－２０℃以下のアクリル系共重合体を有機溶剤で溶解したアクリル系粘着剤などを挙げることができる。 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 mixture of 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, with an organic solvent.
（実施例１）
　基材層（Ａ）、第一の中間層（Ｂ）及びシール層（Ｄ）の各層を形成する樹脂成分として、各々下記の樹脂を使用して、各層を形成する樹脂混合物を調整した。各層を形成する樹脂混合物を３台の押出機に各々供給し、基材層（Ａ）／第一の中間層（Ｂ）／シール層（Ｄ）にて形成される積層フィルムの各層の平均厚さが２５μｍ／３μｍ／７μｍとなるように、押出温度２５０℃でＴダイから共押出して、４０℃の水冷金属冷却ロールで冷却し、全厚が３５μｍの積層フィルムを成形した。 (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 μm / 3 μm / 7 μm to form a laminated film having a total thickness of 35 μm.
　基材層（Ａ）：プロピレン単独重合体（密度０．９００ｇ／ｃｍ３、ＭＦＲ８．０ｇ／１０ｍｉｎ）（以下、ＨＯＰＰ（１）と称する。）５０質量部と、プロピレン－エチレンランダム共重合体（密度０．９００ｇ／ｃｍ３、ＭＦＲ７．０ｇ／１０ｍｉｎ）（以下、ＣＯＰＰ（１）と称する。）５０質量部との混合物。
第一の中間層（Ｂ）：ノルボルネン系共重合体（密度１．０１０ｇ／ｃｍ３、ＭＦＲ７．０ｇ／１０ｍｉｎ）（以下、ＣＯＣ（１）と称する。）１００質量部。 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.
First intermediate layer (B): 100 parts by mass of a norbornene-based copolymer (density 1.010 g / cm 3 , MFR 7.0 g / 10 min) (hereinafter referred to as COC (1)).
　シール層（Ｄ）：直鎖状低密度ポリエチレン（密度０．９３５／ｃｍ３、ＭＦＲ４．０ｇ／１０ｍｉｎ（以下、ＬＬＤＰＥ（１）と称する。）１００質量部。
（実施例２）
　基材層（Ａ）、第二の中間層（Ｃ）、第一の中間層（Ｂ）及びシール層（Ｄ）の各層を形成する樹脂成分として、各々下記の樹脂を使用して、各層を形成する樹脂混合物を調整した。各層を形成する樹脂混合物を４台の押出機に各々供給し、基材層（Ａ）／第二の中間層（Ｃ）／第一の中間層（Ｂ）／シール層（Ｄ）にて形成される積層フィルムの各層の平均厚さが８μｍ／１７μｍ／３μｍ／７μｍとなるように、押出温度２５０℃でＴダイから共押出して、４０℃の水冷金属冷却ロールで冷却し、全厚が３５μｍの積層フィルムを成形した。 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.
(Example 2)
As the resin component forming each layer of the base material layer (A), the second intermediate layer (C), the first intermediate layer (B), and the seal layer (D), the following resins are used for each layer. The resin mixture to be formed was adjusted. The resin mixture forming each layer is supplied to each of the four extruders and formed of a base material layer (A) / a second intermediate layer (C) / a first intermediate layer (B) / a seal layer (D). 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 μm / 17 μm / 3 μm / 7 μm, and the total thickness is 35 μm. The laminated film of was molded.
　基材層（Ａ）：実施例１の基材層（Ａ）と同じ。 Base material layer (A): Same as the base material layer (A) of Example 1.
　第二の中間層（Ｃ）：ＬＬＤＰＥ（１）６５質量部と、高密度ポリエチレン（密度０．９６０ｇ／ｃｍ３、ＭＦＲ８．０ｇ／１０ｍｉｎ）（以下、ＨＤＰＥ（１）と称する。）３５質量部との混合物。
第一の中間層（Ｂ）：実施例１の第一の中間層（Ｃ）と同じ。 
　シール層（Ｄ）：実施例１の第一の中間層（Ｃ）と同じ。 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)). Mixture with.
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.
（比較例１）
　基材層（Ａ）に使用する樹脂混合物の樹脂成分を下記とした以外は実施例１と同様にして積層フィルムを得た。 (Comparative Example 1)
A laminated film was obtained in the same manner as in Example 1 except that the resin component of the resin mixture used for the base material layer (A) was as follows.
　基材層（Ａ）：ＬＬＤＰＥ（１）６５質量部と、ＨＤＰＥ（１）３５質量部との混合物。 Base material layer (A): A mixture of 65 parts by mass of LLDPE (1) and 35 parts by mass of HDPE (1).
（比較例２）
　基材層（Ａ）、第一の中間層（Ｂ）、及びシール層（Ｄ）に使用する樹脂混合物の樹脂成分を下記として、基材層（Ａ）／第一の中間層（Ｂ）／シール層（Ｄ）にて形成される積層フィルムの各層の平均厚さが６μｍ／２４μｍ／５μｍとなるように共押出しした以外は実施例１と同様にして積層フィルムを得た。 (Comparative Example 2)
The resin components of the resin mixture used for the base material layer (A), the first intermediate layer (B), and the seal layer (D) are as follows, and the base material layer (A) / first intermediate layer (B) / A laminated film was obtained in the same manner as in Example 1 except that the laminated films formed of the seal layer (D) were co-extruded so that the average thickness of each layer was 6 μm / 24 μm / 5 μm.
　基材層（Ａ）：ＨＯＰＰ（１）１００質量部。 Base material layer (A): 100 parts by mass of HOPP (1).
　第一の中間層（Ｂ）：プロピレン単独重合体（密度０．９００ｇ／ｃｍ３、ＭＦＲ７．０ｇ／１０ｍｉｎ）（以下、ＨＯＰＰ（２）と称する。）８５質量部と、直鎖状低密度ポリエチレン（密度０．９０５ｇ／ｃｍ３、ＭＦＲ４．０ｇ／１０ｍｉｎ）（以下、ＬＬＤＰＥ（２）と称する。）１５質量部との混合物。 First intermediate layer (B): propylene homopolymer (density 0.900 g / cm 3 , MFR 7.0 g / 10 min) (hereinafter referred to as HOPP (2)) 85 parts by mass and linear low density polyethylene. (Density 0.905 g / cm 3 , MFR 4.0 g / 10 min) (hereinafter referred to as LLDPE (2)) Mixture with 15 parts by mass.
　シール層（Ｄ）：プロピレン－エチレンランダム共重合体（密度０．９００ｇ／ｃｍ３、ＭＦＲ８．０ｇ／１０ｍｉｎ）（以下、ＣＯＰＰ（２）と称する。）１００質量部。
（比較例３）
　基材層（Ａ）、第二の中間層（Ｃ）、第一の中間層（Ｂ）、及びシール層（Ｄ）に使用する樹脂混合物の樹脂成分を下記として、基材層（Ａ）／第二の中間層（Ｃ）／第一の中間層（Ｂ）／シール層（Ｄ）にて形成される積層フィルムの各層の平均厚さが１２μｍ／７μｍ／１２μｍ／４μｍとなるように共押出しした以外は実施例２と同様にして積層フィルムを得た。 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)).
(Comparative Example 3)
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 μm / 7 μm / 12 μm / 4 μm. A laminated film was obtained in the same manner as in Example 2 except for the above.
　基材層（Ａ）：ＣＯＣ（１）５０質量部と、ノルボルネン系共重合体（密度１．０２０ｇ／ｃｍ３、ＭＦＲ８．０ｇ／１０ｍｉｎ）（以下、ＣＯＣ（２）と称する。）５０質量部。 Base material layer (A): 50 parts by mass of COC (1) and 50 parts by mass of norbornene-based copolymer (density 1.020 g / cm 3 , MFR 8.0 g / 10 min) (hereinafter referred to as COC (2)). ..
　第二の中間層（Ｃ）：ＬＬＤＰＥ（１）１００質量部。 Second intermediate layer (C): 100 parts by mass of LLDPE (1).
　第一の中間層（Ｂ）：比較例３の基材層（Ａ）と同じ。 First intermediate layer (B): Same as the base material layer (A) of Comparative Example 3.
　シール層（Ｄ）：ＬＬＤＰＥ（１）３０質量部と、ＬＬＤＰＥ（２）７０質量部。 Seal layer (D): 30 parts by mass of LLDPE (1) and 70 parts by mass of LLDPE (2).
[アルコール保持性]
　実施例及び比較例にて得られたフィルムを用いて、Ａ４サイズの半分、内容積１００ｃｃの三方シールの包装袋を作製した。続いて、ＰＥＴバック（２Ｌ）中に５０～６０ｐｐｍのエタノールガスを調整し、各包装袋中に該エタノールガス１００ｃｃを投入した後、封入口をニトフロン（登録商標）テープで封じ、指定条件下で放置した。それぞれ１日後、３日後、６日後の封入ガス中のエタノール濃度をＧＣ法で調査した。
 [耐衝撃性]
　実施例及び比較例にて得られたフィルムを、０℃下に調整した恒温室内で４時間静置した。その後、テスター産業製ＢＵ－３０２型フィルムインパクトテスターを用いて、振り子の先端に１．５インチのヘッドを取り付け、フィルムインパクト法による衝撃強度を測定した。 [Alcohol retention]
Using the films obtained in Examples and Comparative Examples, a three-way sealed packaging bag having a half A4 size and an internal volume of 100 cc was prepared. Subsequently, 50 to 60 ppm of ethanol gas was adjusted in the PET bag (2 L), 100 cc of the ethanol gas was put into each packaging bag, and then the sealing port was sealed with Nitoflon (registered trademark) tape under the specified conditions. I left it. The ethanol concentration in the enclosed gas after 1 day, 3 days, and 6 days, respectively, was investigated by the GC method.
[Impact resistance]
The films obtained in Examples and Comparative Examples were allowed to stand in a constant temperature room adjusted to 0 ° C. for 4 hours. Then, using a BU-302 type film impact tester manufactured by Tester Sangyo, a 1.5 inch head was attached to the tip of the pendulum, and the impact strength by the film impact method was measured.
［剛性の測定］
　実施例及び比較例にて得られたフィルムを、２３℃における１％接線モジュラス（単位：ＭＰａ）を、ＡＳＴＭ　Ｄ－８８２に基づき、テンシロン引張試験機〔株式会社エー・アンド・デー製〕を用いて測定した。測定はフィルム製造時の押出方向（以下、「ＭＤ」という）及びフィルム幅方向（以下、「ＣＤ」という）にて実施した。 [Measurement of rigidity]
The films obtained in Examples and Comparative Examples were subjected to 1% tangential modulus (unit: MPa) at 23 ° C. using a Tensilon tensile tester [manufactured by A & D Co., Ltd.] based on ASTM D-882. Was measured. The measurement was carried out in the extrusion direction (hereinafter referred to as "MD") and the film width direction (hereinafter referred to as "CD") at the time of film production.
［透明性］
　実施例及び比較例にて得られたフィルムの曇り度を、ＪＩＳ　Ｋ７１０５に基づきヘーズメーター（日本電飾工業株式会社製）を用いて測定した（単位：％）。透明性は下記基準にて評価した。 [transparency]
The cloudiness of the films obtained in Examples and Comparative Examples was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd.) based on JIS K7105 (unit:%). Transparency was evaluated according to the following criteria.
　上記で得られた結果を表１に示す。 Table 1 shows the results obtained above.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記表から明らかなとおり、実施例１及び２の本発明の多層フィルムは、基材層（Ａ）がポリプロピレン系樹脂を主成分としない比較例１や、一般的に使用されているオレフィン系樹脂である比較例２に比べて、耐衝撃性、剛性、透明性について実用性に問題ない性能を維持した状態で、アルコール透過を抑制することができた。ポリエチレン系樹脂を主成分とする第二の中間層を設けた実施例２は、アルコール透過を実施例１と同等に抑制することができ、且つ、耐衝撃性に優れ、更に剛性、透明性のバランスも優れる結果となった。比較例３はアルコール透過抑制効果は高いものの、耐衝撃性が劣るものであった。 As is clear from the above table, 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. Compared with Comparative Example 2, the alcohol permeation could be suppressed while maintaining the performance of impact resistance, rigidity, and transparency without any problem in practicality. In 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. In Comparative Example 3, although the alcohol permeation suppressing effect was high, the impact resistance was inferior.

Claims (12)

  1. 　環状構造を有さないポリプロピレン系樹脂を主成分とし、該ポリプロピレン系樹脂として、プロピレン単独重合体（ａ１）及びプロピレンと他のオレフィン共重合体（ａ２）とを含有する基材層（Ａ）、
    　環状ポリオレフィン系樹脂を主成分とする第一の中間層（Ｂ）、
    及びポリオレフィン系樹脂を主成分とするシール層（Ｄ）が、（Ａ）／（Ｂ）／（Ｄ）の順に積層された多層フィルムである、アルコール透過抑制フィルム。     A substrate layer (A) containing a polypropylene-based resin having no cyclic structure as a main component and containing the propylene homopolymer (a1) and propylene and another olefin copolymer (a2) as the polypropylene-based resin.
    The first intermediate layer (B) containing a cyclic polyolefin resin as a main component,
    An alcohol permeation inhibitory film, which is a multilayer film in which the seal layer (D) containing a polyolefin resin as a main component is laminated in the order of (A) / (B) / (D).
  2. 　アルコール揮散防止フィルムの全厚に対する前記基材層（Ａ）の厚み比率が１５～７５％である、請求項１に記載のアルコール透過抑制フィルム。 The alcohol permeation suppressing film according to claim 1, wherein the thickness ratio of the base material layer (A) to the total thickness of the alcohol volatilization prevention film is 15 to 75%.
  3. 　前記基材層（Ａ）と第一の中間層（Ｂ）との間に、ポリエチレン系樹脂を主成分とする第二の中間層（Ｃ）を有する請求項１又は２に記載のアルコール透過抑制フィルム。 The alcohol permeation suppression according to claim 1 or 2, wherein a second intermediate layer (C) containing a polyethylene-based resin as a main component is provided between the base material layer (A) and the first intermediate layer (B). the film.
  4. 　前記第二の中間層（Ｃ）のポリエチレン系樹脂として、密度が０．９５０ｇ／ｃｍ２以上の高密度ポリエチレン（ｃ１）及び／又は
    密度が０．９００ｇ／ｃｍ２以上０．９４５ｇ／ｃｍ２未満のエチレン系樹脂（ｃ２）
    を含有する請求項３に記載のアルコール透過抑制フィルム。     As the polyethylene-based resin of the second intermediate layer (C), high-density polyethylene (c1) having a density of 0.950 g / cm 2 or more and / or a density of 0.900 g / cm 2 or more and less than 0.945 g / cm 2 Ethylene resin (c2)
    The alcohol permeation suppressing film according to claim 3.
  5. 　アルコール透過抑制フィルムの全厚に対し、前記第二の中間層（Ｃ）の厚み比率が３５～７０％であり、前記第一の中間層（Ｂ）の厚み比率が５～２５％である、請求項３又は４のいずれかに記載のアルコール透過抑制フィルム。 The thickness ratio of the second intermediate layer (C) is 35 to 70%, and the thickness ratio of the first intermediate layer (B) is 5 to 25% with respect to the total thickness of the alcohol permeation suppressing film. The alcohol permeation suppressing film according to any one of claims 3 or 4.
  6. 　前記第一の中間層（Ｂ）の含有する環状ポリオレフィン系樹脂としてノルボルネン系重合体を含み、
    　前記第一の中間層（Ｂ）に含まれる樹脂成分中の環状ポリオレフィン系樹脂の含有量が７０質量％以上である、請求項１～５のいずれかに記載のアルコール透過抑制フィルム。     The cyclic polyolefin-based resin contained in the first intermediate layer (B) contains a norbornene-based polymer.
    The alcohol permeation suppressing film according to any one of claims 1 to 5, wherein the content of the cyclic polyolefin resin in the resin component contained in the first intermediate layer (B) is 70% by mass or more.
  7. 　前記シール層（Ｄ）の含有するポリオレフィン系樹脂として、ポリエチレン系樹脂（ｄ１）を含有する、請求項１～５のいずれかに記載のアルコール透過抑制フィルム。 The alcohol permeation suppressing film according to any one of claims 1 to 5, which contains a polyethylene resin (d1) as the polyolefin resin contained in the seal layer (D).
  8. 　前記アルコール透過抑制フィルムの総厚みが２０～９０μｍの範囲である、請求項１～７のいずれかに記載のアルコール透過抑制フィルム。 The alcohol permeation suppressing film according to any one of claims 1 to 7, wherein the total thickness of the alcohol permeation suppressing film is in the range of 20 to 90 μm.
  9. 　温度２５℃の条件下で６日間保持した後のアルコール濃度の残存率が１０ｐｐｍ以上である請求項１～８のいずれかに記載のアルコール透過抑制フィルム。 The alcohol permeation suppressing film according to any one of claims 1 to 8, wherein the residual rate of the alcohol concentration after holding for 6 days under the condition of a temperature of 25 ° C. is 10 ppm or more.
  10. 　請求項１～９のいずれかに記載のアルコール透過抑制フィルムからなる包装材。 A packaging material made of the alcohol permeation suppressing film according to any one of claims 1 to 9.
  11. 食品用又は医薬品用である請求項１０に記載の包装材。 The packaging material according to claim 10, which is for food or pharmaceutical products.
  12. 　請求項１～９のいずれかに記載のアルコール透過抑制フィルムを袋状に密閉した内部にアルコール揮散剤を有する包装体。 A package in which the alcohol permeation suppressing film according to any one of claims 1 to 9 is sealed in a bag shape and has an alcohol volatilizer inside.
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JP2002275327A (en) * 2001-03-22 2002-09-25 Grand Polymer Co Ltd Polypropylene resin composition and biaxially oriented film
JP2004107417A (en) * 2002-09-17 2004-04-08 Tohcello Co Ltd Biaxially oriented moistureproof polypropylene film
JP2004315582A (en) * 2003-04-11 2004-11-11 Mitsui Chemicals Inc Polypropylene resin composition and biaxially oriented film
WO2015064653A1 (en) * 2013-10-31 2015-05-07 出光興産株式会社 Polyolefin composition, oriented polyolefin film, and production method for same
JP2016117227A (en) * 2014-12-22 2016-06-30 Dic株式会社 Aroma retention film and packaging material

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JP2007111982A (en) * 2005-10-20 2007-05-10 Toppan Printing Co Ltd Multilayer film and multilayer packaging material

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JP2002275327A (en) * 2001-03-22 2002-09-25 Grand Polymer Co Ltd Polypropylene resin composition and biaxially oriented film
JP2004107417A (en) * 2002-09-17 2004-04-08 Tohcello Co Ltd Biaxially oriented moistureproof polypropylene film
JP2004315582A (en) * 2003-04-11 2004-11-11 Mitsui Chemicals Inc Polypropylene resin composition and biaxially oriented film
WO2015064653A1 (en) * 2013-10-31 2015-05-07 出光興産株式会社 Polyolefin composition, oriented polyolefin film, and production method for same
JP2016117227A (en) * 2014-12-22 2016-06-30 Dic株式会社 Aroma retention film and packaging material

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