WO2019131168A1 - Film multicouche et sac d'emballage d'aliments - Google Patents

Film multicouche et sac d'emballage d'aliments Download PDF

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Publication number
WO2019131168A1
WO2019131168A1 PCT/JP2018/045833 JP2018045833W WO2019131168A1 WO 2019131168 A1 WO2019131168 A1 WO 2019131168A1 JP 2018045833 W JP2018045833 W JP 2018045833W WO 2019131168 A1 WO2019131168 A1 WO 2019131168A1
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Prior art keywords
mass
propylene
resin
layer
laminated film
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PCT/JP2018/045833
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English (en)
Japanese (ja)
Inventor
渡辺　康史
賢人 庄司
松原　弘明
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Dic株式会社
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Priority to JP2019562974A priority Critical patent/JP6863483B2/ja
Publication of WO2019131168A1 publication Critical patent/WO2019131168A1/fr

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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to a laminated film and a food packaging bag using a plant-derived material.
  • a resin film using a plant-derived resin for example, a sealant film using a plant-derived linear low density polyethylene as a sealant film to be laminated on a substrate and used for a laminate tube or a standing pouch (Patent Document 1 And (2), and a lid (patent document 3) and the like provided with a sealant layer using a plant-derived low density biomass polyethylene and a base material.
  • Plant-derived resins often exhibit properties that are highly environmentally compatible but differ from fossil fuel-derived resins, and simply replacing them could reduce heat sealability, impact resistance, bag resistance, etc. .
  • the resin film disclosed in the above document uses a plant-derived resin, when it is applied to applications such as standing pouches and lids, lamination with a laminate base is performed. The impact resistance and the tear resistance, etc., in the film configuration having no laminate substrate are not considered at all.
  • melt-cut sealability in the case of forming a packaging bag by melt-cut sealing, it is necessary to have melt-cut sealability to be applied to various packaging forms, and to realize suitable sealability under manufacturing conditions according to various uses. It is desirable to have good melt seal strength over a wide temperature range.
  • the resin film disclosed in the above document is mainly composed of an ethylene-based resin, it is desirable to replace a fossil fuel-derived resin with a plant-derived resin also in a film configuration mainly composed of a propylene-based resin. It is rare.
  • the problem to be solved by the present invention is that, in a film structure mainly composed of a propylene-based resin, it has suitable seal strength and impact resistance while applying a plant-derived component, and a good melt-cut seal in a wide temperature range
  • An object of the present invention is to provide a laminated film having strength.
  • the present invention is a laminated film in which a surface layer (A), an intermediate layer (B) and a seal layer (C) are laminated, and the surface layer (A), the intermediate layer (B) and the seal layer (C) Is a propylene-based resin, the intermediate layer (B) contains plant-derived biomass polyethylene (b1), and the melt flow rate of the biomass polyethylene (b1) is 1.5 [g / 10 min] or more
  • the film solves the above problems.
  • the laminated film of the present invention is suitably used as various packaging materials because it has suitable seal strength and impact resistance while having resin derived from plants, and has good fused seal strength over a wide temperature range. it can.
  • it since it has excellent impact resistance even when the laminate base is not laminated, it can be suitably used as a packaging bag for pillow packaging and gusset packaging.
  • the laminated film of the present invention is excellent in melting strength, it is suitable for use as a gusset packaging bag used for packaging food such as bread.
  • the laminated film of the present invention has at least a surface layer (A), an intermediate layer (B) and a seal layer (C), one surface layer comprising the surface layer (A) and the other surface layer comprising the seal layer (C) It is a laminated film and contains propylene-based resin in the surface layer (A), the intermediate layer (B) and the seal layer (C), and the intermediate layer (B) contains plant-derived biomass polyethylene (b1), the biomass
  • the melt flow rate of polyethylene (b1) is a laminated film of 1.5 [g / 10 min] or more.
  • the surface layer (A) used for the laminated film of the present invention is a layer constituting a surface layer such as a layer on which printing of a packaging film is provided.
  • the surface layer contains a propylene-based resin as a main resin component, and as the propylene-based resin, for example, a homopolymer of propylene, a propylene- ⁇ -olefin copolymer (propylene- ⁇ -olefin random copolymer, propylene) - ⁇ -olefin block copolymer) etc. can be used.
  • the content of the propylene-based resin in the resin component contained in the surface layer (A) is preferably 50% by mass or more, and 70% by mass or more because it is easy to obtain suitable melting strength and bag-making suitability.
  • the content is more preferably 80% by mass or more, and still more preferably 85% by mass or more.
  • the resin component contained in the surface layer (A) may be a surface layer substantially consisting of only a propylene-based resin.
  • the ⁇ -olefin content in the propylene- ⁇ -olefin copolymer is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass.
  • the ⁇ -olefin content is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 4% by mass or more, since suitable impact resistance can be easily obtained. .
  • a propylene- ⁇ -olefin random copolymer can be preferably used as a propylene-based resin used for the surface layer (A).
  • the propylene- ⁇ -olefin random copolymer include propylene-ethylene random copolymer, propylene-1-butene random copolymer, propylene-ethylene-1-butene random copolymer and the like, and these can be used alone. It may be used or may be used in combination. Among them, a propylene-ethylene random copolymer can be preferably used because it is easy to obtain suitable transparency.
  • the melt flow rate (MFR) of the propylene-ethylene random copolymer is not particularly limited as long as it can form a laminated film, but it is preferably 0.5 g / 10 min or more, and 3 g / 10 min or more. Is more preferable, and 5 g / 10 min or more is more preferable. Further, in order to obtain good moldability, the MFR is preferably 20 g / 10 min or less, more preferably 15 g / 10 min or less, and more preferably 12 g / 10 min or less.
  • Propylene - density of the ethylene random copolymer more it is preferably at most 0.880 g / cm 3 or more 0.905 g / cm 3, is 0.890 g / cm 3 or more 0.900 g / cm 3 or less preferable.
  • the melting point of the propylene-ethylene random copolymer is preferably 110 ° C. or more, and more preferably 115 ° C. or more, from the viewpoint of preventing adhesion to the fused cutting blade during bag making.
  • the temperature is preferably 150 ° C. or less, more preferably 145 ° C. or less.
  • the content of the propylene-ethylene random copolymer in the resin component contained in the surface layer (A) is because it is easy to obtain suitable transparency and packaging suitability.
  • the content is preferably 35% by mass or more, more preferably 45% by mass or more, and still more preferably 50% by mass or more.
  • the content is preferably 75% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less.
  • a random copolymer such as a propylene-1-butene copolymer or a propylene-ethylene-1-butene copolymer, which has a lower melting point, is used as the above-mentioned propylene. It is also preferred to use in combination with an ethylene random copolymer. Among them, propylene-ethylene-1-butene copolymer can be particularly preferably used.
  • the ethylene content and butene content of the propylene-ethylene-1-butene copolymer are each preferably 25% by mass or less, and 15% by mass or less Is more preferably 10% by mass.
  • the ethylene content and the butene content are each preferably 0.5% by mass or more, more preferably 1.5% by mass or more, and 3% by mass, since it is easy to obtain suitable low-temperature sealability. It is more preferable that it is more than.
  • the melt flow rate (MFR) of the propylene-ethylene-1-butene copolymer is not particularly limited as long as it can form a laminated film, but is preferably 0.5 g / 10 min or more, 3.0 g / minute. It is more preferable that it is 10 minutes or more, and it is more preferable that it is 5.0 g / 10 minutes or more. Further, in order to obtain good moldability, the MFR is preferably 20 g / 10 min or less, more preferably 15 g / 10 min or less, and more preferably 12 g / 10 min or less.
  • Propylene - ethylene-density butene copolymer is preferably not more than 0.880 g / cm 3 or more 0.905 g / cm 3, is 0.890 g / cm 3 or more 0.900 g / cm 3 or less Is more preferred.
  • the melting point of the propylene-ethylene-1-butene copolymer is preferably 105 ° C. or more, and more preferably 110 ° C. or more, from the viewpoint of preventing adhesion to the fusion cutting seal blade during bag-making.
  • the temperature is 145 ° C. or less, and more preferably 140 ° C. or less, because it is necessary to form sufficient fused and broken balls in order to develop fused and sealed strength when fused and sealed at the time of bag making.
  • the content of the propylene-ethylene-1-butene copolymer in the resin component contained in the surface layer is that it is easy to obtain a suitable melt-cut seal strength Therefore, the content is preferably 15% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more.
  • the content is preferably 55% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.
  • a propylene-based block copolymer resin particularly a propylene- ⁇ -olefin block copolymer
  • a propylene-based resin used for the surface layer (A) is used as a propylene-based resin used for the surface layer (A).
  • the ⁇ -olefin include ethylene, 1-butene, 1-hexene, 4-methyl 1-pentene, 1-octene and the like.
  • ethylene is preferable because it is excellent in the balance of matte feeling, cold resistance and rigidity.
  • the melt flow rate (MFR) of the propylene-based block copolymer resin is preferably 0.5 g / 10 min or more because it is easy to mold and to obtain suitable impact resistance and matte feeling. More preferably, it is 1 g / 10 min or more. Moreover, it is preferable that it is 20 g / 10 minutes or less, and it is more preferable that it is 10 g / 10 minutes or less.
  • the melting point of the propylene-based block copolymer resin is preferably 155 ° C. or more, and preferably 165 ° C. or less, because it is easy to obtain a suitable bag-making property.
  • the propylene block copolymer resin used for the surface layer (A) may use a single copolymer or a plurality of copolymers. When using two or more, it is preferable to make the total of content of the propylene-type block copolymer resin to be used into the following range.
  • a propylene-based block copolymer resin which is used in the surface layer (A) and is excellent in the balance with the matte feeling, melting strength and bag-making suitability BC8, BC7 (manufactured by Japan Polypropylene Corporation), E150GK, F704V (prime) Polymer Co., Ltd.), PC480A, PC684S, PC380A, VB370A (manufactured by Sun Aroma Co., Ltd.), and the like.
  • the content of the propylene-based block copolymer in the resin component contained in the surface layer (A) has a matte feeling, melting strength and bag-making ability.
  • the balance may be appropriately adjusted, but it is preferably contained in an amount of 50% by mass or more, more preferably 70% by mass or more in the resin component used for the surface layer (A).
  • it becomes easy to acquire the matte feeling which was excellent in the designability and which has uniformity.
  • it is preferable to set it to 80 to 100% by mass, and when improving matte feeling, it is preferable to set it to 70 to 90% by mass.
  • various olefin resins used for packaging films other than the above-mentioned propylene resin may be used.
  • the olefin resin other than the propylene resin include polyethylene resins such as ultra low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), and ethylene-1-butene copolymer.
  • Ethylene-vinyl acetate copolymer Ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate -Ethylene-based copolymers such as maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), etc .; further ethylene-acrylic acid Copolymer ionomer, ethylene-methacrylic acid copolymer Ionomer and the like can be used.
  • olefin resin other than these propylene resin it is preferable that content of the said olefin resin in the resin component contained in surface layer (A) is 20 mass% or less.
  • the present invention among these olefin resins, they have flexibility in a wide temperature range which is effective at the time of bag making, and good dispersibility with propylene resins can be obtained. It can be used preferably.
  • the said copolymer can be especially preferably used, when setting it as a transparent film.
  • the content of the ethylene-1-butene copolymer in the resin component contained in the surface layer is 1 to 1 because it is easy to obtain a suitable low temperature seal.
  • the content is preferably 20% by mass, and more preferably 5 to 15% by mass.
  • the MFR (230 ° C., 21.18 N) of the ethylene-1-butene copolymer is not particularly limited as long as it can form a laminated film, but is preferably 0.5 g / 10 min or more, 2.0 g It is more preferable that it is / 10 minutes or more, and it is more preferable that it is 3.0 g / 10 minutes or more. Further, in order to obtain good moldability, the MFR is preferably 20 g / 10 min or less, more preferably 15 g / 10 min or less, and more preferably 10 g / 10 min or less.
  • the density of the ethylene-1-butene copolymer is preferably at most 0.870 g / cm 3 or more 0.900 g / cm 3, is 0.875 g / cm 3 or more 0.895 g / cm 3 or less More preferable.
  • the content of biomass polyolefin in the resin component contained in the surface layer (A) is preferably 10% by mass or more, and 20 to 50% by mass It is more preferable to
  • the content of biomass polyolefin in the resin component contained in the surface layer (A) should be less than 10% by mass. Is preferable, and it is preferably less than 5% by mass, and it is also preferable to contain substantially no biomass material.
  • various additives may be blended as long as the effects of the present invention are not impaired.
  • the additive include an antioxidant, a weathering stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a lubricant, a nucleating agent, a pigment and the like.
  • the surface roughness (Ra) of the surface layer (A) according to JIS B-0601 is preferably 0.2 to 1.0, and more preferably 0.3 to 0.7.
  • Additives such as a slip agent and an antiblocking agent
  • the film which is excellent in surface slipperiness is As a result, it is possible to improve the bag-making speed, to improve the packing efficiency after packing, to improve the efficiency of the packing operation, and to improve the workability when the contents are filled and then packaged by an automatic packaging machine or the like.
  • the coefficient of friction (ASTM D-1894) of the surface layer (A) surface is preferably 0.05 to 0.7, more preferably 0.07 to 0.6, and more preferably 0.1 to 0.5. Within this range, it is easy to improve the film feedability at the time of packaging, the attachment uniformity after bag making, the packaging workability and the like, and it becomes easy to preferably suppress the film breakage at the time of binding by the closure.
  • the coefficient of friction can be adjusted by appropriately adding additives such as lubricants and antiblocking agents according to the resin component used for the surface layer.
  • the intermediate layer (B) of the laminated film of the present invention is a layer containing a propylene-based resin, and further containing plant-derived biomass polyethylene (b1) having a melt flow rate of 1.5 g / 10 min or more.
  • multilayer film which has suitable impact resistance and tear resistance can be obtained with the favorable heat sealability and the suitable fusion
  • the plant-derived biomass polyethylene (b1) used for the intermediate layer (B) is a polyethylene-based resin produced from plant-derived ethylene which uses sugar cane, corn, beet etc. as a starting material.
  • the biomass polyethylene (b1) include linear low density polyethylene (LLDPE), linear medium density polyethylene (LMDPE), linear high density polyethylene (LHDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE) And high density polyethylene (HDPE) etc. These may be used alone or in combination of two or more.
  • linear low density polyethylene is particularly preferable.
  • the linear low density Porieren preferably density of 0.925 g / cm 3 or less, more preferably 0.920 g / cm 3 or less.
  • the MFR of biomass polyethylene (b1) used for the intermediate layer (B) is 1.5 g / 10 min or more.
  • the MFR is preferably 1.8 g / 10 min or more, and more preferably 2 g / 10 min or more.
  • the upper limit is not particularly limited, but is preferably 25 g / 10 min or less, and more preferably 20 g / 10 min or less. By setting it as the said range, it becomes easy to acquire suitable film forming property and a moldability.
  • the content of plant-derived biomass polyethylene (b1) in the resin component contained in the intermediate layer (B) has a high environmental load reduction effect, while making suitable rigidity and impact resistance, bag processing as a packaging bag It is preferable that the content is 5% by mass or more, more preferably 8% by mass or more, and more preferably 10% by mass or more, because the suitability and the like can be easily obtained.
  • the upper limit is not particularly limited, but in order to obtain particularly excellent impact resistance, processability and the like, it is preferably 60% by mass or less, more preferably 50% by mass or less, and 40% by mass or less Is particularly preferred.
  • the biomass polyethylene (b1) used for the intermediate layer (B) is produced as a monomer by using a plant such as sugar cane as a raw material and can be produced in the same manner as the petroleum-derived production method.
  • a plant such as sugar cane as a raw material
  • It can be manufactured by a well-known method. For example, preparation methods using a Ziegler-Natta catalyst or a metallocene catalyst can be mentioned.
  • a catalyst system using a titanium-containing compound itself or one having a titanium-containing compound supported on a carrier such as a magnesium compound as a main catalyst and a cocatalyst with an organoaluminum compound, propylene alone or a desired ethylene such as ⁇ Mention may be made of the method of polymerization with addition of an olefin. This polymerization may be any process such as slurry polymerization, solution polymerization, gas phase polymerization and the like.
  • a homogeneous catalyst may be used, and a catalyst comprising a vanadium compound and an organoaluminum compound conventionally used, or a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, etc.
  • Metallocene system consisting of transition metal compounds such as zirconium, titanium and hafnium having one or two ligands, transition metal compounds wherein the ligand is geometrically controlled and cocatalysts such as aluminoxane and ionic compounds Mention may also be made of homogeneous catalyst systems, such as catalysts.
  • the metallocene catalyst may be any process such as a slurry polymerization method or a gas phase polymerization method in addition to homogeneous polymerization in the presence of a solvent, using an organic aluminum compound if necessary.
  • biomass polyethylene (b1) examples include SLL 218, SLL 318, SLH 218, SBC 818, SPB 208, SEB 853 and the like manufactured by Blaschem.
  • the biomass polyethylene (b1) may be used in combination with polyethylene (b2) derived from fossil fuel, which is a polyethylene-based resin made from fossil fuel such as petroleum.
  • polyethylene (b2) derived from the fossil fuel linear low density polyethylene (LLDPE), linear medium density polyethylene (LMDPE), linear high density polyethylene (LHDPE), low density polyethylene (LDPE), medium Polyethylene resins such as high density 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),
  • LLDPE linear low
  • LLDPE, LDPE and EBR are preferable, and linear low density polyethylene is particularly preferable.
  • the linear low density Porieren preferably density of 0.915 g / cm 3 or less, more preferably 0.910 g / cm 3 or less, still be at 0.906 g / cm 3 or less preferable.
  • the linear low density polyethylene may be used alone or in combination of two or more.
  • the MFR (190 ° C., 21.18 N) of the linear low density polyethylene derived from fossil fuel is preferably 10 g / 10 min or less, more preferably 1 to 5 g / 10 min.
  • the content of the fossil fuel-derived polyethylene (b2) in the resin component contained in the intermediate layer (B) is a suitable bag-making aptitude or a melt-cut seal strength and
  • the content is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and 10% by mass or more, since it is easy to obtain the bag resistance. Is particularly preferred.
  • the content is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
  • the same one as the propylene-based resin used for the surface layer (A) can be preferably used, and a homopolymer of propylene, a propylene- ⁇ -olefin copolymer (propylene And ⁇ -olefin random copolymers, propylene- ⁇ -olefin block copolymers) and the like can be exemplified.
  • the content of the propylene-based resin in the resin component contained in the intermediate layer (B) is preferably 10% by mass or more, and 20% by mass or more, because it is easy to obtain suitable melting strength and bag-making suitability. It is more preferable that it is 30 mass% or more. Moreover, it is preferable that it is 80 mass% or less, It is more preferable that it is 70 mass% or less, It is more preferable that it is 60 mass% or less.
  • a propylene homopolymer and a propylene- ⁇ -olefin random copolymer can be preferably used as the propylene-based resin.
  • the propylene- ⁇ -olefin random copolymer include propylene-ethylene copolymer, propylene-1-butene copolymer, and propylene-ethylene-1-butene copolymer. These may be used alone or in combination.
  • MFR (230 ° C., 21.18 N) of propylene homopolymer is not particularly limited as long as it can form a laminated film, but it is preferably 0.5 g / 10 min or more, and 2.0 g / 10 min or more Is more preferably 3.0 g / 10 min or more. Further, in order to obtain good moldability, the MFR is preferably 20 g / 10 min or less, more preferably 15 g / 10 min or less, and more preferably 10 g / 10 min or less.
  • the density of the propylene homopolymer is preferably from 0.880 g / cm 3 or more 0.920 g / cm 3, more preferably at most 0.885 g / cm 3 or more 0.915 g / cm 3.
  • the melting point of the propylene homopolymer is preferably 145 ° C. or higher, and more preferably 150 ° C. or higher, from the viewpoint of further maintaining processability such as bag making.
  • propylene-based resin it is also preferable to use a propylene homopolymer and a propylene- ⁇ -olefin random copolymer in combination as the propylene-based resin.
  • the propylene- ⁇ -olefin random copolymer those similar to the above surface layer (A) can be preferably used, and in particular, a propylene-ethylene copolymer can be preferably used.
  • the said propylene-ethylene copolymer the thing similar to the said surface layer (A) at the time of setting it as a transparent film can preferably be used, and preferable ranges, such as ethylene content, MFR, density, and melting point, are also the said surface layer (A). It is similar to the propylene-ethylene copolymer which can be used in
  • the content of the propylene homopolymer in the resin component contained in the intermediate layer (B) is 35% by mass because it is easy to obtain suitable rigidity and transparency. It is preferable that it is more than, 45 mass% or more is more preferable, and 50 mass% or more is more preferable. In addition, it is preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less because a suitable impact strength can be easily obtained.
  • the content of the propylene-ethylene copolymer in the resinous portion contained in the intermediate layer (B) is suitable for bag-making aptitude and tear resistance. In order to obtain easily, it is preferable that it is 5 mass% or more, and it is more preferable that it is 10 mass% or more. Moreover, it is preferable that it is 30 mass% or less, and it is more preferable that it is 25 mass% or less.
  • the above-mentioned various resins may be used at an appropriate content, but it is easy to suppress the deterioration of the rigidity and impact strength when designing the total thickness of the laminated film thin. Therefore, the content of the propylene-based resin in the resin component contained in the intermediate layer (B) is preferably 55% by mass or more, and the content of the ethylene-based resin is preferably 5 to 45% by mass.
  • the content of propylene homopolymer in the resin component contained in the intermediate layer (B) is 50 to 80% by mass
  • the propylene-ethylene random copolymer is 5 to 25% by mass
  • plant-derived biomass polyethylene It is particularly preferable to adjust the total amount of b1) and the fossil fuel-derived polyethylene (b2) to 5 to 45% by mass.
  • a propylene-based block copolymer resin can be preferably used as the propylene-based resin.
  • the thing similar to propylene-type block copolymer resin used for the said surface layer (A) at the time of setting it as a matte film can be used preferably.
  • the propylene block copolymer resin may use a single copolymer or a plurality of copolymers.
  • the content of the propylene-based block copolymer in the resin component contained in the intermediate layer (B) when forming a matte film is 95% by mass or less because it is easy to obtain suitable impact resistance and matte feeling Is more preferably 85% by mass or less, still more preferably 80% by mass or less, and particularly preferably 75% by mass or less.
  • the content is preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more, since it is easy to obtain suitable bag making stability. % Or more is particularly preferred.
  • biomass polyethylene (b1) polyethylene (b2) derived from fossil fuel and propylene-based block copolymer (b3)
  • the ratio of the content of biomass is 2/3/95 to 30/25/45 by mass ratio Is more preferably 10/5/85 to 25/20/55.
  • an olefin resin as described above may be used in combination with the block copolymer resin, and among these, a propylene- ⁇ -olefin random copolymer can be preferably used.
  • a propylene- ⁇ -olefin random copolymer those similar to the above surface layer (A) can be preferably used, and in particular, a propylene-ethylene copolymer can be preferably used.
  • the said propylene-ethylene copolymer the thing similar to the said surface layer (A) at the time of setting it as a transparent film can preferably be used, and preferable ranges, such as ethylene content, MFR, density, and melting point, are also the said surface layer (A). It is similar to the propylene-ethylene copolymer which can be used in
  • the content of the propylene- ⁇ -olefin random copolymer in the resin component contained in the intermediate layer is preferably 5% by mass or more, more preferably 15% by mass or more, and still more preferably 25% by mass or more.
  • the content is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.
  • the above-mentioned various resins may be used at an appropriate content, but it is easy to suppress the deterioration of the rigidity and impact strength when designing the total thickness of the laminated film thin. Therefore, it is preferable to set the content of the propylene-based resin in the resin component contained in the intermediate layer (B) to 55% by mass or more, and the content of the ethylene-based resin to 7 to 45% by mass.
  • propylene-based block copolymer (b3) and propylene-ethylene random copolymer as the propylene-based resin, the total amount of these is 55 mass% or more, and plant-derived biomass as the ethylene-based resin It is particularly preferred to use polyethylene (b1) and polyethylene derived from fossil fuel (b2) to a total amount of 7 to 45% by mass.
  • biomass polyethylene (b1), polyethylene (b2) derived from fossil fuel, propylene-based block copolymer (b3) and propylene-ethylene random copolymer are used as resin components contained in the intermediate layer (B)
  • Ratio of these contents is 2/3 / mass ratio It is preferably 65/30 to 25/20/15/40, and more preferably 10/5/50/35 to 15/15/30/40. By setting the ratio, it is possible to obtain a laminate film having excellent bag-proof resistance, in particular, excellent bag-proof resistance and abrasion resistance at low temperatures, while having a suitable matte tone.
  • additives as exemplified in the surface layer may be appropriately used.
  • the seal layer (C) used in the present invention is a layer used for adhesion of the seal layers of the laminated film, and adhesion of the laminated film to another container, film or the like.
  • a resin type that can obtain a suitable sealing strength may be appropriately selected according to the use mode and the object to be sealed.
  • propylene- ⁇ - such as propylene-ethylene random copolymer, propylene-1-butene copolymer and the like from the viewpoint of obtaining appropriate seal strength.
  • a seal layer containing an ⁇ -olefin-propylene copolymer such as an olefin copolymer or a 1-butene-propylene copolymer can be suitably used. Above all, it is easy to adjust the heat seal temperature and strength at the time of easy opening seal at low temperature, the heat seal temperature range is wide, and it is easy to obtain appropriate heat seal strength as the easy opening seal. Polymers or butene resins such as 1-butene-propylene copolymer are preferred.
  • the 1-butene content in the copolymer is 60 because it is easy to obtain suitable sealability and blocking resistance. It is preferably ⁇ 95 mol%, more preferably 65-95%, still more preferably 70-90 mol%.
  • the propylene content is preferably 2 to 10 mol%, more preferably 3 to 9 mol%, and still more preferably 4 to 8 mol%, since it is easy to obtain suitable low-temperature sealability. preferable.
  • the content of the butene-based resin is 50% by mass or less in the resin component contained in the seal layer It is preferable to set it as 40 mass% or less, It is more preferable to set it as 30 mass% or less. Moreover, it is preferable to be 10 mass% or more, and it is more preferable to be 15 mass% or more.
  • the content of the butene-based resin is in the above range, it is easy to obtain suitable low-temperature sealability, melting strength and tear resistance of bag-formed products, and it is also advantageous for cost reduction.
  • the resin used in combination with the butene-based resin other polyolefin-based resins can be appropriately used.
  • a propylene- ⁇ -olefin copolymer or an ethylene- ⁇ -olefin copolymer is used. Coalescing can be preferably used, and propylene- ⁇ -olefin copolymer can be particularly preferably used.
  • the content of the ⁇ -olefin in the propylene- ⁇ -olefin copolymer is not particularly limited, but is preferably 1 to 20% by mass, and more preferably 1.5 to 15% by mass.
  • ⁇ -olefins include ethylene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.
  • a propylene-ethylene random copolymer as exemplified in the above-mentioned intermediate layer can be preferably used.
  • the MFR is preferably 0.5 to 20 g / 10 min, and more preferably 2 to 10 g / 10 min, because it is easy to obtain good moldability.
  • the content of the other olefin resin is preferably 90% by mass or less, and more preferably 85% by mass or less, in the resin component contained in the seal layer, because it is easy to obtain suitable low-temperature sealability. . Moreover, it is preferable to set it as 50 mass% or more, and it is more preferable to set it as 60 mass% or more.
  • a butene-based resin and a propylene- ⁇ -olefin copolymer in the case of providing an easy-to-open portion in which seal layers are heat-sealed together, a butene-based resin and a propylene- ⁇ -olefin copolymer, It is preferable to use together in a ratio that the mass ratio represented by butene resin / propylene- ⁇ -olefin copolymer is 20/80 to 50/50.
  • the resin which used the plant origin raw material for various resin used in a sealing layer (C).
  • the content of biomass polyolefin in the resin component contained in the seal layer (C) is preferably 10% by mass or more, and 20 to 50% by mass It is more preferable to
  • the content of biomass polyolefin in the resin component contained in the seal layer (C) should be less than 10% by mass. Is preferable, and it is preferably less than 5% by mass, and it is also preferable to contain substantially no biomass material.
  • various additives may be blended as long as the effects of the present invention are not impaired.
  • the additive include an antioxidant, a weathering stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a lubricant, a nucleating agent, a pigment and the like.
  • the coefficient of friction (ASTM D1894) of the surface of the seal layer (C) is preferably 0.01 to 0.4, more preferably 0.02 to 0.35, and still more preferably 0.05 to 0.30. By setting it as the said range, it becomes easy to improve the packing operation
  • the coefficient of friction can be adjusted by appropriately adding additives such as lubricants and antiblocking agents according to the resin component used for the seal layer.
  • the laminate film of the present invention is a laminate film having at least the surface layer (A), the intermediate layer (B) and the seal layer (C), one surface layer of the laminate film is a surface layer, and the other surface layer is It is a laminated film which consists of a seal layer.
  • the laminated film of the said structure has suitable fusion
  • the thickness of the laminated film of the present invention may be appropriately adjusted according to the application and mode of use, but the total thickness is 20 because it is easy to simultaneously achieve volume reduction in packaging application and resistance to breakage during distribution. It is preferably 60 to 60 ⁇ m, more preferably 25 to 50 ⁇ m.
  • each layer are not particularly limited, but for example, the thickness of the surface layer is preferably 2 to 20 ⁇ m, and more preferably 3 to 15 ⁇ m.
  • the thickness of the intermediate layer is preferably 3 to 30 ⁇ m, and more preferably 5 to 20 ⁇ m.
  • the thickness of the seal layer is preferably 1 to 10 ⁇ m, more preferably 2 to 8 ⁇ m.
  • the thickness ratio of the surface layer is preferably 15% or more of the total thickness of the laminated film, and more preferably 20% or more, because it is easy to obtain suitable melting strength and bag-making suitability. Moreover, it is preferable to set it as 35% or less, and it is more preferable to set it as 30% or less.
  • the thickness ratio of the intermediate layer is preferably 30% or more of the total thickness of the laminated film, and more preferably 40% or more, because it is easy to obtain suitable rigidity, melting strength, and bag-making suitability. Further, the content is preferably 70% or less, more preferably 65% or less.
  • the thickness ratio of the sealing layer is preferably 5% to 30% of the total thickness of the laminated film, and more preferably 10 to 25%, because it is easy to obtain suitable easy openability, melting strength and bag-making suitability.
  • the content of plant-derived biomass polyethylene in the resin component contained in the entire laminated film is preferably 2% by mass or more, and 3% by mass or more from the viewpoint of environmental load reduction. Is more preferable, and 5% by mass or more is more preferable.
  • the haze of the laminated film of the present invention is preferably 10% or less, more preferably 5.5% or less, and preferably 4.5% or less, because the content to be packaged is easily visible. Is more preferred. Even when the laminated film of the present invention has such high transparency, it has a suitable packaging aptitude, but is less likely to be broken due to a friction between the contents and the film or a tear due to rubbing.
  • a resin component for increasing the haze such as a block copolymer, is not used, or the content is preferably 10% even when used.
  • the transparency can be improved by setting the content to 5% or less, more preferably.
  • the laminated film of the present invention may be laminated with any other resin layer other than the surface layer, the intermediate layer and the seal layer, but the thickness of the other resin layer is 20% or less of the total thickness.
  • the structure comprising the surface layer, the intermediate layer and the seal layer is particularly preferable.
  • the intermediate layer on which the intermediate layer was laminated in multiple numbers may be sufficient.
  • the layer configuration include a three-layer configuration of surface layer / intermediate layer / seal layer in which an intermediate layer is provided between the surface layer and the seal layer, or a surface layer in which the intermediate layer is composed of a plurality of layers
  • a four-layer structure of / intermediate layer 1 / intermediate layer 2 / seal layer, etc. can be preferably exemplified.
  • a three-layer structure consisting of a surface layer / intermediate layer / seal layer can be preferably used because adjustment of the film properties and production of the film are easy.
  • the method for producing the laminated film of the present invention is not particularly limited.
  • the resin or resin mixture used for each layer is heated and melted by separate extruders, and the method such as coextrusion multilayer die method or feed block method After laminating in a molten state, a coextrusion method of forming into a film by inflation, T-die / chill roll method or the like may be mentioned.
  • This co-extrusion method is preferable because the ratio of the thickness of each layer can be adjusted relatively freely, and a multilayer film excellent in hygiene and cost performance can be obtained. Since the laminated film obtained by the said manufacturing method is obtained as a substantially non-stretching multilayer film, secondary formation, such as deep draw forming by vacuum forming, is also attained.
  • a surface treatment to the surface layer in order to improve the adhesion to the printing ink and the like.
  • examples of such surface treatment include surface oxidation treatment such as corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment and the like, and surface unevenness treatment such as sand blast and the like.
  • it is a corona treatment.
  • the packaging bag used for applications such as foodstuffs, medicine, industrial parts, miscellaneous goods, a magazine, a container, the lid material of a container, etc. are mentioned.
  • a packaging material similar to Japanese paper and the like can be provided because it has an excellent matte feeling and is superior to conventional ones, and can be suitably used for food and the like used to bring out a high-class feeling.
  • the packaging bag has the seal layer of the present invention as a heat seal layer, and the seal layers are stacked one on another and heat sealed, or the surface layer and the seal layer are laminated and heat sealed to make the seal layer inside. It is preferable that it is a formed packaging bag. For example, two laminated films are cut out to the size of a desired packaging bag, and they are stacked and heat sealed on three sides to form a bag, and then the contents are filled from one side which is 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 top and bottom of the rolled film in a cylindrical shape after sealing the rolled film with an automatic packaging machine.
  • the packaging bag when setting it as the packaging bag for breads, it can be set as the packaging bag which has a gusset part by folding and sealing a printing surface. Specifically, it is processed into a bottom gusset bag by a bag making machine such as HK-40 manufactured by Totani Giken Kogyo Co., Ltd. so that the seal layer of the laminated film of the present invention is on the inside of the bag.
  • the laminated film of the present invention can be particularly suitably used as a bottom gusset bag application because it can realize suitable melt-cutting strength and bag-making suitability.
  • Adjusting the melting and sealing temperature and the bag-making speed so that the melting and sealing strength of the bottom gusset bag's side and bottom gusset (folded bottom) is 7.5 N to 30 N / 15 mm, preferably 10 to 30 N / 15 mm. Is preferred.
  • the bottom gusset bag obtained is supplied to an automatic bread filling machine, and after being filled with the bread filling, it is easy to open and has a heat seal strength of 0.1 to 5 N / 15 mm, preferably 0.2 to 4 N / 15 mm.
  • the sealing layer should be on the inside of the bag in a horizontal pillow type automatic packing machine, such as FW-3400 ⁇ V made by Fuji Kikai Co., Ltd. Supplied in roll form.
  • the laminated film of the present invention is excellent in heat sealability and easy openability at the time of pillow packaging, and therefore, can be particularly suitably used for a pillow packaging bag.
  • the heat sealing surface of the film is overlapped and heat sealed to form a bag, and the pan is contained.
  • the easily openable seal portion may be formed by heat sealing under the condition that the easy opening property and the heat seal strength are 0.1 to 5 N / 15 mm, preferably 0.2 to 4 N / 15 mm, and the vicinity thereof May be bound using a tie such as a plastic plate, tape, or string.
  • lid of the packaging bag / container / container by overlapping and heat sealing the sealing layer and another heat-sealable film.
  • films of relatively weak mechanical strength such as LDPE, EVA, polypropylene and the like can be used.
  • laminated films in which films of LDPE, EVA, polypropylene, etc., and stretched films with relatively good tearability such as biaxially stretched polyethylene terephthalate film (OPET), biaxially stretched polypropylene film (OPP), etc., are also used. It can be used.
  • the laminated film of the present invention can realize suitable impact resistance and tear resistance, it can be suitably applied to various packaging applications.
  • excellent impact resistance can be realized even at low temperatures, it is suitable for food packaging applications where packaging and distribution are often performed at low temperatures.
  • the laminated film of the present invention when the laminated film of the present invention is applied to bread packaging such as bread and confectionery bread in which a binding tool (closure) having a sharp tip portion or a heel portion is used, a break in bag is hardly generated.
  • pinholes and tears are less likely to occur when contact with the tie or transport container occurs during transfer.
  • it is hard to produce a pinhole and a tear by friction with the food which is the contents, and the film inner surface (seal surface), rubbing with the plastic tray mixed, and piercing.
  • the laminated film of the present invention can be particularly suitably applied to bread packaging applications because it can ensure a suitable melt-sealed seal strength even when the gusset portion is formed.
  • Example 1 The following resin was used as a resin component which forms each layer of a surface layer, an intermediate
  • COPP (2) 10 parts by mass of linear low density polyethylene
  • LLDPE (1) linear low density polyethylene
  • bioPE (1) 10 parts by weight of a resin mixture Seal layer: 70 parts by weight of COPP (2), 1-butene-propylene copolymer (density: 0.90 g / cm 3)
  • MFR measurement temperature 230 ° C.
  • Example 2 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 intermediate layer was changed to the following.
  • Example 3 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 intermediate layer was changed to the following.
  • Middle layer HOPP (1) 60 parts by mass, COPP (2) 15 parts by mass, LLDPE (1) 10 parts by mass, bio-PE (1) 15 parts by mass
  • Example 4 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 intermediate layer was changed to the following.
  • Middle layer HOPP (1) 55 parts by mass, COPP (2) 20 parts by mass, LLDPE (1) 10 parts by mass, bio PE (2) 15 parts by mass
  • Example 5 The resin component of the resin mixture used for the surface layer and the intermediate layer is as follows, and co-extrusion so that the average thickness of each layer of the laminated film formed of the surface layer / interlayer / seal layer is 7/18/5 ⁇ m A laminated film was formed in the same manner as in Example 1 except for the above.
  • propylene-based block copolymer (1) 100 parts by mass Intermediate Layer: 35 parts by mass of COPP (2), propylene-ethylene block copolymer (density: 0.90 g / cm 3 , MI: 6 g / 10 min, melting point 160 ° C.) (hereinafter, propylene-based block copolymer (2) ) 40 parts by weight, LLDPE (1) 10 parts by weight, bio PE (1) 15 parts by weight
  • Example 6 A laminated film was obtained in the same manner as in Example 5 except that the resin component of the resin mixture used for the intermediate layer was changed to the following.
  • Intermediate layer 35 parts by mass of COPP (2), 40 parts by mass of propylene-based block copolymer (2), 10 parts by mass of LLDPE (1), 15 parts by mass of bio-PE (2)
  • Example 7 A laminated film was obtained in the same manner as in Example 5 except that the resin component of the resin mixture used for the intermediate layer was changed to the following.
  • Intermediate layer 35 parts by mass of COPP (2), 35 parts by mass of propylene-based block copolymer (2), 10 parts by mass of LLDPE (1), 20 parts by mass of bio-PE (1)
  • Example 8 A laminated film was obtained in the same manner as in Example 5 except that the resin component of the resin mixture used for the intermediate layer was changed to the following.
  • Intermediate layer 35 parts by mass of COPP (2), 40 parts by mass of propylene-based block copolymer (2), 5 parts by mass of LLDPE (1), 20 parts by mass of bio-PE (2)
  • 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 intermediate layer was changed to the following.
  • Example 2 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 intermediate layer was changed to the following.
  • Intermediate layer 60 parts by mass of HOPP (1), 15 parts by mass of COPP (2), 10 parts by mass of LLDPE (1), 15 parts by mass of bioPE (3)
  • Example 3 A laminated film was obtained in the same manner as in Example 5 except that the resin component of the resin mixture used for the intermediate layer was changed to the following.
  • Intermediate layer 35 parts by mass of COPP (2), 40 parts by mass of propylene-based block copolymer (2), 10 parts by mass of LLDPE (1), 15 parts by mass of bio-PE (3)
  • Example 4 A laminated film was obtained in the same manner as in Example 5 except that the resin component of the resin mixture used for the intermediate layer was changed to the following.
  • Intermediate layer 35 parts by mass of COPP (2), 35 parts by mass of propylene-based block copolymer (2), 10 parts by mass of LLDPE (1), 20 parts by mass of bio-PE (3)
  • ⁇ The film follows at a bag-making speed of 120 shots, and there is no problem with the alignment.
  • ⁇ The film follows at a bag-making speed of 120 shots, but the alignment with a part becomes a problem.
  • ⁇ 120 shots There are things that can not keep up with the bag speed, and the alignment is bad
  • the melting strength of the gusset portion and the side portion is 16 N / 15 mm or more for all ⁇ :
  • the melting strength of the gusset portion and the side portion is 15 N / 15 mm to 16 N / 15 mm for all ⁇ ⁇ ⁇ ⁇ : the melting strength of the gusset portion and the side portion 14.5 N / 15 mm or more and 15 N / 15 mm or less ⁇ :
  • the melting strength of both the gusset portion and the side portion is 13 N / 15 mm or more and less than 14.5 N / 15 mm ⁇ :
  • the melting strength of at least one of the gusset portion and the side portion is 13 N Less than 15 mm
  • Heat seal strength A bottom gusset bag was produced in the same manner as the above-mentioned bag making suitability evaluation using the films obtained in Examples and Comparative Examples.
  • a heat sealer manufactured by Tester Sangyo Co., Ltd .: 50 mm from the upper end of the bottom bottom of the bottom gusset bag and parallel to the bottom of the bottom gusset bag: pressure 0.2 MPa, time 1 second, seal temperature: upper seal bar 95 ° C., The lower seal bar was heat sealed at 50 ° C., seal bar shape: 300 m ⁇ 10 mm flat surface).
  • Test pieces of 70 mm in length and 15 mm in width are cut out from each of the obtained two bottom gusset bags, 10 sheets each at 23 ° C.
  • the maximum load at the time of peeling off with a Tensilon tensile tester (manufactured by A & D Co., Ltd.) at a tensile speed of 300 mm / min was measured as the heat seal strength.
  • Heat seal strength is less than 5 N / 15 mm, no film breakage when peeled off.
  • ⁇ Heat seal strength is 5 N / 15 mm or more, or film tear when peeled.
  • the laminated films of the present invention of Examples 1 to 8 have suitable seal strength, impact resistance, and good melt-sealed seal strength over a wide temperature range. .
  • the laminated films of Comparative Examples 1 to 4 it was difficult to obtain good fused seal strength in a wide temperature range.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Wrappers (AREA)
  • Bag Frames (AREA)
  • Laminated Bodies (AREA)
  • Packaging Frangible Articles (AREA)

Abstract

La présente invention concerne un film multicouche comprenant des couches superposées comprenant une couche de surface (A), une couche intermédiaire (B) et une couche d'étanchéité (C), la couche de surface (A), la couche intermédiaire (B) et la couche d'étanchéité (C) comprenant chacune une résine à base de propylène et la couche intermédiaire (B) comprenant du polyéthylène de biomasse d'origine végétale (b1), le polyéthylène de biomasse (b1) ayant un indice de fluidité de 1,5 g/10 min ou plus. Le film multicouche, bien que comprenant un ingrédient de résine d'origine végétale, confère non seulement une force d'étanchéité et une résistance aux chocs appropriées, mais également une résistance d'étanchéité à la fusion satisfaisante dans une large plage de températures.
PCT/JP2018/045833 2017-12-26 2018-12-13 Film multicouche et sac d'emballage d'aliments WO2019131168A1 (fr)

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JP7558766B2 (ja) 2020-11-19 2024-10-01 アールエム東セロ株式会社 易開封性フィルム
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JPWO2019230417A1 (ja) * 2018-05-31 2020-08-20 Dic株式会社 積層フィルム及び食品包装袋
JPWO2019230416A1 (ja) * 2018-05-31 2020-07-30 Dic株式会社 積層フィルム及び食品包装袋
JP2021031563A (ja) * 2019-08-22 2021-03-01 福助工業株式会社 樹脂組成物及び樹脂成形体
JP7155484B2 (ja) 2019-08-22 2022-10-19 福助工業株式会社 樹脂組成物及び樹脂成形体
JPWO2021039352A1 (ja) * 2019-08-23 2021-10-07 Dic株式会社 積層フィルム、および、包装方法
WO2021039352A1 (fr) * 2019-08-23 2021-03-04 Dic株式会社 Film stratifié et procédé d'emballage
JP2021066107A (ja) * 2019-10-24 2021-04-30 大日本印刷株式会社 樹脂フィルム、積層体および袋
JP7545648B2 (ja) 2019-10-24 2024-09-05 大日本印刷株式会社 樹脂フィルム、積層体および袋
JP2021102277A (ja) * 2019-12-25 2021-07-15 Dic株式会社 積層フィルム及び包装袋
JP7380189B2 (ja) 2019-12-25 2023-11-15 Dic株式会社 積層フィルム及び包装袋
CN116018375A (zh) * 2020-08-31 2023-04-25 三菱化学株式会社 树脂组合物
EP4201836A4 (fr) * 2020-10-30 2024-10-09 Daio Seishi Kk Emballage de paquet de mouchoirs emballé sous film et matériau d'emballage de paquet de mouchoirs emballé sous film
EP4249245A4 (fr) * 2020-11-19 2024-08-21 Toyo Boseki Film de résine à base de polyoléfine, et stratifié mettant en ouvre celui-ci
JP7558766B2 (ja) 2020-11-19 2024-10-01 アールエム東セロ株式会社 易開封性フィルム
JP7558767B2 (ja) 2020-11-19 2024-10-01 アールエム東セロ株式会社 易開封性フィルム
JPWO2022145364A1 (fr) * 2020-12-28 2022-07-07
JP7268804B2 (ja) 2020-12-28 2023-05-08 王子ホールディングス株式会社 延伸フィルム及び溶断シール袋並びに積層体

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JP6863483B2 (ja) 2021-04-21

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