WO2021205812A1 - Film composite, et film stratifié et corps stratifié l'utilisant - Google Patents

Film composite, et film stratifié et corps stratifié l'utilisant Download PDF

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Publication number
WO2021205812A1
WO2021205812A1 PCT/JP2021/010113 JP2021010113W WO2021205812A1 WO 2021205812 A1 WO2021205812 A1 WO 2021205812A1 JP 2021010113 W JP2021010113 W JP 2021010113W WO 2021205812 A1 WO2021205812 A1 WO 2021205812A1
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Prior art keywords
layer
composite film
film
weight
propylene
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PCT/JP2021/010113
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English (en)
Japanese (ja)
Inventor
村田太一
豊島裕
安岡涼
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東レフィルム加工株式会社
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Priority to JP2021514650A priority Critical patent/JPWO2021205812A1/ja
Publication of WO2021205812A1 publication Critical patent/WO2021205812A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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 a composite film and a laminated film and a laminated body using the composite film. More specifically, the present invention relates to a composite film having excellent low-temperature heat-sealing property and blocking resistance, a laminated film in which a functionality-imparting layer is laminated on the composite film, and a laminated film using the composite film or the laminated film.
  • a laminate for food packaging a laminate in which a polypropylene film as a sealant film is laminated on a base film such as a polyethylene terephthalate (PET) film or a nylon (Ny) film, particularly a stretched PET film or a stretched nylon film (ONy).
  • PET polyethylene terephthalate
  • Ny nylon
  • PET polyethylene terephthalate
  • ONy stretched nylon film
  • unstretched polypropylene-based film is excellent as a food packaging material because it can be heat-sealed at low temperature and has excellent heat resistance and workability. It can be used in a wide range of applications, mainly for packaging, by adding functionality such as light blocking property.
  • the laminate of biaxially stretched polypropylene / non-stretched polypropylene sealant film is inferior in heat resistance, and the laminate melts at the temperature at the time of high-speed filling after conventional bag making, so the bag making temperature is lowered and the filling speed is lowered. Also need to be lowered. Therefore, it is a major obstacle to the development of applications.
  • Patent Document 1 a single-layer film made of a propylene / ⁇ -olefin copolymer (see Patent Document 1) and a base layer (see Patent Document 1) for the purpose of improving low-temperature sealing properties during bag making and high-speed filling.
  • Patent Document 2 A film having a two-layer structure of A) and a seal layer (B) and having a lower melting point of the seal layer (Patent Document 2) is known.
  • Patent Document 1 and Patent Document 2 are used when a packaging bag is manufactured by heat-sealing with a hot plate, or when a food or the like is sealed in a bag-made product and heat-sealed (the end of the hot plate).
  • Insufficient melting of the sealant resin and insufficient adhesive strength at the composite interface that is, insufficient low-temperature heat-sealing property and inferior sealing property, have solved the problems of obtaining productivity at conventional bag making and high-speed filling speed. No.
  • the problems of the present invention are excellent low-temperature heat-sealing property and blocking resistance, good sealing property at conventional bag making and high-speed filling speed, and excellent processability when laminating a functional imparting layer on a film surface. It is an object of the present invention to provide a composite film and a laminated film and a laminated body using the same composite film.
  • the heat-sealed layer (B) is made of a resin composition obtained by mixing 1 to 10 parts by weight of a polyethylene-based polymer (a2) with 100 parts by weight, and the heat-sealed layer (B) is a propylene / random copolymer (b1) having a melting point of 145 ° C. or lower.
  • the propylene / random copolymer (a1) of the base layer (A) is composed of an ethylene / propylene random copolymer, an ethylene / propylene / 1-butene ternary copolymer or a mixture thereof (1). ) Or (2).
  • the propylene / random copolymer (b1) of the heat-sealed layer (B) is an ethylene / propylene random copolymer, a propylene / 1-butene random copolymer, or an ethylene / propylene / 1-butene ternary.
  • a biaxially stretched polypropylene film having a thickness of 20 ⁇ m is laminated on the composite film according to any one of (1) to (8) by a dry laminating method using an adhesive, and the heat-sealing layer of the composite film
  • a laminated film in which a function-imparting layer that imparts a specific function is provided on the surface of the base layer (A) of the composite film according to any one of (1) to (9).
  • the composite film according to the present invention has excellent low-temperature heat-sealing properties and blocking resistance, good sealing properties at conventional bag making and high-speed filling speeds, and a function-imparting layer is laminated on the film surface. It is excellent in workability, and by laminating a function-imparting layer on the surface of the base layer (A) and further laminating another base material on it to form a laminated film or laminate for packaging, a high speed is achieved. It is possible to have filling suitability, and excellent productivity is realized without causing trouble at the time of packaging filling.
  • the propylene / random copolymer (a1) used for the base layer (A) in the present invention is an ethylene / propylene random copolymer, an ethylene / propylene block copolymer, an ethylene / propylene / 1-butene ternary copolymer or A mixture thereof may be used, and an ethylene / propylene / butene random copolymer is preferable from the viewpoint of adhesion to the functional imparting layer and secondary processability.
  • the melting point of the propylene / random copolymer (a1) is 140 ° C. or higher, preferably 140 to 155 ° C., which is excellent in high-speed filling during bag making, and the function-imparting layer is laminated. It is preferable because it has good workability and adhesion.
  • the melt flow rate (hereinafter abbreviated as MFR) of the propylene / random copolymer (a1) is preferably in the range of 2 to 20 g / 10 minutes, preferably 5 to 15 g / 10 minutes. If the MFR is less than 2 g / 10 minutes, the polymer fluidity in extrusion may be insufficient, and if it exceeds 20 g / 10 minutes, a problem may occur in the film formation stability in the film formation cast.
  • the rigidity of the film is increased by mixing 1 to 10 parts by weight of the polyethylene-based polymer (a2) with 100 parts by weight of the propylene / random copolymer (a1) in the base layer (A).
  • the effect of imparting rigidity is not seen when the amount is less than 1 part by weight, and the effect of imparting rigidity does not change even if more than 10 parts by weight is mixed.
  • the polyethylene-based polymer (a2) is preferably high-density polyethylene.
  • the density of the high-density polyethylene is preferably in the range of 0.935 to 0.965 g / cm 3 from the viewpoint of improving the blocking resistance and slipperiness of the film. If the density is less than 0.935 g / cm 3 , the addition effect is not seen, and if the density exceeds 0.965 g / cm 3 , the surface of the film may become too rough and the adhesion when laminating the function-imparting layer may deteriorate. be.
  • the MFR of the polyethylene-based polymer (a2) is preferably in the range of 2 to 20 g / 10 minutes, particularly preferably 5 to 15 g / 10 minutes. If the MFR is less than 2 g / 10 minutes, the dispersibility in the propylene / random copolymer (a1) deteriorates and the polymer fluidity in extrusion deteriorates, and if it exceeds 20 g / 10 minutes, melt fracture occurs and the product is manufactured. Membrane stability may decrease.
  • the base layer (A) in the present invention as described above is a heat-sealing layer as described below as a self-recovering component of the composite film according to the present invention (that is, as a component of scraps of the composite film and the edge portion to be recovered).
  • the constituent component (B) may be contained in an amount of 30% by weight or less.
  • the present invention ensures the target performance of the composite film according to the present invention by allowing the self-recovery component of the composite film to be recovered without significantly changing the composition or proportion of the main component of the base layer (A). It becomes possible to keep the production yield of the composite film according to the above high.
  • the propylene / random copolymer (b1) used for the heat seal layer (B) in the present invention is an ethylene / propylene random copolymer, a propylene / 1-butene random copolymer, or an ethylene / propylene / 1-butene ternary.
  • a polymer or a mixture thereof is preferable, and a mixture of a chillene / propylene random copolymer and a propylene / 1-butene random copolymer is particularly preferable because it can achieve both blocking resistance and low-temperature heat-sealing property.
  • the melting point of the propylene / random copolymer (b1) is 145 ° C. or lower. If the melting point exceeds 145 ° C., the low temperature heat sealability may deteriorate.
  • the lower limit of the melting point is not limited, but is about 115 ° C. If it is less than this, the slipperiness of the film deteriorates and the coefficient of friction becomes large, which makes it easy for wrinkles to occur in the film forming process and the vapor deposition process. Trouble may occur.
  • the MFR of the propylene / random copolymer (b1) is preferably in the range of 3 to 20 g / 10 minutes, particularly preferably 5 to 15 g / 10 minutes. If the MFR is less than 3 g / 10 minutes, the melt viscosity is too high and it becomes difficult to stably extrude from the base during film formation, and if it exceeds 20 g / 10 minutes, a problem of melt fracture occurs and the film formation stability occurs. May cause problems.
  • the mixing amount of the ethylene / ⁇ -olefin copolymer (b2) of the heat seal layer (B) in the present invention may be 5 to 50 parts by weight mixed with 100 parts by weight of the propylene / random copolymer (b1). It is necessary, preferably 11 parts by weight to 50 parts by weight. If the mixing amount of the ethylene / ⁇ -olefin copolymer (b2) is less than 5 parts by weight, the low-temperature heat-sealing property deteriorates, and this composite film is laminated with another base material to produce a package by heat-sealing with a hot plate. Insufficient melt-filling of the sealant resin may cause poor sealing performance. On the other hand, if the mixing amount exceeds 50 parts by weight, uneven flow occurs at the interface with the base layer (A), the film formation stability is inferior, the slack of the film becomes large, and the secondary processability deteriorates.
  • the melting point of the ethylene / ⁇ -olefin copolymer (b2) is 130 ° C. or lower. If the melting point exceeds 130 ° C., the curl of the film becomes large, which may cause troubles during secondary processing such as bag making or providing a function-imparting layer. In addition, poor sealing performance occurs due to insufficient melt-filling of the sealant resin when the composite film is laminated with another base material and heat-sealed with a hot plate to produce a package, or when food or the like is packed in a bag-making product. In some cases.
  • the lower limit of the melting point is not limited, but is about 100 ° C. If it is less than this, the slipperiness of the film is deteriorated and blocking is likely to occur, and when the contents are filled in the bag-making product, the openability of the bag is lowered and a trouble may occur.
  • the ⁇ -olefin of the ethylene / ⁇ -olefin copolymer (b2) of the heat seal layer (B) in the present invention is composed of butene, hexene, octene, or a mixture thereof, and is an ethylene / ⁇ -olefin copolymer (b2).
  • the linear low-density polyethylene those produced by a metallocene-based catalyst are preferably used from the viewpoint of seal strength.
  • the density of the linear low-density polyethylene is preferably 0.9900 to 0.935 g / cm 3 , more preferably 0.915 to 0.930 g / cm 3 . If the density of the linear low-density polyethylene is less than 0.900 g / cm 3 , the blocking resistance may be lowered, and if it is larger than 0.935 g / cm 3 , the dispersibility may be lowered.
  • the heat seal layer (B) in the present invention contains 5 to 30 parts by weight of a thermoplastic elastomer because the productivity and the seal start temperature are further lowered.
  • thermoplastic elastomer has a hard segment phase and a soft segment phase, so that it has rubber elasticity at 25 ° C., while it has a general thermoplastic molding temperature range of 100 ° C. to 300 ° C. It refers to a high molecular weight material that can be molded in the same manner as a general thermoplastic resin by developing fluidity in the hard segment phase.
  • thermoplastic elastomer used for the seal layer for example, polyester-based elastomers, polyolefin-based elastomers, polyamide-based elastomers, polyurethane-based elastomers, styrene-based elastomers, polyacrylic elastomers, and the like can be used alone or in combination of two or more. Above all, from the viewpoint of low-temperature sealing property of the obtained film, it is preferable to use a polyolefin-based elastomer or a hydrogenated styrene-based elastomer.
  • polystyrene-based elastomer propylene-based elastomer and ethylene-based elastomer are preferable.
  • the propylene-based elastomer is an elastomer containing a propylene-derived structural unit, and in one embodiment, is a copolymer containing a propylene-derived structural unit.
  • the content ratio of the propylene-derived structural unit is preferably 30% by weight to 90% by weight, more preferably 50% by weight to 90% by weight. Within such a range, an adhesive sheet having excellent elasticity can be obtained.
  • Examples of other copolymerization components constituting the propylene-based elastomer include ethylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene and 4-methyl-1-. Examples thereof include structural units derived from monomers such as butene and 1-octene. Among them, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene and the like are preferable, and ethylene and 1-butene are particularly preferable. These may be used alone or in combination of two or more.
  • the propylene-based elastomer comprises a building block derived from ethylene.
  • the content ratio of the ethylene-derived structural unit is preferably 5% by weight to 20% by weight, and more preferably 8% by weight to 15% by weight.
  • the ethylene-based elastomer is preferably a low-crystalline random copolymer of ethylene and an ⁇ -olefin having 3 to 8 carbon atoms, and more preferably a low crystal of ethylene and an ⁇ -olefin having 3 to 4 carbon atoms. It is a sex random copolymer.
  • As the low crystalline random copolymer of ethylene and ⁇ -olefin having 3 to 8 carbon atoms an ethylene-butene random copolymer having excellent low-temperature sealing properties is preferable, and an ethylene-butene-1 random copolymer is more preferable.
  • the content of the ⁇ -olefin having 3 to 8 carbon atoms is in the range of 5 to 25% by weight, preferably 10 to 20% by weight, because both blocking resistance and low temperature sealing property can be achieved.
  • the density of the ethylene-based elastomer (B) is 0.865 to 0.890 g / cm 3 , and the heat absorption of melting in the heating process by the differential scanning calorimeter (DSC) based on JIS K7122 is in the range of 5 to 30 J / g. It is preferable to have. Density blocking resistance is deteriorated is less than 0.865 g / cm 3, there is a case where the impact resistance is deteriorated when the density exceeds 0.890 g / cm 3.
  • the hydrogenated styrene-based elastomer has a structure composed of a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one hydrogenated conjugated diene compound.
  • Examples thereof include hydrogenated block copolymers composed of ABAA, BABBA, BABBA, and mixtures thereof.
  • the hydrogenated block copolymer preferably contains 10 to 40% by weight of a vinyl aromatic compound.
  • Examples of the vinyl aromatic compound constituting the polymer block A include styrene and ⁇ -methylstyrene, and styrene is particularly preferable.
  • Examples of the conjugated diene compound before hydrogenation of the hydrogenated conjugated diene compound constituting the polymer block B include butadiene, isoprene, and 1,3-pentadiene, and butadiene and isoprene are particularly preferable.
  • 80%, preferably 90% or more of the aliphatic double bonds based on the conjugated diene compound are hydrogenated to obtain olefin compound polymer block B. ..
  • Typical hydrogenated styrene-based elastomers include styrene, ethylene, butylene, which is a hydrogenated additive in which hydrogen is added to a double bond to improve the weather resistance and heat resistance of styrene, butadiene, and styrene block copolymers.
  • examples thereof include a styrene block copolymer (hereinafter abbreviated as SEBS) and a hydrogenated additive of a styrene / isoprene / styrene block copolymer (hereinafter abbreviated as SEBS is particularly preferable.
  • SEBS those with low styrene content and high ethylene and butylene content have excellent compatibility with the sea component consisting of ethylene / propylene copolymer of the seal layer.
  • JSR Co., Ltd. Dynalon "8601P, Asahi Kasei Co., Ltd.” Tough Tech “H1062, Clayton Polymer Japan Co., Ltd. G1660, etc. can be preferably used, and the total weight ratio of ethylene and butylene to styrene is in the range of 12/88 to 67/33. Is preferable.
  • an antioxidant in the base layer (A) and the heat seal layer (B), an antioxidant, a heat stabilizer, a neutralizing agent, and an antistatic agent are used as long as the heat sealability and the stackability of the functional imparting layer are not impaired.
  • Hydrochloric acid absorber, blocking agent, lubricant and the like can be included. These additives may be used alone or in combination of two or more.
  • inorganic particles or organic particles it is preferable to add 300 to 5000 ppm of inorganic particles or organic particles as the blocking resistant agent because defects due to wrinkles and poor air bleeding are reduced when the composite film of the present invention is wound into a long length. If the content of the inorganic particles or organic particles is less than 300 ppm, the blocking resistance imparting effect may not be observed, and if it exceeds 5000 ppm, the heat sealing force may decrease.
  • Preferred examples of the inorganic particles include silica, zeolite, calcium carbonate and the like, and examples of the organic particles include crosslinked polystyrene particles and crosslinked polymethylmethacrylate particles.
  • Their average particle size is preferably in the range of 1 to 5 ⁇ m. If the average particle size is less than 1 ⁇ m, the addition effect may not be observed, and if it exceeds 5 ⁇ m, the heat sealing force may decrease.
  • antioxidants examples include 2,6-di-t-butylphenol (BHT) and n-octadecyl-3- (3', 5'-di-t-butyl-4) as hindered phenols.
  • BHT 2,6-di-t-butylphenol
  • n-octadecyl-3- 3', 5'-di-t-butyl-4
  • hindered phenols 2,6-di-t-butylphenol (BHT) and n-octadecyl-3- (3', 5'-di-t-butyl-4) as hindered phenols.
  • '-Hydroxyphenyl) propionate (“Irganox” 1076, "Sumilizer” BP-76)
  • Irganox tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane
  • phosphite-based antioxidants tris (2,4-di-t-butylphenyl) phosphite ("Irgafos" 168, Mark 2112), tetrakis (2,4-di-t-butyl).
  • Phenyl) -4-4'-biphenylene-diphosphonite ("Sandstab” P-EPQ)
  • bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (“Ultranox" 626, Mark PEP-24G)
  • Examples thereof include distearyl pentaerythritol diphosphite (Mark PEP-8).
  • 6- [3- (3-t-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra- which has both functions of hindered phenol and phosphite.
  • t-Butyldibenz [d, f] [1,3,2] -dioxaphosphepine (“Sumilizer” GP) and 2 [1-2-hydroxy-3,5-di-t-pentylphenyl acrylate) ] Ethyl] -4,6-di-t-pentylphenyl (“Sumilizer” GS) is preferable, and in particular, the combined use of both is effective in suppressing oxidative deterioration during film formation, and has blocking resistance and low temperature. It is preferable because it contributes to both heat-sealing properties.
  • the amount of the antioxidant added depends on the type of the antioxidant used, but may be appropriately set in the range of 100 to 10000 ppm.
  • the composite film of the present invention may have a two-layer laminated structure of the base layer (A) and the heat seal layer (B) as described above, or may have a laminated structure of three or more layers in which another intermediate layer is interposed between the two layers. It is also possible to do.
  • the intermediate layer the same propylene-based polymer as the base layer (A), a film laminate such as homopolypropylene that improves the strength and rigidity, and the composite film of the present invention in terms of quality stabilization and cost reduction. It is possible to mix flake or recycled pellets obtained by crushing the film or slit debris whose thickness is being adjusted, which is generated in the process of manufacturing.
  • the method of laminating the composite film having the base layer (A), the heat seal layer (B) and the intermediate layer in the present invention is not particularly limited, but melt extrusion is performed using separate extruders, and a pinole, a feed block method, etc.
  • a method of laminating by a method such as a pipe composite method or a coextrusion multi-layer die method is used.
  • the thickness of the composite film in the present invention is not particularly limited, but is usually about 15 ⁇ m to 80 ⁇ m, particularly preferably 20 ⁇ m to 40 ⁇ m from the viewpoint of handleability, and the thickness ratio of the heat seal layer (B) is the overall thickness. It is preferably 10 to 50%, and more preferably 15 to 40%. If the thickness ratio of the heat seal layer (B) is less than 10%, the heat seal force may decrease and the sealability may be inferior. Further, if it exceeds 50%, the heat resistance is lowered, and the high-speed filling property and the secondary processability at the time of laminating the functional imparting layer or laminating with another base material may be deteriorated.
  • the composite film of the present invention can be a laminated film in which a function-imparting layer that imparts a specific function is provided on the surface of the base layer (A).
  • the function-imparting layer in the present invention refers to a layer that imparts a specific function to the composite film.
  • the specific function is at least one function selected from gas barrier property, light shielding property, glossiness, easy adhesion to other base materials, and easy printing property.
  • the specific function may have only one function or may have several functions.
  • the gas barrier property refers to the barrier property against oxygen gas, water vapor, nitrogen gas, and carbon dioxide gas, but is preferably the gas barrier property of oxygen gas and water vapor.
  • the barrier property of oxygen gas can be measured by the method described in the Japanese Industrial Standards (JIS K-7126), and the oxygen gas barrier property in the present invention is the oxygen permeability at a temperature of 23 ° C. and a relative humidity of 0%. It means that.
  • the barrier property of water vapor can be measured by the method described in Japanese Industrial Standards (JIS K-7129B), and refers to the water vapor permeability at a temperature of 40 ° C. and a relative humidity of 90%.
  • the oxygen permeability is preferably 50 cc / m 2 ⁇ day ⁇ atm or less, and more preferably 30 cc / m 2 ⁇ day ⁇ atm or less.
  • the light-shielding property means a function in which the total light transmittance measured by the method described in the Japanese Industrial Standards (JIS K-7361) is 5% or less. More preferably, the total light transmittance is 3% or less.
  • the glossiness refers to the glossiness measured at 60 ° for both incident light and reflected light by the method described in Japanese Industrial Standards (JIS Z-8741).
  • the glossiness after aluminum vapor deposition is preferably 300% or more, more preferably 400% or more.
  • the easy adhesion to other base materials means the ease of adhesion to other base materials, which will be described later.
  • the ease of adhesion refers to the ease of adhesion of the composite film of the present invention to the base layer (A).
  • the ease of adhesion is not particularly limited, but the adhesive used when bonding to another base material is the ease of adhesion to the base layer (A) of the composite film of the present invention, and during extrusion laminating.
  • Ease of adhesion of extruded resin to the base layer (A) of the composite film of the present invention ease of adhesion of the extruded resin to the base layer (A) of the composite film of the present invention during extrusion coating processing, sputtering Ease of adhesion of the vapor deposition components to the base layer (A) of the composite film of the present invention during vacuum vapor deposition, and adhesion of the resin to be coated during coating processing to the base layer (A) of the composite film of the present invention. Ease of use, etc.
  • the method of imparting easy adhesiveness is not particularly limited, and examples thereof include a method of treating the surface of the base layer (A) of the composite film.
  • Examples of the method for treating the surface include corona treatment, flame treatment, plasma treatment, ozone treatment, ion treatment, sputtering treatment, sandblasting treatment, surface modification treatment with a resin such as anchor coat, and the like.
  • the surface of the base layer (A) is formed by a method of forming chemically reactive functional groups or the like on the surface of the base layer (A), adding particulate matter to a resin such as an anchor coat, sputtering treatment, sand brass treatment, or the like.
  • the method for treating the surface of the base layer (A) may be carried out in-line at the time of forming the composite film of the present invention, or may be carried out offline after forming the composite film. Further, only the surface treatment may be performed, or when the function-imparting layer is formed, the function-imparting layer may be continuously formed after the surface treatment of the base layer (A) is performed. After forming the function-imparting layer, the surface treatment thereof may be performed.
  • the ease of printing means the ease of printing on the base layer (A) of the composite film of the present invention.
  • Printing is performed to display character information, a pattern, etc. required for a packaging body such as a packaging bag.
  • the printing components are, for example, additives such as various pigments, extender pigments and plasticizers, desiccants, stabilizers, etc. in conventionally used ink binder resins such as urethane-based, acrylic-based, nitrocellulose-based, and rubber-based. It is composed of ink to which the above is added, and the ease of printing means that the printing components are easily attached at the time of printing, and the ink is less likely to come off such as dot omission.
  • the method of imparting easy printability is not particularly limited, and examples thereof include a method of treating the surface of the base layer (A) of the composite film.
  • the method for treating the surface include corona treatment, flame treatment, plasma treatment, ozone treatment, ion treatment, surface modification treatment with a resin such as anchor coat, and the like.
  • the method for treating the surface of the base layer (A) may be carried out before printing, may be carried out in-line at the time of forming the composite film of the present invention, or may be carried out offline after forming the composite film. May be good. Moreover, only the surface treatment may be carried out. Further, the composite film of the present invention may be unwound, the surface treatment of the base layer (A) may be performed, and then printing may be continuously performed.
  • the function-imparting layer is an inorganic substance layer, an organic substance layer, or an inorganic organic mixture layer. It may be any of. Further, these may be one layer or a plurality of laminated layers. When a plurality of layers are laminated, the order in which they are laminated is not particularly limited as long as the desired function is satisfied.
  • the inorganic layer include a metal layer and an inorganic oxide layer. The metal layer is not particularly limited, but aluminum is preferable from the viewpoint of gas barrier property, light shielding property, glossiness, and cost. In addition, an inorganic oxide layer is preferable when the contents can be visually recognized and gas barrier properties are imparted.
  • the thickness of the metal layer is preferably 20 nm or more and less than 100 nm, and more preferably 22 nm or more and less than 80 nm. It is practical that the optical density is 1.5 or more and the metallic luster is 600% or more. When the thickness of the metallic aluminum layer is 20 nm or less, the optical density is 1.5 or less and the glossiness is 600% or less, the light-shielding property and metallic luster are lost, and the appearance becomes unusable for practical use.
  • the thickness of the metallic aluminum layer is 100 nm or more, there is no problem in light-shielding property and metallic luster, but when the metallic aluminum layer is thickened, it becomes easy to lose heat to the vapor-deposited layer, and the gas barrier performance and the lamination strength are lowered.
  • an inorganic oxide layer is preferable when the contents can be visually recognized and gas barrier properties are imparted.
  • the inorganic oxide is not particularly limited, but coexistence of zinc oxide or zinc sulfide containing aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, silicon oxide and aluminum oxide, and zinc oxide-silicon dioxide-aluminum oxide. Examples include a layer composed of phases, a layer composed of a coexisting phase of zinc sulfide and silicon dioxide, diamond-like carbon or a mixture thereof, but from the viewpoint of cost, aluminum oxide, silicon oxide, and magnesium oxide are used. Preferable, more preferably, aluminum oxide and silicon oxide.
  • the method for forming these metal layers and inorganic oxide layers is not particularly limited, but the metal is directly heated and evaporated to form the metal layer on the surface of the base layer (A) of the composite film of the present invention.
  • Method of forming, reactive vapor deposition method of forming an inorganic oxide layer by reacting heated and evaporated metal with oxygen gas, ion plating method in an oxygen gas atmosphere, sputtering method using a target material as a target Known methods such as a reactive sputtering method in which the sputtering particles react with oxygen gas during sputtering and a chemical vapor deposition method can be used.
  • the function-imparting layer may be provided on the surface of the base layer (A) of the composite film of the present invention, or the function-imparting treatment may be performed.
  • the thickness of the inorganic oxide layer is preferably 10 nm or more and less than 30 nm. If the film thickness is less than 10 nm, the desired lamination strength may not be achieved or the gas barrier performance may be insufficient. If the film thickness is 30 nm or more, the amount of heat of reaction increases during the oxidation reaction of aluminum, so that the base film may be deformed by the heat of reaction and the appearance may not be practical.
  • the thickness of the aluminum oxide layer and the metallic aluminum layer can be calculated from the composition distribution (so-called depth profile) at the sputter depth of aluminum and oxygen obtained by X-ray photoelectron spectroscopy or Auger electron spectroscopy.
  • Examples of the organic material layer include an organic resin layer, and examples thereof include vinylidene chloride resin, polyvinyl alcohol resin, polyurethane resin, polyepoxy resin, polyester resin, polyacrylic resin, and ethylene vinyl alcohol copolymer.
  • the inorganic-organic mixture layer examples include those in which an inorganic substance is mixed with the organic resin, or those in which an organic resin and an inorganic component are bonded.
  • the inorganic substance to be mixed may be either a flat inorganic substance or a particulate inorganic substance.
  • titanium oxide or the like is preferable as the particulate inorganic substance for the purpose of reflecting and blocking light.
  • the film thickness of the inorganic-organic mixture layer is preferably 0.5 to 1000 ⁇ m, more preferably 1 to 500 ⁇ m, further preferably 1 to 100 ⁇ m, and particularly preferably 1 to 50 ⁇ m.
  • the inorganic-organic mixed layer examples include those in which a metal alkoxide is mixed and bonded to a polyvinyl alcohol-based resin, and those in which a metal alkoxide is mixed and bonded to an ethylene vinyl alcohol copolymer. Further, a material such as an oxygen absorber may be contained in these organic substances and inorganic organic mixtures.
  • the method for forming these organic layer and inorganic organic mixture layer is not particularly limited, and the function-imparting layer and the base layer (A) on the base layer (A) and the base layer (A) of the composite film of the present invention are not particularly limited. It can be formed on the functionally treated surface above. For example, it can be formed by using a roll coating method, a dip coating method, a bar coating method, a die coating method, a knife edge coating method, a gravure coating method, a kiss coating method, a spin coating method, a spray method, or a combination of these methods. can.
  • Another base material layer can be laminated on the base layer (A) of the composite film of the present invention or on the surface of the base layer (A) on which the function-imparting layer is laminated to further improve the functionality.
  • the laminated structure of these laminates has the required characteristics of the packaging bag (for example, gas barrier performance for satisfying the quality retention period of the food to be packaged, size / impact resistance corresponding to the weight of the contents, visibility of the contents, etc.). It is appropriately selected accordingly.
  • the above-mentioned other base material layer is not particularly limited as long as the characteristics such as mechanical strength, heat resistance, and light resistance are taken into consideration depending on the application, but typical examples are polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene 2, Polyester such as 6-naphthalate, polyvinyl alcohol, saponified ethylene / vinyl acetate copolymer, polystyrene, polycarbonate, polyethylene, polypropylene such as polypropylene, polyamide such as 6 nylon and 12 nylon, aromatic polyamide, homopolymer such as polyimide Alternatively, a film or sheet made of a copolymer may be mentioned.
  • a plastic film such as a polyamide film or a paper base material, a film laminate obtained by laminating these plastic films with an adhesive or the like, and a polymer film and a paper base material are bonded together.
  • a paper laminate body laminated with an agent or the like there is a growing demand for recycling of plastic packaging materials after use against the background of the increase in marine plastic waste worldwide, and in order to make the entire packaging recyclable in the laminate with the above other base materials.
  • the biaxially stretched polypropylene is preferably made of a polypropylene resin having a stereoregularity in the range of 90 to 98%, which indicates the ratio of methyl groups of propylene arranged regularly in one direction. If the stereoregularity is less than 90%, the rigidity of the film decreases, and when the film is laminated with the composite film, the film stretches due to tension and wrinkles are likely to occur. The performance of the imparting layer may deteriorate. If the stereoregularity exceeds 98%, the crystallinity becomes high, the surface roughness of the film becomes large, and the adhesion of the function-imparting layer may decrease.
  • the method of laminating the composite film of the present invention with the other base material layer is a dry laminating method, a wet laminating method, a non-solvent laminating method that does not use a solvent, and a method of laminating the composite film of the present invention using an adhesive such as a two-component curable urethane resin.
  • an adhesive such as a two-component curable urethane resin.
  • a laminate obtained by laminating the above-mentioned other base material layer, the composite film of the present invention, and the laminated film using the same can be suitably used as a packaging bag and a packaging container.
  • the packaging bag and packaging container include a gusset bag, a standing pouch, a brick type, a flat type, and various foods, foods and drinks, adhesives, chemicals such as adhesives, cosmetics, and miscellaneous goods such as pharmaceuticals. It is possible to fill and wrap various articles such as.
  • the resin composition in which 5 to 50 parts by weight is mixed is melted at a temperature of 220 to 270 ° C.
  • the base layer (A) and the heat seal layer (B) are laminated by a pipe composite or a co-extruded multilayer die, extruded into a film from a base, and cast-cooled and solidified with a cooling roll at 30 to 80 ° C. to form a composite film.
  • the cast film is melt-oriented in the longitudinal direction, and further, the cast film is heat-treated at 40 to 80 ° C. for 0.01 to 1 second with a heated mirror surface roll to obtain the Young's modulus (rigidity) of the film. Can be improved.
  • the surface of the base layer (A) of this composite film as an example of the function-imparting layer, 20 to 60 W in an atmosphere of a mixed gas of nitrogen and carbon dioxide gas (volume ratio of carbon dioxide gas 0.5 to 50%).
  • the composite film of the present invention can be obtained by subjecting it to a corona discharge treatment of 1 minute / m 2 and winding it.
  • the function-imparting layer on the composite film it is set in a vacuum vapor deposition apparatus, and aluminum is applied to the surface of the base layer (A) of the film at a vacuum degree of 1.3 ⁇ 10-2 Pa or more to a thickness of 30 nm.
  • a metal-deposited laminated film can be obtained by subjecting metal-deposited film to the film.
  • Examples 1 to 16, Comparative Examples 1 to 10 The following polyolefin resins were used in Examples 1 to 16 and Comparative Examples 1 to 10 of the composite film, the laminated film, and the laminated body of the present invention.
  • Homopolypropylene Melting point 162 ° C., MFR 7.0 g / 10 minutes (this is abbreviated as h-PP).
  • Ethylene-propylene random copolymer melting point 141 ° C., MFR 7.0 g / 10 minutes, ethylene content 4 mol% (this is abbreviated as r-EPC).
  • Ethylene-propylene-butene random copolymer melting point 145 ° C., ethylene content 2 mol%, butene content 5 mol% (this is abbreviated as r-EPBC ⁇ 1).
  • Ethylene-propylene-butene random copolymer melting point 127 ° C., MFR 7.0 g / 10 minutes, ethylene content 4 mol%, butene content 8 mol% (this is abbreviated as r-EPBC ⁇ 2).
  • Propylene 1-butene random copolymer melting point 125 ° C., MFR 9.0 g / 10 minutes, butene content 19 mol% (this is abbreviated as r-PBC).
  • Ethylene / ⁇ -olefin linear low-density polyethylene, melting point 124 ° C., MFR 5.0 g / 10 minutes ( ⁇ -olefin: butene, which is abbreviated as L-LDPE ⁇ 1).
  • Ethylene / ⁇ -olefin linear low-density polyethylene, melting point 113 ° C., MFR 2.0 g / 10 minutes ( ⁇ -olefin: hexene, which is abbreviated as L-LDPE ⁇ 2).
  • Polyethylene-based polymer high-density polyethylene, melting point 134 ° C., MFR 1.5 g / 10 minutes (this is abbreviated as HDPE).
  • Thermoplastic Elastomer propylene / ⁇ -olefin elastomer, melting point 110 ° C., MFR 3.0 g / 10 minutes ( ⁇ -olefin: 1-butene, which is abbreviated as elastomer).
  • MFR Melt flow rate According to JIS K-7210-1999, propylene / random copolymer and homopropylene have a temperature of 230 ° C, polyethylene-based polymer and polyethylene / ⁇ -olefin copolymer have a temperature of 190 ° C, and each has a load of 21.18 N. It was measured.
  • Thickness of each layer A cross section of the film was cut out with a microtome, and the cross section was magnified 1000 times using a digital microscope VHX-100 (manufactured by KEYENCE CORPORATION) and photographed using a cross-sectional photograph. The distance in the thickness direction of each layer was measured, and the thickness of each layer was obtained by back calculation from the magnification. In determining the thickness of each layer, a total of five cross-sectional photographs of a total of five locations arbitrarily selected from different measurement fields of view were used, and the average value was calculated.
  • a 20 ⁇ m biaxially stretched polypropylene film (U-0 manufactured by Mitsui Chemicals, Inc.) was laminated on the adhesive layer so that the corona-treated surface faced the adhesive layer as another base material, and Fujitec Co., Ltd.
  • the heat roll was heated to 40 ° C. and bonded using "Lamipacker” (registered trademark) LPA330 manufactured by ).
  • This laminated film was stored in an oven heated to 40 ° C. for 2 days to obtain a laminated body.
  • the heat-sealing layers (B) of the laminated film are overlapped with each other, and heat-sealed using a flat plate heat sealer under the conditions of a sealing temperature of 120 ° C., single-sided heating, a sealing pressure of 0.1 MPa, and a sealing time of 1 second.
  • the heat seal strength of the sample was measured at a tensile speed of 300 mm / min using "Tencilon" manufactured by Orientec. When the heat seal strength at this time was 3 N / 15 mm or more, the low temperature heat seal property was considered to be good.
  • Blocking resistance A film sample having a width of 30 mm and a length of 100 mm is prepared, and the base layer (A), the heat seal layer (B), and the heat seal layer (B) are overlapped with each other in a range of 30 mm ⁇ 40 mm.
  • the shear peeling force was measured at a tensile rate of 300 mm / min. In this measurement method, when the shear peeling force was 10 N / 12 cm 2 or less, the blocking resistance was “ ⁇ ”, and when 12 N / 12 cm 2 or more was “x”.
  • Gas barrier performance As a function-imparting layer on the base layer (A) of the composite film, the gas barrier performance of a film in which metal vapor deposition, metal oxide vapor deposition, and an organic substance layer are laminated is as follows: MOCON in the United States under the conditions of temperature 23 ° C. and humidity 0% RH.
  • the oxygen permeability was measured based on the B method (isopressure method) described in JIS K7126 (2000 version) using an oxygen permeability measuring device (OXTRAN 2/20) manufactured by ). Samples were taken from three locations at both ends and the center in the film width direction, and the average value of the three measured values was used as the oxygen transmittance value in each Example and Comparative Example.
  • the value of the oxygen permeability was gas barrier properties good following 50cc / m 2 ⁇ 24hr ⁇ atm .
  • the glossiness is 60 ° / reflection with respect to the vapor deposition surface in the film longitudinal direction (MD direction) according to JIS Z8741 (1983) using a variable-angle glossimeter type: UGV-5D manufactured by Suga Test Instruments Co., Ltd.
  • the measurement was performed at an angle of 60 °, and the measured value was the average value of three points in the width direction of the film. 600% or more was accepted.
  • the above-mentioned adhesive solution was applied to the function-imparting layer surface of the laminated film by the bar coating method, and dried at 80 ° C. for 45 seconds to form an adhesive layer having a thickness of 2 ⁇ m.
  • a 25 ⁇ m biaxially stretched polypropylene film (“Trefan” (registered trademark) YT42 manufactured by Toray Film Processing Co., Ltd.) was applied to the adhesive layer as another base material so that the corona-treated surface faces the adhesive layer.
  • the heat roll was heated to 40 ° C. and bonded using "Lamipacker” (registered trademark) LPA330 manufactured by Fuji Tech Co., Ltd.
  • This laminated film was stored in an oven heated to 40 ° C. for 2 days to obtain a laminated body.
  • the laminated film was cut to a width of 15 mm and a length of 150 mm to prepare a cut sample, and a tensile tester (RTG-1210 type) manufactured by A & D Co., Ltd.
  • Thickness of function-imparting layer The observation method with a transmission electron microscope is to use a focused ion beam processing device (manufactured by Hitachi, Ltd., FB-2000) after sampling the film to be observed by the microsampling method. It was used to make a thin film. Then, for protection, a carbon and tungsten protective film was formed. This sample was observed with a field emission transmission electron microscope (manufactured by Hitachi, Ltd., HF-2200, hereinafter referred to as TEM).
  • TEM field emission transmission electron microscope
  • Example 1 As the base layer (A) of the composite film, 95 parts by weight of the propylene / random copolymer (r-EPC), 5 parts by weight of high-density polyethylene (HDPE), and an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy). ) A resin composition obtained by mixing 0.125 parts by weight and 0.3 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as an antiblocking agent is supplied to one extruder heated to 240 ° C., melted, and heated.
  • r-EPC propylene / random copolymer
  • HDPE high-density polyethylene
  • antioxidant Irganox 1010 manufactured by Ciba Geigy
  • seal layer (B) 80 parts by weight of the above ethylene / propylene / butene random copolymer (r-EPBC ⁇ 2), 20 parts by weight of linear low density polyethylene (L-LDPE ⁇ 1), and an antioxidant. (“Irganox” 1010 manufactured by Ciba Geigy Co., Ltd.) A resin composition obtained by mixing 0.125 parts by weight and 0.2 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent was heated to another 240 ° C.
  • a co-extruded two-layer composite film having a thickness of 20 ⁇ m, a thickness of the heat-sealed layer (B) of 5 ⁇ m, and a total thickness of 25 ⁇ m was obtained.
  • the obtained composite film had good film-forming properties, no slack in the film, and was excellent in blocking resistance and low-temperature heat-sealing property.
  • Example 2 As the base layer (A) of the composite film, ethylene / propylene / butene random copolymer (r-EPBC ⁇ 1), 5 parts by weight of high-density polyethylene (HDPE), antioxidant (“Irganox” manufactured by Ciba Geigy). 1010) A co-extruded two-layer composite film was obtained in the same manner as in Example 1 except that a resin composition was prepared by mixing 0.125 parts by weight and 0.3 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as an antiblocking agent. rice field. The obtained composite film had good film-forming properties, no slack in the film, and was excellent in blocking resistance and low-temperature heat-sealing property.
  • r-EPBC ⁇ 1 ethylene / propylene / butene random copolymer
  • HDPE high-density polyethylene
  • antioxidant Irganox manufactured by Ciba Geigy
  • Example 3 As the base layer (A) of the composite film, 91 parts by weight of ethylene / propylene / butene random copolymer (r-EPBC ⁇ 1), 9 parts by weight of high-density polyethylene (HDPE), and an antioxidant (Ciba Geigy Co., Ltd. “Irga” Knox "1010) Co-extruded two-layer composite in the same manner as in Example 1 except that a resin composition containing 0.125 parts by weight and 0.3 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m was used as an antiblocking agent. I got a film. The obtained composite film had good film-forming properties, no slack in the film, and was excellent in blocking resistance and low-temperature heat-sealing property.
  • r-EPBC ⁇ 1 91 parts by weight of ethylene / propylene / butene random copolymer
  • HDPE high-density polyethylene
  • antioxidant Ciba Geigy Co., Ltd
  • Example 4 The same as in Example 1 except that the base layer (A) of the composite film was 98 parts by weight of ethylene / propylene / butene random copolymer (r-EPBC ⁇ 1) and 2 parts by weight of high-density polyethylene (HDPE). To obtain a co-extruded two-layer composite film. The obtained composite film had good film-forming properties, no slack in the film, and was excellent in blocking resistance and low-temperature heat-sealing property.
  • r-EPBC ⁇ 1 ethylene / propylene / butene random copolymer
  • HDPE high-density polyethylene
  • Example 5 95 parts by weight of ethylene / propylene / butene random copolymer (r-EPBC ⁇ 1) as the base layer (A) of the composite film, and linear low-density polyethylene (L-LDPE ⁇ 1) 5 as the polyethylene-based polymer.
  • a resin composition obtained by mixing 0.125 parts by weight of an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy) and 0.3 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as an antiblocking agent.
  • a co-extruded two-layer composite film was obtained in the same manner as in Example 1. The obtained composite film had good film-forming properties, no slack in the film, and was excellent in blocking resistance and low-temperature heat-sealing property.
  • Example 6 the heat-sealed layer (B) is 95 parts by weight of an ethylene / propylene / butene random copolymer (r-EPBC ⁇ 1) and 5 parts by weight of a linear low-density polyethylene (L-LDPE ⁇ 1). And 0.125 parts by weight of an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy Co., Ltd.) and 0.2 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent were mixed to prepare a resin composition of Examples. A co-extruded two-layer composite film was obtained in the same manner as in 1. The obtained composite film had good film-forming properties, no slack in the film, and was excellent in blocking resistance and low-temperature heat-sealing property.
  • an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy Co., Ltd.)
  • silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent were mixed to
  • Example 7 the heat-sealed layer (B) is 50 parts by weight of an ethylene / propylene / butene random copolymer (r-EPBC ⁇ 2) and 50 parts by weight of a linear low-density polyethylene (L-LDPE ⁇ 1). And 0.125 parts by weight of an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy Co., Ltd.) and 0.2 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent were mixed to prepare a resin composition of Examples. A co-extruded two-layer composite film was obtained in the same manner as in 1. The obtained composite film had good film-forming properties, no slack in the film, and was excellent in blocking resistance and low-temperature heat-sealing property.
  • an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy Co., Ltd.)
  • silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent were mixed to
  • the heat-sealed layer (B) is composed of 80 parts by weight of an ethylene / propylene / butene random copolymer (r-EPBC ⁇ 2) and a linear low-density polyethylene (L-LDPE ⁇ ) having a melting point of 113 ° C. 2)
  • a resin composition prepared by mixing 20 parts by weight, 0.125 parts by weight of an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy Co., Ltd.), and 0.2 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent.
  • a co-extruded two-layer composite film was obtained in the same manner as in Example 1 except for the above. The obtained composite film had good film-forming properties, no slack in the film, and was excellent in blocking resistance and low-temperature heat-sealing property.
  • Example 9 the heat-sealed layer (B) is 80 parts by weight of a propylene / butene random copolymer (r-EPC) and 20 parts by weight of a linear low-density polyethylene (L-LDPE ⁇ 2) having a melting point of 113 ° C.
  • the resin composition was obtained by mixing 0.125 parts by weight of an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy) and 0.2 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent.
  • a co-extruded two-layer composite film was obtained in the same manner as in Example 1. The obtained composite film had good film-forming properties, no slack in the film, and was excellent in blocking resistance and low-temperature heat-sealing property.
  • Example 10 the heat-sealed layer (B) was composed of 80 parts by weight of a propylene / 1-butene random copolymer (r-PBC) and a linear low-density polyethylene (L-LDPE ⁇ 2) having a melting point of 113 ° C.
  • a resin composition obtained by mixing 20 parts by weight of an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy), 0.125 parts by weight, and 0.2 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent.
  • Irganox an antioxidant
  • silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent.
  • a co-extruded two-layer composite film was obtained in the same manner as in Example 1. The obtained composite film had good film-forming properties, no slack in the film, and was excellent in blocking resistance and low-temperature heat-sealing property.
  • Example 11 the heat-sealed layer (B) has 30 parts by weight of a propylene / butene random copolymer (r-EPC), 50 parts by weight of a propylene / 1-butene random copolymer (r-PBC), and a melting point of 113. 20 parts by weight of linear low-density polyethylene (L-LDPE ⁇ 2) at ° C, 0.125 parts by weight of antioxidant (“Irganox” 1010 manufactured by Ciba Geigy), silica fine particles with an average particle diameter of 3 ⁇ m as a blocking agent
  • L-LDPE ⁇ 2 linear low-density polyethylene
  • antioxidant Irganox” 1010 manufactured by Ciba Geigy
  • silica fine particles with an average particle diameter of 3 ⁇ m as a blocking agent
  • Example 12 the heat-sealed layer (B) has 20 parts by weight of a propylene / butene random copolymer (r-EPC), 50 parts by weight of a propylene / butene random copolymer (r-PBC), and a melting point of 113. 20 parts by weight of linear low-density polyethylene (L-LDPE ⁇ 2) at ° C and propylene / 1-butene elastomer with ⁇ -olefin of 1-butene at a melting point of 110 ° C and MFR of 3.0 g / 10 minutes as a thermoplastic elastomer.
  • L-LDPE ⁇ 2 linear low-density polyethylene
  • an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy)
  • silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent.
  • Comparative Example 1 As the base layer (A) of the composite film, 5 parts by weight of high-density polyethylene (HDPE) is added to homopolypropylene (h-PP) having a melting point of 162 ° C., and an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy Co., Ltd.) 0.125.
  • a co-extruded two-layer composite film was obtained in the same manner as in Example 1 except that a resin composition was prepared by mixing 0.3 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as an anti-blocking agent.
  • the main raw material of the base layer (A) of the obtained composite film is homopolypropylene (h-PP) having a melting point of 162 ° C., the laminated interface with the heat seal layer (B) is disturbed and the film formation stability is generated. Was inferior to.
  • Comparative Example 2 As the base layer (A) of the composite film, 95 parts by weight of an ethylene / propylene / butene random copolymer (r-EPBC ⁇ 2) having a melting point of 127 ° C., 5 parts by weight of high-density polyethylene (HDPE), and an antioxidant. ("Irganox" 1010 manufactured by Ciba Geigy Co., Ltd.) The same as in Example 1 except that a resin composition was prepared by mixing 0.125 parts by weight and 0.3 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as an antiblocking agent. A co-extruded two-layer composite film was obtained. The obtained composite film was inferior in blocking resistance because the melting point of r-EPBC in the base layer (A) was low.
  • r-EPBC ⁇ 2 ethylene / propylene / butene random copolymer having a melting point of 127 ° C.
  • HDPE high-density polyethylene
  • antioxidant antioxidant
  • Comparative Example 3 As the base layer (A) of the composite film, 88 parts by weight of ethylene / propylene / butene random copolymer (r-EPBC ⁇ 1), 12 parts by weight of high-density polyethylene (HDPE), and an antioxidant (manufactured by Ciba Geigy Co., Ltd.) Irganox "1010) 0.125 parts by weight and 0.3 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as an anti-blocking agent were mixed to prepare a resin composition, which was coextruded in the same manner as in Example 1. I got a film. In the obtained composite film, since the amount of high-density polyethylene (HDPE) mixed in the base layer (A) was large, the laminated interface with the heat-sealing layer (B) was disturbed, and the film-forming stability was inferior.
  • HDPE high-density polyethylene
  • Comparative Example 4 As the base layer (A) of the composite film, 100 parts by weight of ethylene / propylene / butene random copolymer (r-EPBC ⁇ 1) and 0.125 parts by weight of an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy), A co-extruded two-layer composite film was obtained in the same manner as in Example 1 except that a resin composition was prepared by mixing 0.3 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as an antiblocking agent. The obtained composite film was inferior in blocking resistance because high-density polyethylene (HDPE) was not mixed in the base layer (A).
  • HDPE high-density polyethylene
  • Example 2 the heat-sealed layer (B) was added to 100 parts by weight of an ethylene / propylene / butene random copolymer (r-EPBC ⁇ 2) and 0.125 parts by weight of an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy Co., Ltd.).
  • r-EPBC ⁇ 2 an ethylene / propylene / butene random copolymer
  • Irganox 1010 manufactured by Ciba Geigy Co., Ltd.
  • a co-extruded two-layer composite film was obtained in the same manner as in Example 1 except that 0.2 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m were mixed as a blocking agent.
  • the obtained composite film had low low-temperature heat-sealing strength and was inferior in low-temperature heat-sealing property.
  • Example 2 the heat-sealed layer (B) was formed by 45 parts by weight of an ethylene / propylene / butene random copolymer (r-EPBC ⁇ 2) and 55 parts by weight of a linear low-density polyethylene (L-LDPE ⁇ 1). And 0.125 parts by weight of an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy Co., Ltd.) and 0.2 parts by weight of silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent were mixed to prepare a resin composition of Examples. A co-extruded two-layer composite film was obtained in the same manner as in 1.
  • an antioxidant (“Irganox” 1010 manufactured by Ciba Geigy Co., Ltd.)
  • silica fine particles having an average particle diameter of 3 ⁇ m as a blocking agent were mixed to prepare a resin composition of Examples.
  • a co-extruded two-layer composite film was obtained in the same manner as in 1.
  • Example 13 Using the composite film according to Example 11, aluminum is evaporated at a vacuum degree of 1.3 ⁇ 10 ⁇ 2 Pa in a normal roll-to-roll type vapor deposition machine, and the base layer of the composite film is obtained. An aluminum layer of 40 nm was formed on the surface (A) to obtain a laminated film.
  • This laminated film has an oxygen transmittance of 15 cc / m 2 ⁇ day ⁇ atm at 23 ° C. and 0% humidity, a total light transmittance of 1.3%, and a glossiness of 600%, and has gas barrier property, light shielding property, and gloss property. Was good.
  • Comparative Example 7 Using the composite film described in Comparative Example 2, aluminum is evaporated at a vacuum degree of 1.3 ⁇ 10 ⁇ 2 Pa in a normal roll-to-roll type vapor deposition machine, and the base layer of the composite film is obtained. An aluminum layer of 40 nm was formed on the surface (A) to obtain a laminated film. The oxygen transmittance of this laminated film was measured, and the oxygen transmittance at 23 ° C. and 0% humidity was 60 cc / m 2 ⁇ day ⁇ atm, the total light transmittance was 10%, and the glossiness was 450%. Since the melting point of the base layer (A) of the composite film is low, the laminated film is inferior in gas barrier property, light-shielding property, and gloss property due to a heat loss phenomenon during aluminum vapor deposition.
  • Example 14 Using the composite film described in Example 2, aluminum is evaporated at a vacuum degree of 1.3 ⁇ 10 ⁇ 2 Pa in a normal roll-to-roll type vapor deposition machine, and oxidized while introducing oxygen. An aluminum vapor-deposited layer was formed on the base layer (A) surface of the composite film at 10 nm to obtain a laminated film. The oxygen transmittance of the laminated film was measured, and the oxygen transmittance at 23 ° C. and 0% humidity was 48 cc / m 2 ⁇ day ⁇ atm, and the gas barrier property was good. Further, a laminate was prepared on the prepared aluminum oxide by the method described in the evaluation of easy adhesiveness, and the adhesion strength was measured. The adhesion strength was 2.1 N / 15 mm, and the easy adhesion was good.
  • Comparative Example 8 Using the composite film described in Comparative Example 3, aluminum is evaporated at a vacuum degree of 1.3 ⁇ 10 ⁇ 2 Pa in a normal roll-to-roll type vapor deposition machine, and oxidized while introducing oxygen. An aluminum vapor-deposited layer was formed on the base layer (A) surface of the composite film at 10 nm to obtain a laminated film.
  • This laminated film had an oxygen transmittance of 55 cc / m 2 ⁇ day ⁇ atm at 23 ° C. and 0% humidity, and an adhesion strength of 0.7 N / 15 mm.
  • the surface of the base layer (A) is roughened due to the disorder of the laminated interface between the composite film and the base layer (A) and the heat seal layer (B). The adhesion strength was inferior.
  • Example 15 As the lamination of the organic material layer on the base layer (A) of the composite film of Example 2, the ethylene content was 27 mol%, the saponification degree was 99.8%, and the MFR was 4.0 g / 10 minutes (under a load of 2160 g, 210).
  • Ethylene vinyl alcohol (“EVAL” L171B manufactured by Kuraray Co., Ltd.) and interfacial adhesive resin (hereinafter abbreviated as AD) (Admer QF500, manufactured by Mitsui Chemicals Co., Ltd.) Separately melt-kneaded in individual extruders, and using a 4-layer co-extruder, at an extrusion temperature of 220 ° C., 4 types of 4 layers of EVOH / AD / base layer (A) / heat seal layer (B) A multilayer film was obtained. Their thickness was 10/5 ⁇ m / 20 ⁇ m / 5 ⁇ m, respectively.
  • EVAL Ethylene vinyl alcohol
  • AD interfacial adhesive resin
  • the measured oxygen permeability of the laminated film 23 ° C., the oxygen permeability at 0% humidity is 5cc / m 2 ⁇ day ⁇ atm , the gas barrier property was good.
  • a laminate was prepared on the prepared EVOH by the method described in the evaluation of easy adhesion, and the adhesion strength was measured. The adhesion strength was 2.5 N / 15 mm, and the adhesiveness was good.
  • Comparative Example 9 As the lamination of the organic substance layer on the base layer (A) of the composite film described in Comparative Example 3, the EVOH layer / AD layer was laminated in the same manner as in Example 14 above.
  • the oxygen permeability of the laminated film was measured, 23 ° C., the oxygen permeability at 0% humidity is 5cc / m 2 ⁇ day ⁇ atm , although the gas barrier properties were good, the composite film base layer (A)
  • the surface of the base layer (A) was roughened due to the disorder of the laminated interface with the heat seal layer (B), and the adhesion strength was as low as 0.7 N / 15 mm.
  • Example 16 To impart easy printability on the base layer (A) of the composite film of Example 2, an organic-inorganic mixture was prepared by the following method to obtain a laminated film.
  • modified PVA polymerization degree 1,700, saponification degree 93.0%
  • ethyl silicate 40 average pentamer ethyl silicate oligomer manufactured by Corcote Co., Ltd. as a linear polysiloxane
  • Comparative Example 10 As an easy-to-print property on the base layer (A) of the composite film described in Comparative Example 3, an organic-inorganic mixture was formed in the same manner as in Example 15 to obtain a laminated film. Since the surface of the base layer (A) of this laminated film is rough, the evaluation of easy printability was grade 3, and the printability was poor.
  • the composite film of the present invention is excellent in low-temperature heat-sealing property and blocking resistance, and is excellent in processability when laminating a functionalizing layer on the film surface, and also functions on the surface of the base layer (A).
  • a functionalizing layer on the film surface and also functions on the surface of the base layer (A).

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

Abstract

L'invention concerne : un film composite ayant au moins deux couches, qui sont une couche de base (A) et une couche de thermoscellage (B), la couche de base (A) comprend une composition de résine obtenue par mélange de 1 à 10 parties en poids d'un polymère à base de polyéthylène (a2) avec 100 parties en poids d'un copolymère aléatoire de propylène (a1) ayant un point de fusion de 140 °C ou plus, et la couche de thermoscellage (B) comprend une composition de résine obtenue par mélange de 5 à 50 parties en poids d'un copolymère d'éthylène-α-oléfine (b2) ayant un point de fusion de 130 °C ou moins avec 100 parties en poids d'un copolymère aléatoire de propylène (b1) ayant un point de fusion de 145 °C ou moins ; et un film stratifié et un corps stratifié utilisant le film composite. L'invention peut concerner : un film composite présentant une excellente aptitude au thermoscellage à basse température et une excellente résistance au blocage, une étanchéité à l'air adaptée même lorsque les procédés de production de sac selon l'état de la technique et la vitesse de remplissage rapide sont utilisés, et une excellente aptitude au traitement lors de la stratification d'une couche pour conférer une fonctionnalité à la surface du film ; et un film stratifié et un corps stratifié utilisant le film composite.
PCT/JP2021/010113 2020-04-08 2021-03-12 Film composite, et film stratifié et corps stratifié l'utilisant WO2021205812A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7153255B1 (ja) * 2021-05-07 2022-10-14 東レフィルム加工株式会社 複合フィルム、積層フィルムおよびそれを用いた積層体
WO2022234761A1 (fr) * 2021-05-07 2022-11-10 東レフィルム加工株式会社 Film composite, et film stratifié ainsi que corps stratifié mettant en œuvre celui-ci
WO2023157881A1 (fr) * 2022-02-15 2023-08-24 大日本印刷株式会社 Film barrière stratifié, film stratifié, corps stratifié et récipient d'emballage
WO2024084928A1 (fr) * 2022-10-19 2024-04-25 東洋紡株式会社 Film d'étanchéité stratifié

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10166526A (ja) * 1996-12-05 1998-06-23 Toyobo Co Ltd ポリプロピレン系複合無延伸フィルム
JP2006299229A (ja) * 2005-03-24 2006-11-02 Prime Polymer:Kk フィルムおよび多層二軸延伸フィルム
JP2017132186A (ja) * 2016-01-29 2017-08-03 東レフィルム加工株式会社 耐衝撃性フィルムおよびそれを用いた積層体
JP2018118744A (ja) * 2017-01-23 2018-08-02 グンゼ株式会社 青果物包装体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10166526A (ja) * 1996-12-05 1998-06-23 Toyobo Co Ltd ポリプロピレン系複合無延伸フィルム
JP2006299229A (ja) * 2005-03-24 2006-11-02 Prime Polymer:Kk フィルムおよび多層二軸延伸フィルム
JP2017132186A (ja) * 2016-01-29 2017-08-03 東レフィルム加工株式会社 耐衝撃性フィルムおよびそれを用いた積層体
JP2018118744A (ja) * 2017-01-23 2018-08-02 グンゼ株式会社 青果物包装体

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7153255B1 (ja) * 2021-05-07 2022-10-14 東レフィルム加工株式会社 複合フィルム、積層フィルムおよびそれを用いた積層体
WO2022234761A1 (fr) * 2021-05-07 2022-11-10 東レフィルム加工株式会社 Film composite, et film stratifié ainsi que corps stratifié mettant en œuvre celui-ci
WO2023157881A1 (fr) * 2022-02-15 2023-08-24 大日本印刷株式会社 Film barrière stratifié, film stratifié, corps stratifié et récipient d'emballage
WO2024084928A1 (fr) * 2022-10-19 2024-04-25 東洋紡株式会社 Film d'étanchéité stratifié

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TW202146225A (zh) 2021-12-16

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