WO2015005279A1 - Easily openable laminated film and use therefor - Google Patents

Easily openable laminated film and use therefor Download PDF

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Publication number
WO2015005279A1
WO2015005279A1 PCT/JP2014/068043 JP2014068043W WO2015005279A1 WO 2015005279 A1 WO2015005279 A1 WO 2015005279A1 JP 2014068043 W JP2014068043 W JP 2014068043W WO 2015005279 A1 WO2015005279 A1 WO 2015005279A1
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WO
WIPO (PCT)
Prior art keywords
ethylene
layer
easy
polymer
laminated film
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PCT/JP2014/068043
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French (fr)
Japanese (ja)
Inventor
田口 栄一
和臣 石井
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三井化学東セロ株式会社
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Application filed by 三井化学東セロ株式会社 filed Critical 三井化学東セロ株式会社
Priority to JP2015526324A priority Critical patent/JP5968543B2/en
Priority to KR1020157030244A priority patent/KR101749854B1/en
Publication of WO2015005279A1 publication Critical patent/WO2015005279A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558Impact strength, toughness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/70Food packaging

Definitions

  • the present invention relates to an easily-openable resin laminated film having improved sealing properties and various uses, as well as excellent sealing properties and easy-opening properties to various materials.
  • Packaging for snacks such as rice crackers and potato chips, food packaging such as jelly, milk, yogurt, pudding, tofu, and lactic acid beverages, blister packaging, and other medicines, medical equipment, daily necessities, sundries, etc.
  • Packaging in which a tray-like plastic container is sealed with a lid made of a plastic laminate film or an aluminum foil laminate film is widely used. What is required for such packaging is mechanical strength that can withstand distribution channels, sealing strength that can maintain hygiene, and good openability during use.
  • a film in the category called easy-opening (easy peelability, easy peel) film is used as a bag with a heat-sealing layer as the innermost layer, or as a cover material.
  • the package used is widely used.
  • various heat-sealing layers proposed so far have high heat-sealing strength for sealing, but easy peelability at the time of opening is not always sufficient, and an appropriate balance between them can be obtained. It has been demanded.
  • an easy-opening packaging body in which an easy-peeling layer is composed of a mixture layer of polypropylene resin and polyethylene resin and a high-density polyethylene resin layer
  • an easy-opening packaging body in which an easy-peeling layer is composed of a mixture layer of polypropylene resin and polyethylene resin and a high-density polyethylene resin layer
  • Patent Document 1 A sealant film for a lid of a polypropylene container comprising an adhesive layer (easy peeling layer) and a support layer (laminate layer) made of a mixed resin of polypropylene and polyethylene, an ethylene- ⁇ -olefin copolymer, Resin composition for easy-open heat seal comprising propylene-ethylene copolymer and low density polyethylene (see Patent Document 3), polypropylene resin, ethylene / ⁇ -olefin random copolymer resin having a density of 930 kg / m 3 or less, and A multilayer sheet having a sealing layer made of a polyethylene resin composition (
  • the object of the present invention is to maintain sealing performance and easy opening, while maintaining sealing performance, that is, pressure from outside (external pressure) and pressure from inside (internal pressure) even at a temperature higher than room temperature.
  • Another object of the present invention is to obtain an easy-open laminated film having a sealing strength that can withstand the above.
  • the present invention relates to an easily openable laminated film and its use.
  • the easy-open laminated film is composed of a heat-sealing layer, an intermediate layer, and a laminate layer.
  • Thermal fusion layer Propylene polymer (A-1) 79.8 to 94% by mass, 4 to 10% by mass of an ethylene polymer (B-1) having a density of 900 kg / m 3 or more, Ethylene / ⁇ -olefin random copolymer (C-1) having a density of 860 kg / m 3 or more and less than 900 kg / m 3 1.5 to 7.5% by mass
  • the heat seal strength (peeling strength) stable in a wide temperature range, and the packaging body from the outside even at a temperature higher than room temperature. Sealing strength that can withstand pressure (external pressure) and pressure from the inside (internal pressure), and can be easily peeled when peeled (opened), and there is no stringing on the peeled surface, giving it a soft feel. is doing.
  • a commercially available resin usually a homopolymer of propylene having a density of about 890 to 930 kg / m 3 or a propylene copolymer, that is, at least one selected from propylene and a small amount of other ⁇ -olefins It is a copolymer comprising the comonomer.
  • the copolymer may be a random copolymer or a block copolymer.
  • ⁇ -olefins in the definition of this copolymer of propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and the like. And ⁇ -olefins having about 4 to 20 carbon atoms. Such other ⁇ -olefins may be copolymerized singly or in combination of two or more ⁇ -olefins.
  • the melting point based on a differential scanning calorimeter (DSC) is 110 to 145 ° C., particularly 115, because of the balance of heat-fusibility and heat resistance of the easily openable laminated film obtained.
  • a propylene / ⁇ -olefin random copolymer in the range of ⁇ 140 ° C. is preferred.
  • the propylene polymer (A-1) according to the present invention includes an ethylene polymer (B-1), an ethylene / ⁇ -olefin random copolymer (C-1), and a tackifier resin (D-1) described later.
  • the melt flow rate (MFR) (ASTM D1238, 230 ° C., 2160 g load) is not particularly limited as long as the olefin polymer composition (E) formed by mixing with the film has an ability to form a film. Therefore, it is usually in the range of 0.01 to 100 g / 10 minutes, preferably 0.1 to 70 g / 10 minutes.
  • the propylene polymer (A-1) according to the present invention two or more propylene polymers can be used in combination.
  • the propylene polymer (A-1) according to the present invention is produced using various known production methods, specifically, for example, using an olefin polymerization catalyst such as a Ziegler-Natta catalyst or a single site catalyst. Can do. In particular, it can be produced using a single site catalyst.
  • the single site catalyst is a catalyst having a uniform active site (single site), and examples thereof include a metallocene catalyst (so-called Kaminsky catalyst) and a Brookhart catalyst.
  • the metallocene catalyst is a catalyst composed of a metallocene transition metal compound, an organoaluminum compound, and at least one compound selected from the group consisting of compounds that react with the metallocene transition metal compound to form an ion pair. It may be supported.
  • an ethylene homopolymer or ethylene and a small amount of an ⁇ -olefin having 3 to 10 carbon atoms such as propylene, 1- Random copolymers with butene, 1-heptene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc., so-called high-pressure low-density polyethylene (HP-LDPE), linear or linear Ethylene low polymer (L-LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) Is Ren ⁇ alpha-olefin copolymer.
  • HP-LDPE high-pressure low-density polyethylene
  • L-LDPE linear or linear Ethylene low polymer
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • the ethylene polymer (B-1) according to the present invention may be a single polymer or a composition (mixture) of two or more ethylene polymers.
  • the melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) of the ethylene polymer (B-1) according to the present invention is the same as that of the propylene polymer (A-1), ethylene / ⁇ -olefin described later.
  • MFR melt flow rate
  • ASTM D12308 190 ° C., 2160 g load
  • the olefin polymer composition (E) is mixed with the random copolymer (C-1) and the tackifier resin (D-1), it is not particularly limited as long as it has a film-forming ability. 0.01 to 100 g / 10 min, preferably 0.1 to 70 g / 10 min.
  • the ethylene / ⁇ -olefin random copolymer (C-1) which is one of the constituent components of the olefin polymer composition (E) that serves as the heat-sealing layer of the easy-open laminated film of the present invention, has a density of 860 kg / m 3 or more ⁇ 900 kg / m less than 3, preferably ⁇ - olefin 860 kg / m 3 or more ⁇ 895kg / m of less than 3 ethylene and carbon 3-10, such as propylene, 1-butene, 1-heptene, 1 -Random copolymers with ⁇ -olefins such as hexene, 1-octene, 4-methyl-1-pentene.
  • the ethylene / ⁇ -olefin random copolymer (C-1) is preferably at least one ethylene / ⁇ -olefin having a density in the range of 860 to 895 kg / m 3 and an ⁇ -olefin having 4 to 10 carbon atoms. It is composed of an ⁇ -olefin random copolymer (C1-1) and an ethylene / propylene random copolymer (C1-2) having a density in the range of 865 to 875 kg / m 3 .
  • the ethylene / ⁇ -olefin random copolymer (C1-1) is preferably a polymer having at least one of the following physical properties (c-1a) to (c-1c).
  • an ethylene / ⁇ -olefin random copolymer (C1-1) an ethylene / ⁇ -olefin random copolymer having the physical properties of (c1-1a), (c1-1b), or (c1-1c) (C1-1) and further physical properties of (c1-1a) and (c1-1b), physical properties of (c1-1a) and (c1-1c), or (c1-1b) and (c1-1c)
  • the ethylene / propylene random copolymer (C1-2) is preferably a polymer having at least one of the following physical properties (c1-2a) and (c1-2b).
  • crystallinity by X-ray is less than 5% amorphous or slightly crystalline
  • Such an ethylene / propylene random copolymer (C1-2) includes an ethylene / propylene random copolymer (C1-2) having the physical properties of (c1-2a) or (c1-2b),
  • the ethylene / ⁇ -olefin random copolymer (C-1) has an ethylene content of 85 to 93 mol%, X-rays in consideration of the heat-sealing characteristics of the resulting easy-open laminated film.
  • Low crystalline ethylene ⁇ - having a melting point in the range of 60 to 90 ° C.
  • composition determined from an endothermic curve with a crystallinity of 7 to 30% and a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min Olefin random copolymer (C1-1) and ethylene / propylene random having an amorphous content or a slight crystallinity in which ethylene content is in the range of 75 to 85 mol% and crystallinity by X-ray is less than 5%
  • a composition (mixture) comprising the copolymer (C1-2) is preferred.
  • Examples of the ethylene / ⁇ -olefin random copolymer (C-1) according to the present invention include the propylene polymer (A-1), the ethylene polymer (B-1), and a tackifier resin (D described later).
  • the melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) is not particularly limited as long as it has film-forming ability.
  • the melt flow rate (MFR) is preferably 0.01 to 20 g / 10 min.
  • the ethylene / ⁇ -olefin random copolymer (C-1) according to the present invention comprises, for example, a transition metal compound catalyst component, for example, a catalyst comprising a vanadium compound or a zirconium compound and an organoaluminum compound catalyst component, It can be obtained by copolymerizing an ⁇ -olefin.
  • a transition metal compound catalyst component for example, a catalyst comprising a vanadium compound or a zirconium compound and an organoaluminum compound catalyst component, It can be obtained by copolymerizing an ⁇ -olefin.
  • the tackifier resin (D-1) which is one of the constituent components of the olefin polymer composition (E) that serves as the heat-sealing layer of the easy-open laminate film of the present invention, is manufactured and sold as a tackifier.
  • Examples of the aliphatic hydrocarbon resin include polymerization of a fraction containing at least one mono- or diolefin having 4 to 5 carbon atoms, such as 1-butene, isobutene, butadiene, 1,3-pentadiene, and isoprene.
  • the resulting resin can be mentioned.
  • alicyclic hydrocarbon resins include resins obtained by polymerization after dimerization of diene components in spent C4 to C5 fractions, resins obtained by polymerizing cyclic monomers such as cyclopentadiene, aromatic carbonization Examples thereof include a resin obtained by hydrogenating a hydrogen resin.
  • aromatic hydrocarbon resins include resins obtained by polymerizing a fraction containing at least one C8-C10 vinyl aromatic hydrocarbon such as vinyltoluene, indene, ⁇ -methylstyrene, or the like. And resins obtained by copolymerizing the above aliphatic hydrocarbon fractions.
  • polyterpene resins include ⁇ -pinene polymers, ⁇ -pinene polymers, dipentene polymers, terpene / phenol copolymers, ⁇ -pinene / phenol copolymers, and hydrogenated products thereof. it can.
  • rosins include rosins such as gum rosin, wood rosin and tall oil, and modified products thereof. Examples of modified products include those subjected to modification such as hydrogenation, disproportionation, dimerization, and esterification. it can.
  • Styrenic hydrocarbon resins are low molecular weight resinous polymers obtained by polymerizing one or more styrene monomers such as high-purity styrene, vinyltoluene, ⁇ -methylstyrene, and isopropyltoluene. Can be mentioned.
  • the olefin polymer composition (E) according to the present invention is used as an easily openable sealing material for food and beverage packaging, the fragrance is considered in consideration of odorlessness, food hygiene, miscibility with other components, etc. It is preferable to use a resin obtained by intra-nuclear hydrogenation of a group hydrocarbon resin or a polyterpene resin.
  • the ethylene polymer (B-2) which is one of the components of the ethylene polymer composition (F) constituting the intermediate layer of the easy-open laminated film of the present invention, has a density of 940 to 970 kg / m 3 , Preferably, a homopolymer of ethylene in the range of 945 to 967 kg / m 3 or ethylene and a small amount of an ⁇ -olefin having 3 to 10 carbon atoms such as propylene, 1-butene, 1-heptene, 1-hexene, 1 -Random copolymer with octene, 4-methyl-1-pentene, etc., and is usually a polymer mainly composed of ethylene manufactured and sold as high density polyethylene (HDPE).
  • HDPE high density polyethylene
  • the melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) of the ethylene-based polymer (B-2) according to the present invention is ethylene mixed with a high-pressure method low-density polyethylene (B-3) described later.
  • the polymer composition (F) is not particularly limited as long as it has a film-forming ability, but is usually in the range of 0.01 to 100 g / 10 minutes, preferably 0.1 to 70 g / 10 minutes.
  • the high-pressure low-density polyethylene (B-3) which is one of the components of the ethylene polymer composition (F) constituting the intermediate layer of the easy-open laminate film of the present invention, has a density of 905 to 935 kg / m 3. Preferably, it is in the range of 910 to 925 kg / m 3 .
  • the high-pressure method low-density polyethylene (B-3) is an ethylene homopolymer usually produced and sold as a high-pressure method low-density polyethylene (HP-LDPE), or a copolymer of ethylene and a small amount of vinyl acetate. It is a polymer.
  • the melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) of the high-pressure method low-density polyethylene (B-3) according to the present invention is an ethylene-based mixture obtained by mixing with the ethylene-based polymer (B-2).
  • the polymer composition (F) is not particularly limited as long as it has a film-forming ability, but is usually in the range of 0.01 to 100 g / 10 minutes, preferably 0.1 to 70 g / 10 minutes.
  • the ethylene polymer (B-4) constituting the laminate layer of the easy-open laminate film of the present invention has a density of 900 to 950 kg / m 3 , preferably 920 to 940 kg / m 3 , and ethylene and carbon number Is a random copolymer with 4 to 10 ⁇ -olefin, such as 1-butene, 1-heptene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc., usually linear or linear It is a polymer mainly composed of ethylene and manufactured and sold as a low-density polyethylene (L-LDPE).
  • L-LDPE low-density polyethylene
  • the ethylene polymer (B-4) according to the present invention is preferably a random copolymer of ethylene and an ⁇ -olefin having 4 or more carbon atoms.
  • the melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) of the ethylene-based polymer (B-4) according to the present invention is not particularly limited as long as it has a film-forming ability. It is in the range of 100 g / 10 min, preferably 0.1 to 70 g / 10 min.
  • a polymer including other ethylene polymers may be used in combination.
  • the other polymer is generally a laminate layer.
  • the content of the polymer component is less than 50% by mass, of which 30% by mass or less, and more preferably 10% by mass or less.
  • additives can be blended in the ethylene polymer (B-4) according to the present invention as long as the object of the present invention is not impaired. Examples of such additives include inorganic fillers such as silica and talc, antioxidants, weathering stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents, and pigments.
  • an organic compound type anti-blocking agent or slip agent is also effective in improving workability and workability during film forming, laminating, and packaging operations.
  • organic compound type anti-blocking agents and slip agents include palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, oleyl palmamide, stearyl palmamide, methylenebisstearylamide, methylene
  • examples thereof include various amides such as bisoleylamide, ethylenebisoleylamide, and ethylenebiserucamide, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and hydrogenated castor oil.
  • ⁇ Olefin polymer composition (E)> The olefin polymer composition (E) that forms the heat-sealing layer of the easy-open laminate film of the present invention, 79.8 to 94% by mass of the propylene polymer (A-1), Preferably 81.1 to 91.3% by mass, 4 to 10% by mass of the ethylene polymer (B-1), Preferably 5.5 to 9% by mass, 1.5 to 7.5% by mass of the ethylene / ⁇ -olefin random copolymer (C-1), Preferably 2.5 to 7.5% by mass, And 0.5 to 2.7% by mass of the tackifier resin (D-1), Preferably 0.7 to 2.4 mass% [However, (A-1) + (B-1) + (C-1) + (D-1) 100 mass%) It is a composition containing.
  • the propylene polymer (A-1), the ethylene polymer (B-1), the ethylene / ⁇ -olefin random copolymer (C-1) body, and the olefin polymer composition (E) When a composition in which the tackifying resin (D-1) satisfies the above range is used, the resulting easy-open laminated film has an excellent balance between easy-open property and sealing strength.
  • additives can be blended with the olefin polymer composition (E) according to the present invention as long as the object of the present invention is not impaired.
  • additives include inorganic fillers such as silica and talc, antioxidants, weathering stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents, and pigments.
  • the compounding of an organic compound type anti-blocking agent or slip agent is also effective in improving workability and workability during film forming, laminating, and packaging operations.
  • organic compound type anti-blocking agents and slip agents examples include palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, oleyl palmamide, stearyl palmamide, methylenebisstearylamide, methylene
  • examples thereof include various amides such as bisoleylamide, ethylenebisoleylamide, and ethylenebiserucamide, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and hydrogenated castor oil.
  • the olefin polymer composition (E) comprises a propylene polymer (A-1), an ethylene polymer (B-1), an ethylene / ⁇ -olefin random copolymer (C-1) and Each component of the tackifying resin (D-1) and an additive that is optionally blended can be prepared by mixing simultaneously or sequentially.
  • other polymers such as ethylene polymers may be used in combination.
  • the other polymer is generally 50% by mass of the polymer component constituting the heat-sealing layer. Among them, it is 30% by mass or less, more preferably 10% by mass or less.
  • it is preferable to melt and mix using a single screw extruder, a twin screw extruder, a Banbury mixer, various kneaders, etc., and the mixing order is not particularly limited.
  • ⁇ Ethylene polymer composition (F)> The ethylene-based polymer composition (F) that forms the intermediate layer of the easy-open laminate film of the present invention, 50 to 95% by mass of the ethylene polymer (B-2), Preferably 70 to 92% by mass, And 5-50% by mass of the high pressure method low density polyethylene (B-3), Preferably 8-30% by mass [However, (B-2) + (B-3) 100 mass%. ] It is a composition containing. When a composition having an ethylene polymer (B-2) amount of less than 50% by mass is used as the intermediate layer, the film-forming property of the resulting easy-open laminated film is reduced, film strength, heat resistance, etc. Other than the easy open function, there is a risk of inferiority.
  • a polymer such as an ethylene polymer other than these may be used in combination.
  • the other polymer is generally less than 50% by mass of the polymer component constituting the intermediate layer, of which 30% by mass or less, and more preferably 10% by mass or less.
  • additives can be blended in the ethylene-based polymer composition (F) constituting the intermediate layer according to the present invention as long as the object of the present invention is not impaired.
  • additives may include inorganic fillers such as silica and talc, antioxidants, weathering stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents, pigments and the like.
  • an organic compound type anti-blocking agent or slip agent is also effective in improving workability and workability during film forming, laminating, and packaging operations.
  • organic compound type anti-blocking agents and slip agents include palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, oleyl palmamide, stearyl palmamide, methylenebisstearylamide, methylene
  • examples thereof include various amides such as bisoleylamide, ethylenebisoleylamide, and ethylenebiserucamide, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and hydrogenated castor oil.
  • the easy-open laminate film of the present invention includes a heat-sealing layer composed of the olefin polymer composition (E), an intermediate layer composed of the ethylene polymer composition (F), and the ethylene heavy layer. It consists of a laminate layer composed of the union (B-4). As long as the intermediate layer constituting the easy-open laminate film of the present invention is composed of the ethylene polymer composition (F), it may be composed of one layer or two or more layers.
  • the thickness of the easy-open laminated film of the present invention is variously determined depending on the application.
  • the thickness of the heat-sealing layer is usually 1 to 80 ⁇ m, preferably 2 to 50 ⁇ m, The thickness is 8 to 498 ⁇ m, preferably 16 to 96 ⁇ m, the thickness of the laminate layer is 1 to 80 ⁇ m, preferably 2 to 50 ⁇ m, and the total thickness of the easy-open laminated film is 10 to 500 ⁇ m, preferably It is in the range of 20-100 ⁇ m.
  • the easy-open laminate film of the present invention is a surface of a laminate layer, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, etc., in order to improve the printability or adhesion with a base material layer.
  • An activation process may be performed.
  • the easy-open laminated film of the present invention can be laminated with a base material layer and used for various applications.
  • stacked with the laminate layer of the easily openable laminated film of this invention consists of a sheet-like or film-like thing which consists of thermoplastic resins, paper, aluminum foil, etc.
  • the thermoplastic resin include various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate).
  • thermoplastic resins having good stretchability and transparency such as polypropylene, polyethylene terephthalate, and polyamide, are preferable.
  • the substrate made of such a thermoplastic resin film may be an unstretched film or a stretched film, and a laminate of one or more coextruded products, extruded laminate products, dry laminate products, etc. It may be the body.
  • the base material layer in order to improve the adhesiveness of one side or both sides of the base material layer with the laminate layer of the easy-open laminate film of the present invention, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, frame treatment, etc.
  • the surface activation treatment may be performed.
  • the thickness of the base material layer is usually in the range of 5 to 1000 ⁇ m, preferably 9 to 100 ⁇ m.
  • the olefin polymer composition (E) having the above composition constituting the heat-sealing layer may be prepared in advance, or the propylene polymer (A-1), A predetermined amount of the ethylene polymer (B-1), the ethylene / ⁇ -olefin random copolymer (C-1), and the tackifier resin (D-1) may be weighed and directly fed to the film forming machine.
  • an ethylene polymer composition (F) having the above composition may be prepared in advance for the intermediate layer, or an ethylene polymer (B-2) and a high-pressure method low density polyethylene (B-3) may be prepared. A predetermined amount may be measured and put directly into the film forming machine. Such laminated films may be individually laminated after being molded, but the method of coextrusion molding using a multilayer die having at least a three-layer structure is most preferable.
  • the easy-open laminated film or the easy-open laminated film laminated with the base material layer of the present invention can be used as various packaging materials.
  • An example of a suitable packaging material is a container lid that uses a heat-sealing layer as the container innermost layer.
  • the easy-open laminated film may be used as it is as a lid material, or may be printed and used. Further, it may be bonded to paper that is printed or not, aluminum foil, or the like to form a lid. Further, depending on the application, it may be cut in advance according to the shape of the container to form a lid.
  • the easy-open laminated film of the present invention can form a heat seal layer by heat-sealing to various adherends.
  • adherends include a propylene polymer, polystyrene, polyester, polycarbonate, polyvinyl chloride and the like. These adherends can be of various shapes such as films, sheets, trays, cups, bottles and the like.
  • a propylene-based polymer is particularly preferably used as the adherend because it is excellent in the sealing property, easy-opening property, heat resistance, oil resistance and the like of the heat seal layer.
  • propylene-based polymers are in the same category as the propylene-based polymer (A-1), but the individual physical properties may be the same or different.
  • a propylene polymer formed into various shapes such as a film, a sheet, a tray, a cup, and a bottle by a known method according to the packaging material should be used.
  • Can do In the case of a film or a sheet, it can be produced by the same method as that for the easy-open laminated film.
  • a tray or a cup In the case of a tray or a cup, it can be produced by once producing a sheet by the above method and then forming a container such as a tray or a cup by thermoforming such as vacuum forming or pressure forming.
  • a cup or bottle it can be molded as a container by injection molding, injection hollow molding (injection blow), hollow molding or the like.
  • the easy-open laminated film of the present invention When the easy-open laminated film of the present invention is used as a packaging material, for example, the easy-open laminated film itself can be folded and sealed in three directions, or two easy-open laminated films can be sealed in four directions to form a package. Alternatively, the easy-open laminated film may be formed with the above-mentioned various adherends and a heat seal layer to form a package.
  • the shape of the package of the present invention can take various shapes depending on the shape, form or application of the material to be packaged.
  • a packaging material is filled in a three-sided sealing bag composed of an easy-open laminated film and a film having a heat sealing layer composed of a propylene-based polymer layer, and then the mouth is heat sealed.
  • a heat sealing layer made of a propylene polymer layer
  • a four-side sealed package After filling the material to be packaged into a sheet, tray, cup, bottle, etc. having a heat sealing layer made of a propylene polymer layer, a four-side sealed package, and then a heat-sealing layer of an easy-open laminated film
  • Examples thereof include a package body in which the upper surface is sealed with a lid material (seal material) serving as the innermost layer.
  • the manufacturing method of the following package bodies can be provided.
  • the olefin polymer is used by using the easily peelable laminated film of the present invention as a lid.
  • the heat sealing layer of the plastic container which is the surface opposite to the heat-sealing layer composed of the composition (E), has a surface temperature of 160 ° C. to 210 ° C., preferably 170 ° C. to 200 ° C. The method of heat-sealing can be illustrated.
  • Propylene polymer (A-1) (1-1) Propylene / ethylene random copolymer (R-PP-1): Density; 910 kg / m 3 , Melt flow rate (MFR) (230 ° C.); 9 g / 10 minutes, Melting point: 115 ° C.
  • R-PP-2 Propylene / ethylene / 1-butene random copolymer
  • Ethylene polymer (B-1) High density polyethylene (HDPE-1): Density; 954 kg / m 3 , MFR (190 ° C.); 1.1 g / 10 min; Melting point: 132 ° C.
  • HDPE-1 High density polyethylene
  • Ethylene / ⁇ -olefin random copolymer (C-1) (3-1) Ethylene / 1-butene random copolymer (EBR): Ethylene content; 89.1 mol%; Crystallinity: 10%, Density; 886 kg / m 3 , MFR (190 ° C.); 4.0 g / 10 min.
  • EBR Ethylene / 1-butene random copolymer
  • EBR 1-butene random copolymer
  • Crystallinity 10%, Density; 886 kg / m 3 , MFR (190 ° C.); 4.0 g / 10 min.
  • Tackifying resin D-1 Hydrogenated aromatic hydrocarbon resin (Arcon) (manufactured by Arakawa Chemical Co., Ltd., trade name: Alcon P115, Ring Ball Method Softening Point 115 ° C.)
  • Ethylene polymer (B-2) High density polyethylene (HDPE-2): Density; 954 kg / m 3 , MFR (190 ° C.); 1.1 g / 10 minutes, Melting point: 132 ° C. (6) High pressure method low density polyethylene (B-3) High pressure low density polyethylene (HP-LDPE): Density; 917 kg / m 3 , MFR; 7.2 g / 10 min.
  • Ethylene polymer (B-4) Linear or linear low density polyethylene (L-LDPE) Ethylene 4-methyl-1-pentene random copolymer (this belongs to L-LDPE): Density; 935 kg / m 3 , MFR; 2.3 g / 10 minutes, Melting point: 124 ° C.
  • L-LDPE Linear or linear low density polyethylene
  • the physical properties of the heat-fusible laminated films obtained in the examples and comparative examples of the present invention were measured by the following methods.
  • (1) Evaluation of easy peelability In order to evaluate easy peelability, a 12 ⁇ m thick biaxially stretched polyethylene terephthalate film (PET) was subjected to corona treatment of the films obtained in each of the Examples and Comparative Examples.
  • a laminated film was prepared by laminating by dry lamination using a urethane adhesive on the surface, and a polypropylene sheet having a thickness of 300 ⁇ m was prepared as a heat seal layer.
  • the heat-sealing layer and the polypropylene sheet of each laminated film were overlapped, and sealed at a predetermined temperature shown in Table 1 at a pressure of 0.2 MPa for 1 second using a sealer having a width of 5 mm. And then left to cool. Thereafter, the heat-sealed test specimen was treated at 115 ° C. for 30 minutes using a high-temperature and high-pressure sterilizer (retort treatment equipment), and then the specimen was cooled. A test piece having a width of 15 mm was cut from this, and the heat seal portion was peeled off at a crosshead speed of 500 mm / min, and the strength thereof was defined as heat seal strength (N / 15 mm).
  • the evaluation of easy peelability was evaluated as ⁇ when the heat seal strength did not exceed 15.0 N / 15 mm, and it was not peeled off in a thread-like manner or a film form due to delamination with a tendency to cohesive peeling. Even if the heat seal strength exceeded 15.0 N / 15 mm even if the peeled state had no problem, it was rated as ⁇ . The case where the heat seal strength exceeded 15.0 N / 15 mm and a tendency to complete sealing was indicated as x.
  • sealing strength The strength at the time of peeling from the material seal portion or cutting the edge and opening was defined as sealing strength (Mpa). This measurement was evaluated using a sealing strength measuring instrument (JIS-Z0238 compliant) manufactured by Sun Science Co., Ltd. The sealing evaluation was evaluated as “ ⁇ ” when the average strength was 0.045 MPa or more and “ ⁇ ” when the average was less than 0.045 MPa.
  • the peeled state is not threaded or filmy and does not peel off, the heat seal strength does not exceed 15.0 N / 15 mm, and the average value of the sealing strength is 0.045 MPa or more.
  • the thing was ⁇ .
  • the case where the peeled state was peeled off in a stringy manner or in the form of a film, or the heat seal strength, which tends to be completely sealed, exceeding 20 N / 15 mm was marked as x.
  • a heat seal strength exceeding 15.0 N / 15 mm or a seal strength of 0.045 MPa or less was indicated by ⁇ .
  • An olefin polymer composition (E) prepared by adjusting the R-PP-1, R-PP-2, HDPE-1, EBR, EPR, and alkone with the blending amounts shown in Table 1 as a heat-sealing layer.
  • An intermediate polymer layer (F) obtained by dry blending 85% by mass of HDPE-2 and HP-LDPE; 15% by mass was used as an intermediate layer, and L-LDPE was used as a laminate layer.
  • the physical properties of the obtained easily openable laminated film were measured by the method described above. The results are shown in Table 1.
  • the physical properties of the obtained easily openable laminated film were measured by the method described above. The results are shown in Table 2.
  • Laminated films similar to those of Comparative Examples 1 to 3 were obtained except that an ethylene polymer composition comprising 100% by mass of HDPE-2 was used. The results are shown in Table 2.
  • the easy-open laminate films obtained in Examples 1 to 5 have a heat-sealing strength of about 10 to 15 N / 15 mm and are easy to open, with no peeling or stringing, and a clean state.
  • the sealing strength was high even though the contents were at a high temperature of about 60 ° C.
  • the easy-open laminated films obtained in Comparative Examples 1 to 4 have a high heat seal strength of about 18 to 38 N / 15 mm and are not suitable as easy open films. If the strength is weak and the contents are transferred at a high temperature, leakage may occur during the transfer.
  • the easy-open laminate film of the present invention is a packaging film as it is as an easy-open laminate film having low-temperature heat sealability, blocking resistance, impact resistance suitable for packaging materials, slip properties, rigidity, transparency, etc.
  • it is suitable as a lid material for polypropylene sheets, trays, cups, bottles, etc., packaging for snacks such as rice crackers, potato chips, etc., or food packaging such as jelly, milk, yogurt, pudding, tofu, lactic acid beverages, etc.
  • containers made of polypropylene such as pulp jelly, pudding, tofu, and other various container lid packaging using this easy-open laminated film, and packaging such as vertical and horizontal pillow bags that do not use containers are high. It has sealing properties and sealing properties and is suitable as a packaging material.

Landscapes

  • Wrappers (AREA)
  • Packages (AREA)
  • Laminated Bodies (AREA)

Abstract

An easily openable laminated film comprising a hot-melt layer composed of an olefin polymer composition (E), an intermediate layer composed of an ethylene polymer composition (F), and a laminate layer composed of an ethylene polymer (B-4). The olefin polymer composition (E) comprises a propylene polymer (A-1), an ethylene polymer (B-1), an ethylene-α-olefin random copolymer (C-1), and a adhesion-imparting resin (D-1). The ethylene polymer composition (F) comprises an ethylene polymer (B-2) and a high-pressure-process low-density polyethylene (B-3). The easily openable laminated film has sealing strength capable of resisting pressure from outside (external pressure) and pressure from inside (internal pressure), even when the seal; i.e., the casing, is at a temperature above room temperature, while maintaining excellent sealing properties and easy-opening properties.

Description

易開封性積層フィルム及びその用途Easy-open laminated film and use thereof
 本発明は、種々の材料に対し、優れた密封性及び易開封性を示すと共に、封緘性が改良された易開封性樹脂積層フィルム及びその用途に関する。 The present invention relates to an easily-openable resin laminated film having improved sealing properties and various uses, as well as excellent sealing properties and easy-opening properties to various materials.
 せんべい、ポテトチップス等のスナック菓子包装、あるいはゼリー、ミルク、ヨーグルト、プリン、豆腐、乳酸飲料等の食品包装や、ブリスター包装、その他、医薬品、医療器具、日用品、雑貨等の包装として、ボトル、カップないしトレー状のプラスチック容器をプラスチックラミネートフィルムないしアルミ箔ラミネートフィルムからなる蓋材でシールした包装が広く採用されている。このような包装に要求されることは、流通経路に耐える機械的な強度、衛生性の保持ができるシール強度及び使用時における開封性の良さである。 Packaging for snacks such as rice crackers and potato chips, food packaging such as jelly, milk, yogurt, pudding, tofu, and lactic acid beverages, blister packaging, and other medicines, medical equipment, daily necessities, sundries, etc. Packaging in which a tray-like plastic container is sealed with a lid made of a plastic laminate film or an aluminum foil laminate film is widely used. What is required for such packaging is mechanical strength that can withstand distribution channels, sealing strength that can maintain hygiene, and good openability during use.
 そのような包装に使われる資材の一つとして、易開封性(易剥離性、イージーピール性)フィルムと呼ばれる範疇のフィルムを、最内層である熱融着層とした袋に、あるいは蓋材に用いた包装体が広く利用されている。しかし、これまで提案されている各種の熱融着層は、密封するためのヒートシール強度は高いが、開封時のイージーピール性は必ずしも十分ではなく、両者の間に適度なバランスをとることが求められている。 As one of the materials used for such packaging, a film in the category called easy-opening (easy peelability, easy peel) film is used as a bag with a heat-sealing layer as the innermost layer, or as a cover material. The package used is widely used. However, various heat-sealing layers proposed so far have high heat-sealing strength for sealing, but easy peelability at the time of opening is not always sufficient, and an appropriate balance between them can be obtained. It has been demanded.
 かかる易開封性(易剥離性)を有するフィルムとして、例えば、易剥離層をポリプロピレン系樹脂とポリエチレン樹脂との混合物層と高密度ポエチレン樹脂層とからなる易開封性包装体(特許文献1参照)、ポリプロピレンとポリエチレンとの混合樹脂からなる接着剤層(易剥離層)と支持層(ラミネート層)からなるポリプロピレン容器の蓋材シーラントフィルム(特許文献2参照)、エチレン-α-オレフィン共重合体、プロピレン-エチレン共重合体及び低密度ポリエチレンからなる易開封性ヒートシール用樹脂組成物(特許文献3参照)、ポリプロピレン系樹脂、密度が930kg/m以下のエチレン・α-オレフィンランダム共重合樹脂及びポリエチレン樹脂組成物からなるシール層を有する多層シート(特許文献4参照)等、数多く提案されている。しかしながら、単にポリプロピレン系樹脂とポリエチレン樹脂との混合物層を熱融着層としたフィルムは、未だ密封性、易開封性、耐熱性、耐油性のバランスの点で必ずしも満足できるものではない。 As a film having such an easy-opening property (easy-peeling property), for example, an easy-opening packaging body in which an easy-peeling layer is composed of a mixture layer of polypropylene resin and polyethylene resin and a high-density polyethylene resin layer (see Patent Document 1) A sealant film for a lid of a polypropylene container comprising an adhesive layer (easy peeling layer) and a support layer (laminate layer) made of a mixed resin of polypropylene and polyethylene, an ethylene-α-olefin copolymer, Resin composition for easy-open heat seal comprising propylene-ethylene copolymer and low density polyethylene (see Patent Document 3), polypropylene resin, ethylene / α-olefin random copolymer resin having a density of 930 kg / m 3 or less, and A multilayer sheet having a sealing layer made of a polyethylene resin composition (see Patent Document 4), etc. It has been proposed. However, a film having a mixture layer of a polypropylene resin and a polyethylene resin as a heat-sealing layer is not always satisfactory in terms of the balance of sealing property, easy opening property, heat resistance, and oil resistance.
 かかる不具合を改良する方法として、プロピレン系重合体とエチレン系重合体に、エチレン・α―オレフィンランダム共重合体及び粘着付与剤を添加したポリオレフィン組成物からなる熱融着層を用いた易開封性積層フィルムが提案されている(特許文献5参照)。
 特許文献5に記載された易開封性積層フィルムは、優れた密封性及び易開封性を示すものの、封緘性をより要求される分野には、性能が不十分であることがわかった。
As a method of improving such problems, easy opening using a heat-sealing layer comprising a polyolefin composition in which an ethylene / α-olefin random copolymer and a tackifier are added to a propylene polymer and an ethylene polymer. A laminated film has been proposed (see Patent Document 5).
Although the easy-open laminate film described in Patent Document 5 exhibits excellent sealing properties and easy-openability, it has been found that the performance is insufficient in fields where sealing properties are more required.
特公平5-64593号公報Japanese Patent Publication No. 5-64593 特公平5-6513号公報Japanese Patent Publication No. 5-6513 特開平2-185547号公報Japanese Patent Laid-Open No. 2-185547 特開2000-355358号公報JP 2000-355358 A 特開2005-28679号公報JP 2005-28679 A
 本発明の目的は、優れた密封性及び易開封性を維持しながら、封緘性、すなわち、包装体を室温よりも高い温度においても、外部からの圧力(外圧)や内部からの圧力(内圧)にも耐えうる封緘強度を有する易開封性積層フィルムを得ることにある。 The object of the present invention is to maintain sealing performance and easy opening, while maintaining sealing performance, that is, pressure from outside (external pressure) and pressure from inside (internal pressure) even at a temperature higher than room temperature. Another object of the present invention is to obtain an easy-open laminated film having a sealing strength that can withstand the above.
 本発明は、易開封性積層フィルム及びその用途に関する。そのうち、易開封性積層フィルムは、熱融着層、中間層、及びラミネート層からなる。
 熱融着層は、
   プロピレン系重合体(A-1)      79.8 ~94    質量%、
 密度が900kg/m以上の
   エチレン系重合体(B-1)         4    ~10    質量%、
 密度が860kg/m以上
 900kg/m未満の
 エチレン・α―オレフィン
         ランダム共重合体(C-1)      1.5 ~ 7.5質量%
及び
    粘着付与樹脂(D-1)       0.5 ~  2.7質量%
〔但し、(A-1)+(B-1)+(C-1)+(D-1)=100質量%とする。〕からなるオレフィン系重合体組成物(E)から構成される。
 また、中間層は、
密度が940~970kg/mの範囲にある
      エチレン系重合体(B-2)50~95質量%
及び
密度が905~935kg/mの範囲にある
  高圧法低密度ポリエチレン(B-3)  5~50質量%
〔但し、(B-2)+(B-3)=100質量%とする。〕
からなるエチレン系重合体組成物(F)から構成される。
 さらに、ラミネート層は、密度が900~950kg/m3 好ましくは910~940kg/mの、より好ましくは920~940kg/mの範囲にあるエチレン系重合体(B-4)から構成される。
The present invention relates to an easily openable laminated film and its use. Among them, the easy-open laminated film is composed of a heat-sealing layer, an intermediate layer, and a laminate layer.
Thermal fusion layer
Propylene polymer (A-1) 79.8 to 94% by mass,
4 to 10% by mass of an ethylene polymer (B-1) having a density of 900 kg / m 3 or more,
Ethylene / α-olefin random copolymer (C-1) having a density of 860 kg / m 3 or more and less than 900 kg / m 3 1.5 to 7.5% by mass
And tackifying resin (D-1) 0.5 to 2.7% by mass
[However, (A-1) + (B-1) + (C-1) + (D-1) = 100 mass%) And an olefin polymer composition (E).
In addition, the intermediate layer
Density is in the range of 940 to 970 kg / m 3 Ethylene polymer (B-2) 50 to 95% by mass
And high density low density polyethylene (B-3) having a density in the range of 905 to 935 kg / m 3 5 to 50% by mass
[However, (B-2) + (B-3) = 100 mass%. ]
It is comprised from the ethylene-type polymer composition (F) which consists of.
Further, the laminate layer is composed of an ethylene polymer (B-4) having a density in the range of 900 to 950 kg / m 3, preferably 910 to 940 kg / m 3 , more preferably 920 to 940 kg / m 3. .
 本発明の易開封性積層フィルムは、プロピレン系重合体層と熱融着した場合、幅広い温度領域で安定したヒートシール強度(剥離強度)、及び包装体を室温よりも高い温度においても、外部からの圧力(外圧)や内部からの圧力(内圧)にも耐えうる封緘強度を有し、且つ剥離時(開封時)には容易に剥離でき、しかも剥離面に糸曳きがなく、ソフト感を有している。 When the easy-open laminate film of the present invention is heat-sealed with a propylene-based polymer layer, the heat seal strength (peeling strength) stable in a wide temperature range, and the packaging body from the outside even at a temperature higher than room temperature. Sealing strength that can withstand pressure (external pressure) and pressure from the inside (internal pressure), and can be easily peeled when peeled (opened), and there is no stringing on the peeled surface, giving it a soft feel. is doing.
 <プロピレン系重合体(A-1)>
 本発明の易開封性積層フィルムの熱融着層となるオレフィン系重合体組成物(E)の構成成分の一つであるプロピレン系重合体(A-1)は、一般にポリプロピレンの名称で製造・販売されている樹脂で、通常、密度が890~930kg/m程度のプロピレンの単独重合体若しくは、プロピレン共重合体、すなわち、プロピレンと共に、他の少量のα-オレフィンから選ばれる少なくとも1種以上のコモノマーからなる共重合体である。共重合体においては、ランダム共重合体であってもブロック共重合体であってもよい。このプロピレンの共重合体の定義における他のα-オレフィンとしては、エチレン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、1-デセン、4-メチル-1-ペンテンなどの、エチレンと炭素原子数が4~20程度のα-オレフィンを例示することができる。このような他のα-オレフィンは、1種単独で又は2種以上のα-オレフィンを組み合わせて共重合させてもよい。
<Propylene polymer (A-1)>
The propylene polymer (A-1), which is one of the constituent components of the olefin polymer composition (E) that serves as the heat-sealing layer of the easy-open laminate film of the present invention, is generally produced under the name of polypropylene. A commercially available resin, usually a homopolymer of propylene having a density of about 890 to 930 kg / m 3 or a propylene copolymer, that is, at least one selected from propylene and a small amount of other α-olefins It is a copolymer comprising the comonomer. The copolymer may be a random copolymer or a block copolymer. Other α-olefins in the definition of this copolymer of propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and the like. And α-olefins having about 4 to 20 carbon atoms. Such other α-olefins may be copolymerized singly or in combination of two or more α-olefins.
 これらプロピレン系重合体(A-1)の中でも、得られる易開封性積層フィルムの熱融着性と耐熱性のバランスから、示差走査熱量計(DSC)に基づく融点が110~145℃、とくに115~140℃の範囲にあるプロピレン・α-オレフィンランダム共重合体が好ましい。 Among these propylene-based polymers (A-1), the melting point based on a differential scanning calorimeter (DSC) is 110 to 145 ° C., particularly 115, because of the balance of heat-fusibility and heat resistance of the easily openable laminated film obtained. A propylene / α-olefin random copolymer in the range of ˜140 ° C. is preferred.
 本発明に係るプロピレン系重合体(A-1)は、後述のエチレン系重合体(B-1)、エチレン・α―オレフィンランダム共重合体(C-1)及び粘着付与樹脂(D-1)と混合してなるオレフィン系重合体組成物(E)がフィルム形成能を有する限り、メルトフローレート(MFR)(ASTM D1238、230℃、2160g荷重)は特に限定はされないが、押出加工性の点から、通常、0.01~100g/10分、好ましくは0.1~70g/10分の範囲にある。
 本発明に係るプロピレン系重合体(A-1)としては、2種以上のプロピレン系重合体を組合せて使用することもできる。
 本発明に係るプロピレン系重合体(A-1)は、種々公知の製造方法、具体的には、例えば、チーグラー・ナッタ系触媒やシングルサイト触媒のようなオレフィン重合用触媒を用いて製造することができる。特にはシングルサイト触媒を用いて製造することができる。シングルサイト触媒は、活性点が均一(シングルサイト)である触媒であり、例えばメタロセン触媒(いわゆるカミンスキー触媒)やブルックハート触媒などがあげられる。メタロセン触媒は、メタロセン系遷移金属化合物と、有機アルミニウム化合物及び上記メタロセン系遷移金属化合物と反応してイオン対を形成する化合物からなる群から選ばれる少なくとも一種の化合物とからなる触媒であり、無機物に担持されていてもよい。
The propylene polymer (A-1) according to the present invention includes an ethylene polymer (B-1), an ethylene / α-olefin random copolymer (C-1), and a tackifier resin (D-1) described later. The melt flow rate (MFR) (ASTM D1238, 230 ° C., 2160 g load) is not particularly limited as long as the olefin polymer composition (E) formed by mixing with the film has an ability to form a film. Therefore, it is usually in the range of 0.01 to 100 g / 10 minutes, preferably 0.1 to 70 g / 10 minutes.
As the propylene polymer (A-1) according to the present invention, two or more propylene polymers can be used in combination.
The propylene polymer (A-1) according to the present invention is produced using various known production methods, specifically, for example, using an olefin polymerization catalyst such as a Ziegler-Natta catalyst or a single site catalyst. Can do. In particular, it can be produced using a single site catalyst. The single site catalyst is a catalyst having a uniform active site (single site), and examples thereof include a metallocene catalyst (so-called Kaminsky catalyst) and a Brookhart catalyst. The metallocene catalyst is a catalyst composed of a metallocene transition metal compound, an organoaluminum compound, and at least one compound selected from the group consisting of compounds that react with the metallocene transition metal compound to form an ion pair. It may be supported.
 <エチレン系重合体(B-1)>
 本発明の易開封性積層フィルムの熱融着層となるオレフィン系重合体組成物(E)の構成成分の一つであるエチレン系重合体(B-1)は、密度が900kg/m以上、好ましくは910~970kg/m、更に好ましくは930~970kg/mの範囲にある、エチレンの単独重合体若しくはエチレンと少量の炭素数が3~10のα-オレフィン、例えばプロピレン、1-ブテン、1-ヘプテン、1-ヘキセン、1-オクテン、4-メチル-1-ペンテンなどとのランダム共重合体であって、いわゆる、高圧法低密度ポリエチレン(HP-LDPE)、直鎖状あるいは線状低密度ポリエチレン(L-LDPE)、中密度ポリエチレン(MDPE)、高密度ポリエチレン(HDPE)と呼ばれているエチレンの単独重合体若しくはエチレン・α-オレフィン共重合体である。
<Ethylene polymer (B-1)>
The ethylene polymer (B-1), which is one of the constituent components of the olefin polymer composition (E) that serves as the heat-sealing layer of the easy-open laminated film of the present invention, has a density of 900 kg / m 3 or more. Preferably in the range of 910 to 970 kg / m 3 , more preferably 930 to 970 kg / m 3 , an ethylene homopolymer or ethylene and a small amount of an α-olefin having 3 to 10 carbon atoms, such as propylene, 1- Random copolymers with butene, 1-heptene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc., so-called high-pressure low-density polyethylene (HP-LDPE), linear or linear Ethylene low polymer (L-LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) Is Ren · alpha-olefin copolymer.
 本発明に係るエチレン系重合体(B-1)は、それぞれ単一の重合体であっても、2種以上のエチレン系重合体の組成物(混合物)であってもよい。
 本発明に係るエチレン系重合体(B-1)のメルトフローレート(MFR)(ASTM D1238、190℃、2160g荷重)は、前記プロピレン系重合体(A-1)、後述のエチレン・α-オレフィンランダム共重合体(C-1)、及び粘着付与樹脂(D-1)と混合してオレフィン系重合体組成物(E)にした際に、フィルム形成能がある限り特に限定はされないが、通常、0.01~100g/10分、好ましくは0.1~70g/10分の範囲にある。
The ethylene polymer (B-1) according to the present invention may be a single polymer or a composition (mixture) of two or more ethylene polymers.
The melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) of the ethylene polymer (B-1) according to the present invention is the same as that of the propylene polymer (A-1), ethylene / α-olefin described later. When the olefin polymer composition (E) is mixed with the random copolymer (C-1) and the tackifier resin (D-1), it is not particularly limited as long as it has a film-forming ability. 0.01 to 100 g / 10 min, preferably 0.1 to 70 g / 10 min.
 <エチレン・α-オレフィンランダム共重合体(C-1)>
 本発明の易開封性積層フィルムの熱融着層となるオレフィン系重合体組成物(E)の構成成分の一つであるエチレン・α-オレフィンランダム共重合体(C-1)は、密度が860kg/m以上~900kg/m未満、好ましくは860kg/m以上~895kg/m未満のエチレンと炭素数3~10のα-オレフィン、例えばプロピレン、1-ブテン、1-ヘプテン、1-ヘキセン、1-オクテン、4-メチル-1-ペンテンなどのα-オレフィンとのランダム共重合体である。
 エチレン・α―オレフィンランダム共重合体(C-1)は、好ましくは、密度が860~895kg/mの範囲にあり、α―オレフィンが炭素数4~10である少なくとも1種類であるエチレン・α-オレフィンランダム共重合体(C1-1)及び密度が865~875kg/mの範囲にあるエチレン・プロピレンランダム共重合体(C1-2)から構成される。
 さらに、好ましくは、エチレン・α―オレフィンランダム共重合体(C1-1)10~90質量部、中でも30~90質量部、及びエチレン・プロピレンランダム共重合体(C1-2)90~10質量部、中でも70~10質量部 〔但し、(C1-1)+(C1-2)=100質量部とする。〕から構成される。
 なお、エチレン・α-オレフィンランダム共重合体(C1-1)としては、下記の(c-1a)から(c-1c)の物性を少なくとも1個以上有するポリマーが望ましい。

(c1-1a)エチレン含有量が85~93モル%である
(c1-1b)X線による結晶化度が7~30%である
(c1-1c)示差走査熱量計(DSC)による昇温速度10℃/分での吸熱曲線から求めた融点が60~90℃の範囲にある
 
 このようなエチレン・α-オレフィンランダム共重合体(C1-1)として、(c1-1a)、(c1-1b)、または(c1-1c)の物性を有するエチレン・α-オレフィンランダム共重合体(C1-1)があり、さらに(c1-1a)と(c1-1b)の物性、(c1-1a)と(c1-1c)の物性、または(c1-1b)と(c1-1c)の物性を有するエチレン・α-オレフィンランダム共重合体(C1-1)があり、さらに(c1-1a)、(c1-1b)、と(c1-1c)の物性を有するエチレン・α-オレフィンランダム共重合体(C1-1)がある。
 また、エチレン・プロピレンランダム共重合体(C1-2)としては、同様に下記の(c1-2a)、(c1-2b)の物性の少なくともいずれかを有するポリマーが望ましい。
 
(c1-2a)エチレン含有量が75~85モル%である
(c1-2b)X線による結晶化度が5%未満の範囲にある非晶性若しくは僅かに結晶性を有する
 
 このようなエチレン・プロピレンランダム共重合体(C1-2)として、(c1-2a)、または(c1-2b)の物性を有するエチレン・プロピレンランダム共重合体(C1-2)があり、さらに(c1-2a)と(c1-2b)の物性を有するエチレン・プロピレンランダム共重合体(C1-2)がある。
 これらの中では、エチレン・α-オレフィンランダム共重合体(C-1)としては、得られる易開封性積層フィルムの熱融着特性を考慮すると、エチレン含有量が85~93モル%、X線による結晶化度が7~30%及び示差走査熱量計(DSC)による昇温速度10℃/分での吸熱曲線から求めた融点が60~90℃の範囲にある低結晶性のエチレン・α-オレフィンランダム共重合体(C1-1)及び、エチレン含有量が75~85モル%、X線による結晶化度が5%未満の範囲にある非晶性若しくは僅かに結晶性を有するエチレン・プロピレンランダム共重合体(C1-2)からなる組成物(混合物)が好適である。
<Ethylene / α-olefin random copolymer (C-1)>
The ethylene / α-olefin random copolymer (C-1), which is one of the constituent components of the olefin polymer composition (E) that serves as the heat-sealing layer of the easy-open laminated film of the present invention, has a density of 860 kg / m 3 or more ~ 900 kg / m less than 3, preferably α- olefin 860 kg / m 3 or more ~ 895kg / m of less than 3 ethylene and carbon 3-10, such as propylene, 1-butene, 1-heptene, 1 -Random copolymers with α-olefins such as hexene, 1-octene, 4-methyl-1-pentene.
The ethylene / α-olefin random copolymer (C-1) is preferably at least one ethylene / α-olefin having a density in the range of 860 to 895 kg / m 3 and an α-olefin having 4 to 10 carbon atoms. It is composed of an α-olefin random copolymer (C1-1) and an ethylene / propylene random copolymer (C1-2) having a density in the range of 865 to 875 kg / m 3 .
More preferably, the ethylene / α-olefin random copolymer (C1-1) is 10 to 90 parts by mass, especially 30 to 90 parts by mass, and the ethylene / propylene random copolymer (C1-2) 90 to 10 parts by mass. Among them, 70 to 10 parts by mass [provided that (C1-1) + (C1-2) = 100 parts by mass. ].
The ethylene / α-olefin random copolymer (C1-1) is preferably a polymer having at least one of the following physical properties (c-1a) to (c-1c).

(C1-1a) ethylene content is 85-93 mol% (c1-1b) crystallinity by X-ray is 7-30% (c1-1c) heating rate by differential scanning calorimeter (DSC) Melting point determined from endothermic curve at 10 ° C / min is in the range of 60-90 ° C
As such an ethylene / α-olefin random copolymer (C1-1), an ethylene / α-olefin random copolymer having the physical properties of (c1-1a), (c1-1b), or (c1-1c) (C1-1) and further physical properties of (c1-1a) and (c1-1b), physical properties of (c1-1a) and (c1-1c), or (c1-1b) and (c1-1c) There is an ethylene / α-olefin random copolymer (C1-1) having physical properties, and an ethylene / α-olefin random copolymer having physical properties (c1-1a), (c1-1b), and (c1-1c). There is a polymer (C1-1).
Similarly, the ethylene / propylene random copolymer (C1-2) is preferably a polymer having at least one of the following physical properties (c1-2a) and (c1-2b).

(C1-2a) ethylene content is 75 to 85 mol% (c1-2b) crystallinity by X-ray is less than 5% amorphous or slightly crystalline
Such an ethylene / propylene random copolymer (C1-2) includes an ethylene / propylene random copolymer (C1-2) having the physical properties of (c1-2a) or (c1-2b), There is an ethylene / propylene random copolymer (C1-2) having the physical properties of c1-2a) and (c1-2b).
Among these, the ethylene / α-olefin random copolymer (C-1) has an ethylene content of 85 to 93 mol%, X-rays in consideration of the heat-sealing characteristics of the resulting easy-open laminated film. Low crystalline ethylene α- having a melting point in the range of 60 to 90 ° C. determined from an endothermic curve with a crystallinity of 7 to 30% and a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min Olefin random copolymer (C1-1) and ethylene / propylene random having an amorphous content or a slight crystallinity in which ethylene content is in the range of 75 to 85 mol% and crystallinity by X-ray is less than 5% A composition (mixture) comprising the copolymer (C1-2) is preferred.
 本発明に係るエチレン・α-オレフィンランダム共重合体(C-1)としては、前記プロピレン系重合体(A-1)、前記エチレン系重合体(B-1)及び後述の粘着付与樹脂(D-1)と混合してオレフィン系重合体組成物(E)にした際に、フィルム形成能がある限り、メルトフローレート(MFR)(ASTMD1238、190℃、2160g荷重)は、特に限定はされないが、オレフィン系重合体組成物(E)の加工性、耐油性等を考慮すると、メルトフローレート(MFR)(ASTMD1238、190℃、2160g荷重)が、好ましくは0.01~20g/10分、更に好ましくは0.1~10g/10分の範囲のものが好適である。
 本発明に係るエチレン・α-オレフィンランダム共重合体(C-1)は、例えば遷移金属化合物触媒成分、例えばバナジウム化合物やジルコニウム化合物と、有機アルミニウム化合物触媒成分とからなる触媒を用いて、エチレンとα-オレフィンを共重合することによって得ることができる。
Examples of the ethylene / α-olefin random copolymer (C-1) according to the present invention include the propylene polymer (A-1), the ethylene polymer (B-1), and a tackifier resin (D described later). -1) When mixed with olefin polymer composition (E), the melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) is not particularly limited as long as it has film-forming ability. In view of the processability and oil resistance of the olefin polymer composition (E), the melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) is preferably 0.01 to 20 g / 10 min. A range of 0.1 to 10 g / 10 min is preferable.
The ethylene / α-olefin random copolymer (C-1) according to the present invention comprises, for example, a transition metal compound catalyst component, for example, a catalyst comprising a vanadium compound or a zirconium compound and an organoaluminum compound catalyst component, It can be obtained by copolymerizing an α-olefin.
 <粘着付与樹脂(D-1)>
 本発明の易開封性積層フィルムの熱融着層となるオレフィン系重合体組成物(E)の構成成分の一つである粘着付与樹脂(D-1)は、粘着付与剤として製造・販売されている公知の樹脂であり、具体的には、脂肪族系炭化水素樹脂、脂環族系炭化水素樹脂、芳香族系炭化水素樹脂、ポリテルペン系樹脂、ロジン類、スチレン系樹脂、クマロン・インデン樹脂などを挙げることができる。
 脂肪族系炭化水素樹脂の例としては、1-ブテン、イソブテン、ブタジエン、1,3-ペンタジエン、イソプレンなど炭素数4~5のモノ又はジオレフィンの少なくとも1種以上を含む留分を重合して得られる樹脂を挙げることができる。
<Tackifying resin (D-1)>
The tackifier resin (D-1), which is one of the constituent components of the olefin polymer composition (E) that serves as the heat-sealing layer of the easy-open laminate film of the present invention, is manufactured and sold as a tackifier. Specifically, aliphatic resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, polyterpene resins, rosins, styrene resins, coumarone / indene resins And so on.
Examples of the aliphatic hydrocarbon resin include polymerization of a fraction containing at least one mono- or diolefin having 4 to 5 carbon atoms, such as 1-butene, isobutene, butadiene, 1,3-pentadiene, and isoprene. The resulting resin can be mentioned.
 脂環族系炭化水素樹脂の例として、スペントC4~C5留分中のジエン成分を環化二量化後重合させて得られる樹脂、シクロペンタジエンなどの環状モノマーを重合させた樹脂、芳香族系炭化水素樹脂を核内水添した樹脂などを挙げることができる。
 芳香族系炭化水素樹脂の例として、ビニルトルエン、インデン、α-メチルスチレンなどのC8~C10のビニル芳香族炭化水素を少なくとも一種以上含有する留分を重合して得られる樹脂、あるいはこれら留分と上記脂肪族炭化水素留分を共重合して得られる樹脂などを挙げることができる。
Examples of alicyclic hydrocarbon resins include resins obtained by polymerization after dimerization of diene components in spent C4 to C5 fractions, resins obtained by polymerizing cyclic monomers such as cyclopentadiene, aromatic carbonization Examples thereof include a resin obtained by hydrogenating a hydrogen resin.
Examples of aromatic hydrocarbon resins include resins obtained by polymerizing a fraction containing at least one C8-C10 vinyl aromatic hydrocarbon such as vinyltoluene, indene, α-methylstyrene, or the like. And resins obtained by copolymerizing the above aliphatic hydrocarbon fractions.
 ポリテルペン系樹脂の例としては、α-ピネン重合体、β-ピネン重合体、ジペンテン重合体、テルペン・フェノール共重合体、α-ピネン・フェノール共重合体、これらの水素添加物などを挙げることができる。
 ロジン類としては、ガムロジン、ウッドロジン、トール油などのロジン及びその変性物などであり、変性物としては水素添加、不均化、二量化、エステル化などの変性を施したものを例示することができる。
 スチレン系炭化水素樹脂としては、純度の高いスチレン、ビニルトルエン、α-メチルスチレン、イソプロピルトルエンなどのスチレン系単量体の1種又は2種以上を重合して得られる分子量の低い樹脂状重合体を挙げることができる。
 本発明に係るオレフィン系重合体組成物(E)を飲食品包装用の易開封性シール材料として使用する場合には、無臭性、食品衛生性、他成分との混和性などを考慮すると、芳香族系炭化水素樹脂を核内水添した樹脂あるいはポリテルペン系樹脂を使用することが好ましい。
Examples of polyterpene resins include α-pinene polymers, β-pinene polymers, dipentene polymers, terpene / phenol copolymers, α-pinene / phenol copolymers, and hydrogenated products thereof. it can.
Examples of rosins include rosins such as gum rosin, wood rosin and tall oil, and modified products thereof. Examples of modified products include those subjected to modification such as hydrogenation, disproportionation, dimerization, and esterification. it can.
Styrenic hydrocarbon resins are low molecular weight resinous polymers obtained by polymerizing one or more styrene monomers such as high-purity styrene, vinyltoluene, α-methylstyrene, and isopropyltoluene. Can be mentioned.
When the olefin polymer composition (E) according to the present invention is used as an easily openable sealing material for food and beverage packaging, the fragrance is considered in consideration of odorlessness, food hygiene, miscibility with other components, etc. It is preferable to use a resin obtained by intra-nuclear hydrogenation of a group hydrocarbon resin or a polyterpene resin.
 <エチレン系重合体(B-2)>
 本発明の易開封性積層フィルムの中間層を構成するエチレン系重合体組成物(F)の成分の一つであるエチレン系重合体(B-2)は、密度が940~970kg/m、好ましくは945~967kg/mの範囲にあるエチレンの単独重合体、若しくはエチレンと少量の炭素数が3~10のα-オレフィン、例えばプロピレン、1-ブテン、1-ヘプテン、1-ヘキセン、1-オクテン、4-メチル-1-ペンテンなどとのランダム共重合体であり、通常、高密度ポリエチレン(HDPE)として、製造・販売されているエチレンを主体とする重合体である。
 本発明に係るエチレン系重合体(B-2)のメルトフローレート(MFR)(ASTM D1238、190℃、2160g荷重)は、後述の高圧法低密度ポリエチレン(B-3)と混合してなるエチレン系重合体組成物(F)がフィルム形成能を有する限り特に限定はされないが、通常、0.01~100g/10分、好ましくは0.1~70g/10分の範囲にある。
<Ethylene polymer (B-2)>
The ethylene polymer (B-2), which is one of the components of the ethylene polymer composition (F) constituting the intermediate layer of the easy-open laminated film of the present invention, has a density of 940 to 970 kg / m 3 , Preferably, a homopolymer of ethylene in the range of 945 to 967 kg / m 3 or ethylene and a small amount of an α-olefin having 3 to 10 carbon atoms such as propylene, 1-butene, 1-heptene, 1-hexene, 1 -Random copolymer with octene, 4-methyl-1-pentene, etc., and is usually a polymer mainly composed of ethylene manufactured and sold as high density polyethylene (HDPE).
The melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) of the ethylene-based polymer (B-2) according to the present invention is ethylene mixed with a high-pressure method low-density polyethylene (B-3) described later. The polymer composition (F) is not particularly limited as long as it has a film-forming ability, but is usually in the range of 0.01 to 100 g / 10 minutes, preferably 0.1 to 70 g / 10 minutes.
 <高圧法低密度ポリエチレン(B-3)>
 本発明の易開封性積層フィルムの中間層を構成するエチレン系重合体組成物(F)の成分の一つである高圧法低密度ポリエチレン(B-3)は、密度が905~935kg/m、好ましくは910~925kg/mの範囲にある。
 ここで、高圧法低密度ポリエチレン(B-3)は、通常、高圧法低密度ポリエチレン(HP-LDPE)として製造・販売されているエチレンの単独重合体、あるいはエチレンと少量の酢酸ビニルとの共重合体である。
 本発明に係る高圧法低密度ポリエチレン(B-3)のメルトフローレート(MFR)(ASTM D1238、190℃、2160g荷重)は、前記エチレン系重合体(B-2)と混合してなるエチレン系重合体組成物(F)がフィルム形成能を有する限り特に限定はされないが、通常、0.01~100g/10分、好ましくは0.1~70g/10分の範囲にある。
<High pressure low density polyethylene (B-3)>
The high-pressure low-density polyethylene (B-3), which is one of the components of the ethylene polymer composition (F) constituting the intermediate layer of the easy-open laminate film of the present invention, has a density of 905 to 935 kg / m 3. Preferably, it is in the range of 910 to 925 kg / m 3 .
Here, the high-pressure method low-density polyethylene (B-3) is an ethylene homopolymer usually produced and sold as a high-pressure method low-density polyethylene (HP-LDPE), or a copolymer of ethylene and a small amount of vinyl acetate. It is a polymer.
The melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) of the high-pressure method low-density polyethylene (B-3) according to the present invention is an ethylene-based mixture obtained by mixing with the ethylene-based polymer (B-2). The polymer composition (F) is not particularly limited as long as it has a film-forming ability, but is usually in the range of 0.01 to 100 g / 10 minutes, preferably 0.1 to 70 g / 10 minutes.
 <エチレン系重合体(B-4)>
 本発明の易開封性積層フィルムのラミネート層を構成するエチレン系重合体(B-4)は、密度が900~950kg/m、好ましくは920~940kg/mの範囲にあるエチレンと炭素数が4~10のα-オレフィン、例えば1-ブテン、1-ヘプテン、1-ヘキセン、1-オクテン、4-メチル-1-ペンテンなどとのランダム共重合体であり、通常、直鎖状あるいは線状低密度ポリエチレン(L-LDPE)として製造・販売されているエチレンを主体とする重合体である。
 本発明に係るエチレン系重合体(B-4)としては、エチレンと炭素数が4以上のα-オレフィンとのランダム共重合体が好ましい。
 本発明に係るエチレン系重合体(B-4)のメルトフローレート(MFR)(ASTM D1238、190℃、2160g荷重)は、フィルム形成能がある限り特に限定はされないが、通常、0.01~100g/10分、好ましくは0.1~70g/10分の範囲にある。
<Ethylene polymer (B-4)>
The ethylene polymer (B-4) constituting the laminate layer of the easy-open laminate film of the present invention has a density of 900 to 950 kg / m 3 , preferably 920 to 940 kg / m 3 , and ethylene and carbon number Is a random copolymer with 4 to 10 α-olefin, such as 1-butene, 1-heptene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc., usually linear or linear It is a polymer mainly composed of ethylene and manufactured and sold as a low-density polyethylene (L-LDPE).
The ethylene polymer (B-4) according to the present invention is preferably a random copolymer of ethylene and an α-olefin having 4 or more carbon atoms.
The melt flow rate (MFR) (ASTM D1238, 190 ° C., 2160 g load) of the ethylene-based polymer (B-4) according to the present invention is not particularly limited as long as it has a film-forming ability. It is in the range of 100 g / 10 min, preferably 0.1 to 70 g / 10 min.
 ラミネート層には、上記のエチレン系重合体(B-4)と共に、これら以外のエチレン系重合体をはじめとするポリマーを併用する場合があり、その場合、他のポリマーは、一般には、ラミネート層を構成するポリマー成分の50質量%未満であり、その中でも30質量%以下、さらに好ましくは10質量%以下である。
 本発明に係るエチレン系重合体(B-4)には、本発明の目的を損なわない範囲で各種添加剤を配合することができる。
 かかる添加剤としては、シリカ、タルクなどの無機充填剤、酸化防止剤、耐候安定剤、帯電防止剤、防曇剤、アンチブロッキング剤、スリップ剤、顔料等を挙げることができる。また有機化合物型のアンチブロッキング剤やスリップ剤等の配合もフィルム成形時、ラミネート加工時、包装作業時等における加工性や作業性の向上に有効である。
 このような有機化合物型のアンチブロッキング剤やスリップ剤として、例えばパルミチン酸アミド、ステアリン酸アミド、ベヘニン酸アミド、オレイン酸アミド、エルカ酸アミド、オレイルパルミドアミド、ステアリルパルミドアミド、メチレンビスステアリルアミド、メチレンビスオレイルアミド、エチレンビスオレイルアミド、エチレンビスエルカ酸アミドなどの各種アミド類、ポリエチレングリコール、ポリプロピレングリコールなどのポリアルキレングリコール、水添ひまし油などを例示することができる。
In the laminate layer, in addition to the ethylene polymer (B-4), a polymer including other ethylene polymers may be used in combination. In that case, the other polymer is generally a laminate layer. The content of the polymer component is less than 50% by mass, of which 30% by mass or less, and more preferably 10% by mass or less.
Various additives can be blended in the ethylene polymer (B-4) according to the present invention as long as the object of the present invention is not impaired.
Examples of such additives include inorganic fillers such as silica and talc, antioxidants, weathering stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents, and pigments. In addition, the compounding of an organic compound type anti-blocking agent or slip agent is also effective in improving workability and workability during film forming, laminating, and packaging operations.
Examples of such organic compound type anti-blocking agents and slip agents include palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, oleyl palmamide, stearyl palmamide, methylenebisstearylamide, methylene Examples thereof include various amides such as bisoleylamide, ethylenebisoleylamide, and ethylenebiserucamide, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and hydrogenated castor oil.
<オレフィン系重合体組成物(E)>
 本発明の易開封性積層フィルムの熱融着層を形成するオレフィン系重合体組成物(E)は、
 前記プロピレン系重合体(A-1)を79.8 ~94    質量%、
             好ましくは81.1 ~91.3質量%、
 前記エチレン系重合体(B-1)を   4   ~10    質量%、
             好ましくは 5.5 ~ 9    質量%、
 前記エチレン・α―オレフィン
   ランダム共重合体(C-1)を   1.5 ~ 7.5質量%、
             好ましくは 2.5 ~ 7.5質量%、
及び
 前記粘着付与樹脂(D-1)を       0.5 ~ 2.7質量%、
                          好ましくは  0.7 ~ 2.4質量%
〔但し、(A-1)+(B-1)+(C-1)+(D-1)=100質量%とする。〕含む組成物である。
 オレフィン系重合体組成物(E)を構成する前記プロピレン系重合体(A-1)、前記エチレン系重合体(B-1)、前記エチレン・α―オレフィンランダム共重合(C-1)体及び前記粘着付与樹脂(D-1)が上記範囲を満たす組成物を用いた場合は、得られる易開封性積層フィルムは、易開封性と封緘強度のバランスに優れる。
<Olefin polymer composition (E)>
The olefin polymer composition (E) that forms the heat-sealing layer of the easy-open laminate film of the present invention,
79.8 to 94% by mass of the propylene polymer (A-1),
Preferably 81.1 to 91.3% by mass,
4 to 10% by mass of the ethylene polymer (B-1),
Preferably 5.5 to 9% by mass,
1.5 to 7.5% by mass of the ethylene / α-olefin random copolymer (C-1),
Preferably 2.5 to 7.5% by mass,
And 0.5 to 2.7% by mass of the tackifier resin (D-1),
Preferably 0.7 to 2.4 mass%
[However, (A-1) + (B-1) + (C-1) + (D-1) = 100 mass%) It is a composition containing.
The propylene polymer (A-1), the ethylene polymer (B-1), the ethylene / α-olefin random copolymer (C-1) body, and the olefin polymer composition (E) When a composition in which the tackifying resin (D-1) satisfies the above range is used, the resulting easy-open laminated film has an excellent balance between easy-open property and sealing strength.
 本発明に係るオレフィン系重合体組成物(E)には、本発明の目的を損なわない範囲で各種添加剤を配合することができる。
 かかる添加剤としてシリカ、タルクなどの無機充填剤、酸化防止剤、耐候安定剤、帯電防止剤、防曇剤、アンチブロッキング剤、スリップ剤、顔料等を挙げることができる。また有機化合物型のアンチブロッキング剤やスリップ剤等の配合もフィルム成形時、ラミネート加工時、包装作業時等における加工性や作業性の向上に有効である。
 このような有機化合物型のアンチブロッキング剤やスリップ剤として、例えばパルミチン酸アミド、ステアリン酸アミド、ベヘニン酸アミド、オレイン酸アミド、エルカ酸アミド、オレイルパルミドアミド、ステアリルパルミドアミド、メチレンビスステアリルアミド、メチレンビスオレイルアミド、エチレンビスオレイルアミド、エチレンビスエルカ酸アミドなどの各種アミド類、ポリエチレングリコール、ポリプロピレングリコールなどのポリアルキレングリコール、水添ひまし油などを例示することができる。
Various additives can be blended with the olefin polymer composition (E) according to the present invention as long as the object of the present invention is not impaired.
Examples of such additives include inorganic fillers such as silica and talc, antioxidants, weathering stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents, and pigments. In addition, the compounding of an organic compound type anti-blocking agent or slip agent is also effective in improving workability and workability during film forming, laminating, and packaging operations.
Examples of such organic compound type anti-blocking agents and slip agents include palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, oleyl palmamide, stearyl palmamide, methylenebisstearylamide, methylene Examples thereof include various amides such as bisoleylamide, ethylenebisoleylamide, and ethylenebiserucamide, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and hydrogenated castor oil.
 本発明に係るオレフィン系重合体組成物(E)は、プロピレン系重合体(A-1)、エチレン系重合体(B-1)、エチレン・α-オレフィンランダム共重合体(C-1)及び粘着付与樹脂(D-1)の各成分、及び任意に配合される添加剤を、同時に又は逐次的に混合することによって調製することができる。
 熱融着層には、上記のプロピレン系重合体(A-1)、エチレン系重合体(B-1)、エチレン・α-オレフィンランダム共重合体(C-1)及び粘着付与樹脂(D-1)の各成分と共に、これら以外のエチレン系重合体をはじめとするポリマーを併用する場合があり、その場合、他のポリマーは、一般には、熱融着層を構成するポリマー成分の50質量%未満であり、その中でも30質量%以下、さらに好ましくは10質量%以下である。
 この樹脂組成物の調製に際しては、単軸押出機、二軸押出機、バンバリーミキサー、各種ニーダーなどを用いて溶融混合するのが好ましく、その混合順序にとくに制限は無い。
The olefin polymer composition (E) according to the present invention comprises a propylene polymer (A-1), an ethylene polymer (B-1), an ethylene / α-olefin random copolymer (C-1) and Each component of the tackifying resin (D-1) and an additive that is optionally blended can be prepared by mixing simultaneously or sequentially.
In the heat-sealing layer, the propylene polymer (A-1), the ethylene polymer (B-1), the ethylene / α-olefin random copolymer (C-1) and the tackifier resin (D- In addition to the components of 1), other polymers such as ethylene polymers may be used in combination. In that case, the other polymer is generally 50% by mass of the polymer component constituting the heat-sealing layer. Among them, it is 30% by mass or less, more preferably 10% by mass or less.
In preparing this resin composition, it is preferable to melt and mix using a single screw extruder, a twin screw extruder, a Banbury mixer, various kneaders, etc., and the mixing order is not particularly limited.
 <エチレン系重合体組成物(F)>
 本発明の易開封性積層フィルムの中間層を形成するエチレン系重合体組成物(F)は、
 前記エチレン系重合体(B-2)を          50~95質量%、
                 好ましくは70~92質量%、
及び
 前記高圧法低密度ポリエチレン(B-3)を    5~50質量%、
                  好ましくは8~30質量%
〔但し、(B-2)+(B-3)=100質量%とする。〕
含む組成物である。
 エチレン系重合体(B-2)の量が50質量%未満の組成物を中間層として用いた場合は、得られる易開封性積層フィルムの製膜性が低下したり、フィルム強度や耐熱性などイージーオープン機能以外も劣る虞があり、一方、エチレン系重合体(B-2)の量が95質量%を超える組成物を中間層として用いた場合は、得られる易開封性積層フィルムのシール強度が強くなり、完全シールなどイージーオープン性能が無くなる虞がある。
<Ethylene polymer composition (F)>
The ethylene-based polymer composition (F) that forms the intermediate layer of the easy-open laminate film of the present invention,
50 to 95% by mass of the ethylene polymer (B-2),
Preferably 70 to 92% by mass,
And 5-50% by mass of the high pressure method low density polyethylene (B-3),
Preferably 8-30% by mass
[However, (B-2) + (B-3) = 100 mass%. ]
It is a composition containing.
When a composition having an ethylene polymer (B-2) amount of less than 50% by mass is used as the intermediate layer, the film-forming property of the resulting easy-open laminated film is reduced, film strength, heat resistance, etc. Other than the easy open function, there is a risk of inferiority. On the other hand, when a composition in which the amount of the ethylene polymer (B-2) exceeds 95% by mass is used as the intermediate layer, the sealing strength of the resulting easy-open laminate film There is a risk that the easy open performance such as complete seal will be lost.
 中間層には、上記のエチレン系重合体(B-2) 及び高圧法低密度ポリエチレン(B-3)と共に、これら以外のエチレン系重合体をはじめとするポリマーを併用する場合があり、その場合、他のポリマーは、一般には、中間層を構成するポリマー成分の50質量%未満であり、その中でも30質量%以下、さらに好ましくは10質量%以下である。
 本発明に係る中間層を構成するエチレン系重合体組成物(F)には、本発明の目的を損なわない範囲で各種添加剤を配合することができる。
 かかる添加剤としてシリカ、タルクなどの無機充填剤、酸化防止剤、耐候安定剤、帯電防止剤、防曇剤、アンチブロッキング剤、スリップ剤、顔料等を含んでもよい。また有機化合物型のアンチブロッキング剤やスリップ剤等の配合もフィルム成形時、ラミネート加工時、包装作業時等における加工性や作業性の向上に有効である。
 このような有機化合物型のアンチブロッキング剤やスリップ剤として、例えばパルミチン酸アミド、ステアリン酸アミド、ベヘニン酸アミド、オレイン酸アミド、エルカ酸アミド、オレイルパルミドアミド、ステアリルパルミドアミド、メチレンビスステアリルアミド、メチレンビスオレイルアミド、エチレンビスオレイルアミド、エチレンビスエルカ酸アミドなどの各種アミド類、ポリエチレングリコール、ポリプロピレングリコールなどのポリアルキレングリコール、水添ひまし油などを例示することができる。
In the intermediate layer, in addition to the ethylene polymer (B-2) and the high-pressure low-density polyethylene (B-3), a polymer such as an ethylene polymer other than these may be used in combination. The other polymer is generally less than 50% by mass of the polymer component constituting the intermediate layer, of which 30% by mass or less, and more preferably 10% by mass or less.
Various additives can be blended in the ethylene-based polymer composition (F) constituting the intermediate layer according to the present invention as long as the object of the present invention is not impaired.
Such additives may include inorganic fillers such as silica and talc, antioxidants, weathering stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents, pigments and the like. In addition, the compounding of an organic compound type anti-blocking agent or slip agent is also effective in improving workability and workability during film forming, laminating, and packaging operations.
Examples of such organic compound type anti-blocking agents and slip agents include palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, oleyl palmamide, stearyl palmamide, methylenebisstearylamide, methylene Examples thereof include various amides such as bisoleylamide, ethylenebisoleylamide, and ethylenebiserucamide, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and hydrogenated castor oil.
 <易開封性積層フィルム>
本発明の易開封性積層フィルムは、前記オレフィン系重合体組成物(E)から構成される熱融着層、前記エチレン系重合体組成物(F)から構成される中間層及び前記エチレン系重合体(B-4)から構成されるラミネート層からなる。
 本発明の易開封性積層フィルムを構成する中間層は、前記エチレン系重合体組成物(F)から構成される限り、一層でも二層以上から構成されていてもよい。
<Easily openable laminated film>
The easy-open laminate film of the present invention includes a heat-sealing layer composed of the olefin polymer composition (E), an intermediate layer composed of the ethylene polymer composition (F), and the ethylene heavy layer. It consists of a laminate layer composed of the union (B-4).
As long as the intermediate layer constituting the easy-open laminate film of the present invention is composed of the ethylene polymer composition (F), it may be composed of one layer or two or more layers.
 本発明の易開封性積層フィルムの厚さは用途により種々決定されるが、三層構成の場合は、通常、熱融着層の厚さが1~80μm、好ましくは2~50μm、中間層の厚さが8~498μm、好ましくは16~96μm、ラミネート層の厚さが1~80μm、好ましくは2~50μmの範囲にあり、易開封性積層フィルム全体の厚さが、10~500μm、好ましくは20~100μmの範囲にある。
 本発明の易開封性積層フィルムは、印刷性あるいは基材層等との接着性を改良するために、ラミネート層の表面を、例えば、コロナ処理、火炎処理、プラズマ処理、アンダーコート処理等で表面活性化処理を行っておいてもよい。
The thickness of the easy-open laminated film of the present invention is variously determined depending on the application. In the case of a three-layer structure, the thickness of the heat-sealing layer is usually 1 to 80 μm, preferably 2 to 50 μm, The thickness is 8 to 498 μm, preferably 16 to 96 μm, the thickness of the laminate layer is 1 to 80 μm, preferably 2 to 50 μm, and the total thickness of the easy-open laminated film is 10 to 500 μm, preferably It is in the range of 20-100 μm.
The easy-open laminate film of the present invention is a surface of a laminate layer, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, etc., in order to improve the printability or adhesion with a base material layer. An activation process may be performed.
 《基材層》
 本発明の易開封性積層フィルムは、基材層と積層して種々用途に使用し得る。本発明の易開封性積層フィルムのラミネート層と積層される基材層は、熱可塑性樹脂からなるシート状またはフィルム状のもの、紙、アルミニウム箔等からなる。
 熱可塑性樹脂としては、種々公知の熱可塑性樹脂、例えば、ポリオレフィン(ポリエチレン、ポリプロピレン、ポリ4-メチル・1-ペンテン、ポリブテン等)、ポリエステル(ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等)、ポリアミド(ナイロン-6、ナイロン-66、ポリメタキシレンアジパミド等)、ポリ塩化ビニル、ポリイミド、エチレン・酢酸ビニル共重合体もしくはその鹸化物、ポリビニルアルコール、ポリアクリロニトリル、ポリカーボネート、ポリスチレン、アイオノマー、あるいはこれらの混合物等を例示することができる。これらのうちでは、ポリプロピレン、ポリエチレンテレフタレート、ポリアミド等、延伸性、透明性が良好な熱可塑性樹脂が好ましい。又、かかる熱可塑性樹脂フィルムからなる基材は、無延伸フィルムであっても、延伸フィルムであっても良いし、1種或いは2種以上の共押し出し品、押出しラミ品、ドライラミ品等の積層体であっても良い。
<Base material layer>
The easy-open laminated film of the present invention can be laminated with a base material layer and used for various applications. The base material layer laminated | stacked with the laminate layer of the easily openable laminated film of this invention consists of a sheet-like or film-like thing which consists of thermoplastic resins, paper, aluminum foil, etc.
Examples of the thermoplastic resin include various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate). Phthalates, etc.), polyamide (nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene , Ionomers, or a mixture thereof. Of these, thermoplastic resins having good stretchability and transparency, such as polypropylene, polyethylene terephthalate, and polyamide, are preferable. Further, the substrate made of such a thermoplastic resin film may be an unstretched film or a stretched film, and a laminate of one or more coextruded products, extruded laminate products, dry laminate products, etc. It may be the body.
 又、基材層の片面あるいは両面を、本発明の易開封性積層フィルムのラミネート層との接着性を改良するために、例えば、コロナ処理、火炎処理、プラズマ処理、アンダーコート処理、フレーム処理等の表面活性化処理を行っておいてもよい。基材層の厚さは、通常5~1000μm、好ましくは9~100μmの範囲にある。 Moreover, in order to improve the adhesiveness of one side or both sides of the base material layer with the laminate layer of the easy-open laminate film of the present invention, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, frame treatment, etc. The surface activation treatment may be performed. The thickness of the base material layer is usually in the range of 5 to 1000 μm, preferably 9 to 100 μm.
 <易開封性積層フィルムの製造方法>
 本発明の易開封性積層フィルムの製造には公知の種々公知のフィルム成形方法を採用し得る。その際、積層フィルム成形する前に、熱融着層を構成する上記組成のオレフィン系重合体組成物(E)を予め用意しておいてもよいし、プロピレン系重合体(A-1)、エチレン系重合体(B-1)、エチレン・α―オレフィンランダム共重合体(C-1)及び粘着付与樹脂(D-1)を所定量計量して直接フィルム成形機に投入してもよい。又、同じく中間層も前記組成のエチレン系重合体組成物(F)を予め用意しておいてもよいし、エチレン系重合体(B-2)及び高圧法低密度ポリエチレン(B-3)を所定量計量して直接フィルム成形機に投入してもよい。かかる積層フィルムは夫々別個にフィルムを成形後貼り合せてもよいが、少なくとも三層構造の多層ダイを用いて共押出し成形による方法が最も好ましい。
<Method for producing easy-open laminated film>
Various known film forming methods can be employed for producing the easy-open laminated film of the present invention. At that time, before forming the laminated film, the olefin polymer composition (E) having the above composition constituting the heat-sealing layer may be prepared in advance, or the propylene polymer (A-1), A predetermined amount of the ethylene polymer (B-1), the ethylene / α-olefin random copolymer (C-1), and the tackifier resin (D-1) may be weighed and directly fed to the film forming machine. Similarly, an ethylene polymer composition (F) having the above composition may be prepared in advance for the intermediate layer, or an ethylene polymer (B-2) and a high-pressure method low density polyethylene (B-3) may be prepared. A predetermined amount may be measured and put directly into the film forming machine. Such laminated films may be individually laminated after being molded, but the method of coextrusion molding using a multilayer die having at least a three-layer structure is most preferable.
 <容器蓋材>
 本発明の易開封性積層フィルムあるいは基材層と積層した易開封性積層フィルムは各種包装材料として使用することができる。好適な包装材料の例として、熱融着層を容器最内層として用いる容器蓋材がある。容器蓋材として用いる場合は、易開封性積層フィルムをそのまま蓋材として用いても良いし、印刷して用いても良い。更に印刷されたあるいはされていない紙、アルミ箔等と貼り合せて蓋材にしても良い。又、用途によっては予め容器形状に合わせてカットして蓋材にしても良い。容器蓋材とする場合には、基材層を設けた熱融着性積層フィルムを使用するのが好ましい。
<Container lid>
The easy-open laminated film or the easy-open laminated film laminated with the base material layer of the present invention can be used as various packaging materials. An example of a suitable packaging material is a container lid that uses a heat-sealing layer as the container innermost layer. When used as a container lid material, the easy-open laminated film may be used as it is as a lid material, or may be printed and used. Further, it may be bonded to paper that is printed or not, aluminum foil, or the like to form a lid. Further, depending on the application, it may be cut in advance according to the shape of the container to form a lid. When the container lid is used, it is preferable to use a heat-fusible laminated film provided with a base material layer.
 <被着体>
 本発明の易開封性積層フィルムは、各種被着体に熱融着させることにより熱シール層を形成させることができる。このような被着体としてプロピレン系重合体、ポリスチレン、ポリエステル、ポリカーボネート、ポリ塩化ビニル等を例示することができる。これら被着体は、フィルム、シート、トレー、カップ、ボトル等、種々の形状のものであることができる。この中では特にプロピレン系重合体を被着体とすると、熱シール層の密封性、易開封性、耐熱性、耐油性などに優れており好ましい。かかるプロピレン系重合体は、プロピレン系重合体(A-1)と同一の範疇のものであるが、個々の物性は同一であっても異なっていてもよい。例えばプロピレン系重合体からなる被着体においては、被包装材料に合わせてプロピレン系重合体を公知の方法でフィルム、シート、トレー、カップ、ボトル等の種々の形状に成形したものを使用することができる。フィルム若しくはシートの場合は、上記易開封性積層フィルムと同様な方法で製造し得る。トレー若しくはカップの場合は、一旦上記方法でシートを製造した後、真空成形、圧空成形等の熱成形によりトレー、カップ等の容器とすることにより製造し得る。又、カップあるいはボトルの場合は射出成形、射出中空成形(インジェクションブロー)、中空成形等により容器として成形し得る。
<Adherent>
The easy-open laminated film of the present invention can form a heat seal layer by heat-sealing to various adherends. Examples of such an adherend include a propylene polymer, polystyrene, polyester, polycarbonate, polyvinyl chloride and the like. These adherends can be of various shapes such as films, sheets, trays, cups, bottles and the like. Among these, a propylene-based polymer is particularly preferably used as the adherend because it is excellent in the sealing property, easy-opening property, heat resistance, oil resistance and the like of the heat seal layer. Such propylene-based polymers are in the same category as the propylene-based polymer (A-1), but the individual physical properties may be the same or different. For example, in an adherend made of a propylene polymer, a propylene polymer formed into various shapes such as a film, a sheet, a tray, a cup, and a bottle by a known method according to the packaging material should be used. Can do. In the case of a film or a sheet, it can be produced by the same method as that for the easy-open laminated film. In the case of a tray or a cup, it can be produced by once producing a sheet by the above method and then forming a container such as a tray or a cup by thermoforming such as vacuum forming or pressure forming. In the case of a cup or bottle, it can be molded as a container by injection molding, injection hollow molding (injection blow), hollow molding or the like.
 <包装体>
 本発明の易開封性積層フィルムを包装材料として使用する場合、易開封性積層フィルムそのものを、例えば、折りたたんで三方シールしたり、2枚の易開封性積層フィルムを四方シールして包装体としてもよいし、易開封性積層フィルムを上記各種被着体と熱シール層を形成して包装体を形成してもよい。本発明の包装体の形状は、被包装材料の形状、形態あるいは用途に応じて種々の形状を取り得る。例えば、フレキシブルな軟包装体としては、易開封性積層フィルムとプロピレン系重合体層からなる熱シール層を備えたフィルムとからなる三方シール袋に被包装材料を充填した後、口部をヒートシールしてなる四方シール包装体、プロピレン系重合体層からなる熱シール層を備えたシート、トレー、カップ、ボトル等に、被包装材料を充填した後、易開封性積層フィルムの熱融着層を最内層としてなる蓋材(シール材)で上面をシールしてなる包装体等が挙げられる。
 本発明によれば、以下の包装体の製造方法を提供することができる。
すなわち、製造方法の一例としてプロピレン系重合体層からなる熱シール層を備えたプラスチック容器に内容物を収納した後、本発明の易剥離性積層フィルムを蓋材として用いて、そのオレフィン系重合体組成物(E)から構成される熱融着層と相対する面であるプラスチック容器の熱シール層とを、その両者の表面の温度を160℃~210℃、好ましくは170℃~200℃にして、熱融着させる方法を例示することができる。
<Packaging body>
When the easy-open laminated film of the present invention is used as a packaging material, for example, the easy-open laminated film itself can be folded and sealed in three directions, or two easy-open laminated films can be sealed in four directions to form a package. Alternatively, the easy-open laminated film may be formed with the above-mentioned various adherends and a heat seal layer to form a package. The shape of the package of the present invention can take various shapes depending on the shape, form or application of the material to be packaged. For example, as a flexible flexible packaging body, a packaging material is filled in a three-sided sealing bag composed of an easy-open laminated film and a film having a heat sealing layer composed of a propylene-based polymer layer, and then the mouth is heat sealed. After filling the material to be packaged into a sheet, tray, cup, bottle, etc. having a heat sealing layer made of a propylene polymer layer, a four-side sealed package, and then a heat-sealing layer of an easy-open laminated film Examples thereof include a package body in which the upper surface is sealed with a lid material (seal material) serving as the innermost layer.
According to this invention, the manufacturing method of the following package bodies can be provided.
That is, as an example of the production method, after the contents are stored in a plastic container provided with a heat seal layer made of a propylene polymer layer, the olefin polymer is used by using the easily peelable laminated film of the present invention as a lid. The heat sealing layer of the plastic container, which is the surface opposite to the heat-sealing layer composed of the composition (E), has a surface temperature of 160 ° C. to 210 ° C., preferably 170 ° C. to 200 ° C. The method of heat-sealing can be illustrated.
 次に実施例を挙げて本発明を更に具体的に説明するが、本発明はその趣旨を越えない限りこれらの実施例に制約されるものではない。
 実施例及び比較例で使用した重合体を以下に示す。
EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.
The polymers used in Examples and Comparative Examples are shown below.
 (1)プロピレン系重合体(A-1)
 (1-1)プロピレン・エチレンランダム共重合体(R-PP-1):
密度;910kg/m
メルトフローレート(MFR)(230℃);9g/10分、
融点;115℃。
 (1-2)プロピレン・エチレン・1-ブテンランダム共重合体(R-PP-2):
エチレン含有量;3.6モル%(2.4重量%)、
1-ブテン含有量;1.9モル%(2.5重量%)、
密度;910kg/m
メルトフローレート(MFR)(230℃);7.2g/10分、
融点;143℃。
(1) Propylene polymer (A-1)
(1-1) Propylene / ethylene random copolymer (R-PP-1):
Density; 910 kg / m 3 ,
Melt flow rate (MFR) (230 ° C.); 9 g / 10 minutes,
Melting point: 115 ° C.
(1-2) Propylene / ethylene / 1-butene random copolymer (R-PP-2):
Ethylene content; 3.6 mol% (2.4 wt%),
1-butene content: 1.9 mol% (2.5 wt%),
Density; 910 kg / m 3 ,
Melt flow rate (MFR) (230 ° C.); 7.2 g / 10 minutes,
Melting point: 143 ° C.
(2)エチレン系重合体(B-1)
  高密度ポリエチレン(HDPE-1):
密度;954kg/m、MFR(190℃);1.1g/10分、
融点;132℃。
(2) Ethylene polymer (B-1)
High density polyethylene (HDPE-1):
Density; 954 kg / m 3 , MFR (190 ° C.); 1.1 g / 10 min;
Melting point: 132 ° C.
(3)エチレン・α―オレフィンランダム共重合体(C-1)
 (3-1)エチレン・1-ブテンランダム共重合体(EBR):
エチレン含有量;89.1モル%、
結晶化度;10%、
密度;886kg/m
MFR(190℃);4.0g/10分。
 (3-2)エチレン・プロピレン共重合体(EPR):
エチレン含有量;82.6モル%、
密度;870kg/m
MFR(190℃);2.9g/10分。
(3) Ethylene / α-olefin random copolymer (C-1)
(3-1) Ethylene / 1-butene random copolymer (EBR):
Ethylene content; 89.1 mol%;
Crystallinity: 10%,
Density; 886 kg / m 3 ,
MFR (190 ° C.); 4.0 g / 10 min.
(3-2) Ethylene / propylene copolymer (EPR):
Ethylene content; 82.6 mol%,
Density; 870 kg / m 3 ,
MFR (190 ° C); 2.9 g / 10 min.
(4)粘着付与樹脂(D-1)
  水素添加芳香族炭化水素樹脂(アルコン)(荒川化学(株)製、商品名:アルコンP115、環球法軟化点115℃)
(4) Tackifying resin (D-1)
Hydrogenated aromatic hydrocarbon resin (Arcon) (manufactured by Arakawa Chemical Co., Ltd., trade name: Alcon P115, Ring Ball Method Softening Point 115 ° C.)
(5)エチレン系重合体(B-2)
  高密度ポリエチレン(HDPE-2):
密度;954kg/m
MFR(190℃);1.1g/10分、
融点;132℃。
(6)高圧法低密度ポリエチレン(B-3)
  高圧法低密度ポリエチレン(HP―LDPE):
密度;917kg/m
MFR;7.2g/10分。
(7)エチレン系重合体(B-4)
直鎖状あるいは線状低密度ポリエチレン(L-LDPE)
エチレン・4-メチル-1-ペンテンランダム共重合体(これは、L-LDPEに属する。):
密度;935kg/m
MFR;2.3g/10分、
融点;124℃。
(5) Ethylene polymer (B-2)
High density polyethylene (HDPE-2):
Density; 954 kg / m 3 ,
MFR (190 ° C.); 1.1 g / 10 minutes,
Melting point: 132 ° C.
(6) High pressure method low density polyethylene (B-3)
High pressure low density polyethylene (HP-LDPE):
Density; 917 kg / m 3 ,
MFR; 7.2 g / 10 min.
(7) Ethylene polymer (B-4)
Linear or linear low density polyethylene (L-LDPE)
Ethylene 4-methyl-1-pentene random copolymer (this belongs to L-LDPE):
Density; 935 kg / m 3 ,
MFR; 2.3 g / 10 minutes,
Melting point: 124 ° C.
 本発明の実施例及び比較例で得た熱融着性積層フィルムの物性は、以下の方法で測定した。
 (1)易剥離性の評価
 易剥離性を評価するために、厚さ12μmの二軸延伸ポリエチレンテレフタ-トフィルム(PET)に、各実施例、比較例で得られたフィルムのコロナ処理を施した面にウレタン系接着剤を用いてドライラミネ-ションにより積層した積層フィルムを準備し、熱シール層として厚さ300μmのポリプロピレンシ-トを準備した。
 ついで、各積層フィルムの熱融着層とポリプロピレンシ-トを重ね合わせ、表1に記載の所定の温度で、幅5mmのシ-ルバ-を用い、0.2MPaの圧力で1秒間シ-ルした後放冷した。その後ヒートシールした試験片を高温高圧殺菌装置(レトルト処理装置)を用いて、115℃で30分間処理した後、試験片を冷却した。これから15mm幅の試験片を切り取りクロスへッド速度500mm/分でヒ-トシ-ル部を剥離し、その強度をヒ-トシ-ル強度(N/15mm)とした。
The physical properties of the heat-fusible laminated films obtained in the examples and comparative examples of the present invention were measured by the following methods.
(1) Evaluation of easy peelability In order to evaluate easy peelability, a 12 μm thick biaxially stretched polyethylene terephthalate film (PET) was subjected to corona treatment of the films obtained in each of the Examples and Comparative Examples. A laminated film was prepared by laminating by dry lamination using a urethane adhesive on the surface, and a polypropylene sheet having a thickness of 300 μm was prepared as a heat seal layer.
Next, the heat-sealing layer and the polypropylene sheet of each laminated film were overlapped, and sealed at a predetermined temperature shown in Table 1 at a pressure of 0.2 MPa for 1 second using a sealer having a width of 5 mm. And then left to cool. Thereafter, the heat-sealed test specimen was treated at 115 ° C. for 30 minutes using a high-temperature and high-pressure sterilizer (retort treatment equipment), and then the specimen was cooled. A test piece having a width of 15 mm was cut from this, and the heat seal portion was peeled off at a crosshead speed of 500 mm / min, and the strength thereof was defined as heat seal strength (N / 15 mm).
 易剥離性の評価は、ヒートシール強度が15.0N/15mmを超えなく、凝集剥離傾向のある層間剥離で糸引きや膜状に汚く剥がれないものを○とした。ヒートシール強度が剥離状態が問題なくとも15.0N/15mmを超えるものを△とした。ヒートシール強度が15.0N/15mmを超えて完全シール傾向になるものを×とした。 The evaluation of easy peelability was evaluated as ○ when the heat seal strength did not exceed 15.0 N / 15 mm, and it was not peeled off in a thread-like manner or a film form due to delamination with a tendency to cohesive peeling. Even if the heat seal strength exceeded 15.0 N / 15 mm even if the peeled state had no problem, it was rated as Δ. The case where the heat seal strength exceeded 15.0 N / 15 mm and a tendency to complete sealing was indicated as x.
 (2)簡易的封緘性の評価(簡便的に充填した果肉ゼリーの実包品)
 易剥離性を評価するために作成したラミ品を蓋材とし、市販果肉ゼリーなどに利用されているPP系バリア容器(PP/接着層/EVOH/接着層/PP)を使用して、封緘性を評価した。内容物は市販されている果肉ゼリーの内容物を60℃に加温して溶かし、測定する容器に移し、ラミ品を蓋材としてカップシーラーを用いて温度185℃、時間1.0秒×1回、実圧1600N/カップでヒートシールした。ヒートシールした直後に内容物が60℃程度に保持されている状態で蓋材の上面に粘着テープ付きのゴムシート片を貼り付け、このシート面から針を差し込み常温下で内圧をかけて、蓋材シール部分から剥離もしくはエッジ切れし開封した時の強度を封緘強度(Mpa)とした。この測定は株式会社サン科学社製の封緘強度測定器(JIS-Z0238準拠)を用いて評価した。
 封緘評価は、強度の平均値が0.045MPa以上のものを○、平均値が0.045MPa未満のものを△とした。
(2) Evaluation of simple sealing (simple packaged fruit jelly)
Sealed by using a PP-based barrier container (PP / adhesive layer / EVOH / adhesive layer / PP), which is used for commercially available fruit jelly, etc., with a laminated product prepared for evaluating easy peelability. Evaluated. The contents are melted by heating the contents of commercially available pulp jelly to 60 ° C., transferred to a container to be measured, and using a cup sealer with a laminated product as a lid, temperature 185 ° C., time 1.0 seconds × 1 Heat-sealing at an actual pressure of 1600 N / cup. Immediately after heat sealing, with the contents held at about 60 ° C, a piece of rubber sheet with adhesive tape is attached to the top of the lid, and a needle is inserted through this sheet to apply internal pressure at room temperature. The strength at the time of peeling from the material seal portion or cutting the edge and opening was defined as sealing strength (Mpa). This measurement was evaluated using a sealing strength measuring instrument (JIS-Z0238 compliant) manufactured by Sun Science Co., Ltd.
The sealing evaluation was evaluated as “◯” when the average strength was 0.045 MPa or more and “Δ” when the average was less than 0.045 MPa.
 (3)総合評価
 総合的な評価としては、剥離状態が糸引きや膜状に汚く剥がれないもので且つヒートシール強度が15.0N/15mmを超えなく、封緘強度の平均値が0.045MPa以上ものを◎とした。剥離状態が糸引きや膜状に汚く剥がれたり完全シール傾向にあるヒートシール強度が20N/15mmを超えて強いものは×とした。ヒートシール強度が15.0N/15mmを超えて強いか、又は封緘強度が0.045MPa以下のものは△とした。
(3) Comprehensive evaluation As a comprehensive evaluation, the peeled state is not threaded or filmy and does not peel off, the heat seal strength does not exceed 15.0 N / 15 mm, and the average value of the sealing strength is 0.045 MPa or more. The thing was ◎. The case where the peeled state was peeled off in a stringy manner or in the form of a film, or the heat seal strength, which tends to be completely sealed, exceeding 20 N / 15 mm was marked as x. A heat seal strength exceeding 15.0 N / 15 mm or a seal strength of 0.045 MPa or less was indicated by Δ.
 [実施例1~5]
 熱融着層として、前記R-PP-1、R-PP-2、HDPE-1、EBR、EPR、及びアルコンを表1に記載の配合量で調整したオレフィン系重合体組成物(E)を用い、中間層として前記HDPE-2を85質量%及び前記HP-LDPE;15質量%とをドライブレンドしたエチレン系重合体組成物(F)を用い、ラミネート層として前記L-LDPEを用い、夫々別々の押出機に供給し、Tダイ法によって熱融着層/中間層/ラミネ-ト層となる構成の三層共押出フィルムからなる積層フィルムを成形し、ラミネ-ト層にコロナ処理を施して易開封性積層フィルムを得た。易開封性積層フィルムの総厚は50μmで、各層の厚みは熱融着層/中間層/ラミネ-ト層=5.0/40.0/5.0μmであった。
 得られた易開封性積層フィルムの物性を前記記載の方法で測定した。結果を表1に示す。
[Examples 1 to 5]
An olefin polymer composition (E) prepared by adjusting the R-PP-1, R-PP-2, HDPE-1, EBR, EPR, and alkone with the blending amounts shown in Table 1 as a heat-sealing layer. An intermediate polymer layer (F) obtained by dry blending 85% by mass of HDPE-2 and HP-LDPE; 15% by mass was used as an intermediate layer, and L-LDPE was used as a laminate layer. Supply to separate extruders and form a laminated film consisting of a three-layer coextruded film with a structure of heat fusion layer / intermediate layer / laminate layer by the T-die method, and apply corona treatment to the laminate layer An easy-open laminated film was obtained. The total thickness of the easy-open laminated film was 50 μm, and the thickness of each layer was heat fusion layer / intermediate layer / laminate layer = 5.0 / 40.0 / 5.0 μm.
The physical properties of the obtained easily openable laminated film were measured by the method described above. The results are shown in Table 1.
 [比較例1~3]
 熱融着層として、前記R-PP-1、R-PP-2、HDPE-1、EBR、EPR、及びアルコンを表1に記載の配合量で調整したオレフィン系重合体組成物、中間層として前記HDPE-2を85質量%及び前記HP-LDPE;15質量%とをドライブレンドしたエチレン系重合体組成物を用い、ラミネート層として前記L-LDPEを用い、夫々別々の押出機に供給し、Tダイ法によって熱融着層/中間層/ラミネ-ト層となる構成の三層共押出フィルムからなる積層フィルムを成形し、ラミネ-ト層にコロナ処理を施して易開封性積層フィルムを得た。易開封性積層フィルムの総厚は50μmで、各層の厚みは熱融着層/中間層/ラミネ-ト層=5.0/40.0/5.0μmであった。
 得られた易開封性積層フィルムの物性を前記記載の方法で測定した。結果を表2に示す。
 [比較例4]
 熱融着層として、前記R-PP-1、R-PP-2、HDPE-1、EBR、EPR、及びアルコンを表1に記載の配合量で調整したオレフィン系重合体組成物、中間層として100質量%の前記HDPE-2からなるエチレン系重合体組成物を用いた以外は、比較例1~3と同様の積層フィルムを得た。その結果を表2に示す。
[Comparative Examples 1 to 3]
An olefin polymer composition prepared by adjusting the R-PP-1, R-PP-2, HDPE-1, EBR, EPR, and alkone with the blending amounts shown in Table 1 as a heat-fusible layer, as an intermediate layer Using an ethylene polymer composition obtained by dry blending 85% by mass of HDPE-2 and HP-LDPE; 15% by mass, using the L-LDPE as a laminate layer, and feeding them to separate extruders, A laminated film consisting of a three-layer coextruded film with the structure of heat fusion layer / intermediate layer / laminate layer is formed by the T-die method, and a corona treatment is applied to the laminate layer to obtain an easily openable laminate film. It was. The total thickness of the easy-open laminated film was 50 μm, and the thickness of each layer was heat fusion layer / intermediate layer / laminate layer = 5.0 / 40.0 / 5.0 μm.
The physical properties of the obtained easily openable laminated film were measured by the method described above. The results are shown in Table 2.
[Comparative Example 4]
An olefin polymer composition prepared by adjusting the R-PP-1, R-PP-2, HDPE-1, EBR, EPR, and alkone with the blending amounts shown in Table 1 as a heat-fusible layer, as an intermediate layer Laminated films similar to those of Comparative Examples 1 to 3 were obtained except that an ethylene polymer composition comprising 100% by mass of HDPE-2 was used. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 表1に示すように、実施例1~5で得られた易開封性積層フィルムはヒートシール強度は10~15N/15mm程度と開封しやすい強度で剥離状態も糸引きや膜引きがなくきれいな状態であり、封緘強度は内容物が60℃程度と高温状態であるにも関わらず高い封緘強度であった。
 それに対し、表2に示すように、比較例1~4で得られた易開封性積層フィルムでは、ヒートシール強度は18~38N/15mm程度と高くイージーオープンフィルムとしては適切でなかったり、また封緘強度が弱く内容物が高温状態で移送された場合、移送中に漏れが起きる可能性がある。
As shown in Table 1, the easy-open laminate films obtained in Examples 1 to 5 have a heat-sealing strength of about 10 to 15 N / 15 mm and are easy to open, with no peeling or stringing, and a clean state. The sealing strength was high even though the contents were at a high temperature of about 60 ° C.
On the other hand, as shown in Table 2, the easy-open laminated films obtained in Comparative Examples 1 to 4 have a high heat seal strength of about 18 to 38 N / 15 mm and are not suitable as easy open films. If the strength is weak and the contents are transferred at a high temperature, leakage may occur during the transfer.
 本発明の易開封性積層フィルムは、低温ヒートシ-ル性、耐ブロッキング性、包装材料に好適な耐衝撃性、スリップ性、剛性、透明性等を有する易開封性積層フィルムとしてそのままでも包装用フィルムとして、特に、ポリプロピレン製のシート、トレー、カップ、ボトル等の蓋材として好適であり、せんべい、ポテトチップス等のスナック菓子包装、あるいはゼリー、ミルク、ヨーグルト、プリン、豆腐、乳酸飲料等の食品包装や、医薬品、医療用器具等の包装、ブリスター包装、その他日用品や雑貨等の包装の包装材料、特に油脂及び脂肪性食品の包装に適応しており、当該用途にも好適に用いることができる。また、例えばポリプロピレン製の容器など、果肉ゼリーやプリン、豆腐、その他この易開封性積層フィルムを用いた各種容器蓋材包装や容器を使用しない縦ピーローや横ピーロー袋物など包装体とした場合の高い密封性や封緘性を有しており、包装材料として適している。 The easy-open laminate film of the present invention is a packaging film as it is as an easy-open laminate film having low-temperature heat sealability, blocking resistance, impact resistance suitable for packaging materials, slip properties, rigidity, transparency, etc. In particular, it is suitable as a lid material for polypropylene sheets, trays, cups, bottles, etc., packaging for snacks such as rice crackers, potato chips, etc., or food packaging such as jelly, milk, yogurt, pudding, tofu, lactic acid beverages, etc. It is suitable for packaging of pharmaceuticals, medical instruments, blister packaging, packaging materials for other daily necessities and miscellaneous goods, especially for fats and oils and fatty foods, and can be suitably used for such applications. In addition, for example, containers made of polypropylene, such as pulp jelly, pudding, tofu, and other various container lid packaging using this easy-open laminated film, and packaging such as vertical and horizontal pillow bags that do not use containers are high. It has sealing properties and sealing properties and is suitable as a packaging material.

Claims (9)

  1.   熱融着層、中間層、及びラミネート層からなる易開封性積層フィルムであって、
      熱融着層は、
     プロピレン系重合体(A-1)      79.8 ~94    質量%、
      密度が900kg/m以上の
     エチレン系重合体(B-1)         4     ~10    質量%、
     密度が860kg/m以上
    900kg/m未満の
      エチレン・α―オレフィン
          ランダム共重合体(C-1)      1.5 ~ 7.5質量%
    及び
          粘着付与樹脂(D-1)          0.5 ~  2.7質量%
    〔但し、(A-1)+(B-1)+(C-1)+(D-1)=100質量%とする。〕からなるオレフィン系重合体組成物(E)から構成され、
     中間層は、
    密度が940~970kg/mの範囲にある
          エチレン系重合体(B-2)  50~95質量%
    及び
    密度が905~935kg/mの範囲にある
      高圧法低密度ポリエチレン(B-3)    5~50質量%
    〔但し、(B-2)+(B-3)=100質量%とする。〕
    からなるエチレン系重合体組成物(F)から構成され、
     ラミネート層は、密度が900~950kg/mの範囲にあるエチレン系重合体(B-4)から構成される。
    An easy-open laminated film consisting of a heat fusion layer, an intermediate layer, and a laminate layer,
    Thermal fusion layer
    Propylene polymer (A-1) 79.8 to 94% by mass,
    4 to 10% by mass of an ethylene polymer (B-1) having a density of 900 kg / m 3 or more,
    Ethylene / α-olefin random copolymer (C-1) having a density of 860 kg / m 3 or more and less than 900 kg / m 3 1.5 to 7.5% by mass
    And tackifying resin (D-1) 0.5 to 2.7% by mass
    [However, (A-1) + (B-1) + (C-1) + (D-1) = 100 mass%) An olefin polymer composition (E) consisting of
    The middle layer
    Density is in the range of 940 to 970 kg / m 3 Ethylene polymer (B-2) 50 to 95% by mass
    And high density low density polyethylene (B-3) having a density in the range of 905 to 935 kg / m 3 5 to 50% by mass
    [However, (B-2) + (B-3) = 100 mass%. ]
    An ethylene polymer composition (F) comprising:
    The laminate layer is composed of an ethylene polymer (B-4) having a density in the range of 900 to 950 kg / m 3 .
  2.  プロピレン系重合体(A-1)が、融点が110~145℃の範囲にあるプロピレン・α-オレフィンランダム共重合体である請求項1記載の易開封性積層フィルム。 The easy-open laminate film according to claim 1, wherein the propylene polymer (A-1) is a propylene / α-olefin random copolymer having a melting point of 110 to 145 ° C.
  3.  エチレン系重合体(B-1)が、密度が940~970kg/mのエチレン系重合体である請求項1または2に記載の易開封性積層フィルム。 The easy-open laminated film according to claim 1 or 2, wherein the ethylene polymer (B-1) is an ethylene polymer having a density of 940 to 970 kg / m 3 .
  4.  エチレン・α-オレフィンランダム共重合体(C-1)が、密度が880~895kg/mの範囲にあり、α―オレフィンが炭素数4~10である少なくとも1種類であるエチレン・α-オレフィンランダム共重合体(C1-1)及び密度が865~875kg/mの範囲にあるエチレン・プロピレンランダム共重合体(C1-2)から構成されることを特徴とする請求項1記載の易開封性積層フィルム。 The ethylene / α-olefin random copolymer (C-1) has at least one kind of ethylene / α-olefin having a density in the range of 880 to 895 kg / m 3 and an α-olefin having 4 to 10 carbon atoms. The easy-opening according to claim 1, characterized in that it is composed of a random copolymer (C1-1) and an ethylene / propylene random copolymer (C1-2) having a density in the range of 865 to 875 kg / m 3. Laminated film.
  5.  ラミネート層を構成するエチレン系重合体(B-4)が、エチレン・α-オレフィンランダム共重合体である請求項1記載の易開封性積層フィルム。 The easily openable laminated film according to claim 1, wherein the ethylene polymer (B-4) constituting the laminate layer is an ethylene / α-olefin random copolymer.
  6.  熱融着層、中間層及びラミネート層が共押出し成形して得られるものである請求項1~5の何れかに記載の易開封性積層フィルム。 The easily openable laminated film according to any one of claims 1 to 5, wherein the heat-fusible layer, the intermediate layer and the laminate layer are obtained by coextrusion molding.
  7.  請求項1~6の何れかに記載の易開封性積層フィルムのラミネート層に基材層が積層されてなる易開封性積層フィルム。 An easy-open laminated film obtained by laminating a base material layer on the laminate layer of the easy-open laminated film according to any one of claims 1 to 6.
  8.  請求項1~6の何れかに記載の易開封性積層フィルムからなる容器蓋材。 A container lid made of the easy-open laminated film according to any one of claims 1 to 6.
  9.  請求項1~6の何れかに記載の易開封性積層フィルムとプロピレン系重合体層を有する被着部とからなり、該積層フィルムとプロピレン系重合体層間の熱シール構造を有することを特徴とする包装体。 It comprises the easy-open laminate film according to any one of claims 1 to 6 and an adherent part having a propylene polymer layer, and has a heat seal structure between the laminate film and the propylene polymer layer. Packaging.
PCT/JP2014/068043 2013-07-09 2014-07-07 Easily openable laminated film and use therefor WO2015005279A1 (en)

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