WO2019189359A1 - Easy-to-cut multilayer film having high surface hardness - Google Patents

Easy-to-cut multilayer film having high surface hardness Download PDF

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Publication number
WO2019189359A1
WO2019189359A1 PCT/JP2019/013190 JP2019013190W WO2019189359A1 WO 2019189359 A1 WO2019189359 A1 WO 2019189359A1 JP 2019013190 W JP2019013190 W JP 2019013190W WO 2019189359 A1 WO2019189359 A1 WO 2019189359A1
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Prior art keywords
resin
layer
multilayer film
weight
cyclic olefin
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PCT/JP2019/013190
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French (fr)
Japanese (ja)
Inventor
雅生 鈴木
雄太 工藤
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株式会社プライムポリマー
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Application filed by 株式会社プライムポリマー filed Critical 株式会社プライムポリマー
Priority to JP2020509195A priority Critical patent/JP6978588B2/en
Publication of WO2019189359A1 publication Critical patent/WO2019189359A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

  • the present invention relates to a multilayer film having easy cutting properties, high surface hardness, and suitable for packaging applications.
  • Polyethylene blown film is widely used for packaging applications, and heat sealing is performed to seal the packaging bag.
  • Such a packaging film is required to have characteristics depending on the application. For example, an easy tear openability (easy cut property) is required so that the package can be opened and opened by hand (see, for example, Patent Document 1). Further, in the case of heavy weight packaging bags, strength that cannot be broken even when grains and fertilizers in the unit of several tens of kilograms are added is required, so that the dart impact strength is required to be strong (see, for example, Patent Document 2). In addition, if the film itself does not have rigidity at the time of filling, the film will be broken and wrinkled, or the apparatus may be caught and scratched, so that appropriate rigidity is required. However, if the rigidity is high, the dart impact strength is weakened, and there are problems that the film is torn and the contents are spilled, and the transparency is deteriorated and the contents are difficult to see.
  • the object of the present invention is to prevent the occurrence of curling by improving the surface hardness of the film while maintaining transparency, heat sealability, impact strength and tensile elastic modulus in view of the above-mentioned problems of the prior art.
  • Another object of the present invention is to provide a multilayer film having moderate rigidity.
  • MFR Melt mass flow rate
  • the present invention it is possible to provide a multilayer film for packaging in which the surface hardness of the film is improved without curling while maintaining transparency, heat sealability, impact strength and tensile elastic modulus.
  • the multilayer film according to the present invention is Resin composition containing cyclic olefin-based resin (a1) 0.1 to 10% by weight and ethylene-based resin (b1) 90 to 99.9% by weight satisfying the following conditions (i) and (ii) (however, A layer (I) comprising a total of 100% by weight of component (a1) and component (b1); A resin composition containing 10 to 70% by weight of a cyclic olefin resin (a2) and 30 to 90% by weight of an ethylene resin (b2) satisfying the following conditions (i) and (ii) (provided that the component (a2) And the component (b2) is 100% by weight.) And a layer (III) containing an ethylene-based resin (b3).
  • the density is 880 to 970 kg / m 3 .
  • Melt mass flow rate (MFR) at 190 ° C. and a load of 2.16 kg is 0.1 to 50 g / 10 min.
  • the multilayer film according to the present invention comprises a cyclic olefin resin (a3) between at least one of the layer (I) and the layer (II) and between the layer (II) and the layer (III).
  • the layer (I) in the multilayer film of the present invention has a cyclic olefin resin (a1) of 0.1 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 0.8 to 8% by weight, Resin containing 90 to 99.9 wt%, preferably 91 to 99.5 wt%, more preferably 92 to 99.2 wt% of ethylene-based resin (b1) satisfying the above conditions (i) and (ii) It consists of a composition (however, the total of component (a1) and component (b1) is 100% by weight.
  • resin composition (I) herein composition (I)”.
  • the layer (I) is a surface layer of the multilayer film of the present invention.
  • the film can be produced without curling while maintaining transparency, heat sealability, impact strength and tensile elastic modulus.
  • the surface hardness of can be improved.
  • cyclic olefin resin (a1) examples include a norbornene polymer, a vinyl alicyclic hydrocarbon polymer, a cyclic conjugated diene polymer, and the like. Among these, norbornene-based polymers are preferable.
  • the norbornene polymer includes a ring-opening polymer of a norbornene monomer (hereinafter also referred to as “COP”), and a norbornene copolymer obtained by copolymerizing a norbornene monomer and an ⁇ -olefin such as ethylene. (Hereinafter also referred to as “COC”). COP and COC hydrogenated products can also be used.
  • the cyclic olefin-based resin (a1) is preferably COC for reasons of dispersibility with respect to polyethylene.
  • COC examples include a copolymer of ethylene and a cyclic olefin represented by the following general formula (1).
  • n is 0 or a positive integer
  • R 1 to R 12 are each independently a hydrogen atom, a halogen atom or a hydrocarbon group.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.
  • Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.
  • Examples of the group include a cyclohexyl group
  • examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. These hydrocarbon groups may be substituted with a halogen atom.
  • R 9 and R 10 , R 11 and R 12 may be integrated to form a divalent hydrocarbon group, and R 9 or R 10 and R 11 or R 12 may form a ring with each other. Also good.
  • the divalent hydrocarbon group include alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group.
  • the ring formed from R 9 or R 10 and R 11 or R 12 may be monocyclic or condensed polycyclic, may be a polycyclic ring having a bridge, and is a ring having an unsaturated bond. It may also be a ring composed of a combination of these rings.
  • the cyclic olefin represented by the above formula (1) can be easily produced by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by Diels-Alder reaction.
  • cyclic olefin represented by the formula (1) include bicyclo [2.2.1] hept-2-ene, 6-methylbicyclo [2.2.1] hept-2-ene, 5, 6-dimethylbicyclo [2.2.1] hept-2-ene, 1-methylbicyclo [2.2.1] hept-2-ene, 6-ethylbicyclo [2.2.1] hept-2-ene 6-butylbicyclo [2.2.1] hept-2-ene, 6-isobutylbicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] hept-2-ene Ene, tetracyclo [4.4.0.1 2,5 .
  • the COC is, in addition to the ethylene component and the cyclic olefin component represented by the above formula (1), other copolymerizable unsaturated monomer components such as propylene, within a range not impairing the object of the present invention.
  • 3 to 20 carbon atoms such as 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene
  • a cyclic olefin such as ⁇ -olefin, norbornene, ethylidene norbornene, and dicyclopentadiene, and cyclic diene.
  • the structural unit derived from ethylene is preferably in the range of 40 to 85 mol%, more preferably 50 to 75 mol%, and the structural unit derived from the cyclic olefin is preferably 15 to 60 mol%, More preferably, it is in the range of 25-50 mol%.
  • the structural unit derived from ethylene is contained within the above range, the film has excellent rigidity, tearability, processing stability, and impact strength.
  • examples of the ring-opening polymer (COP) of the norbornene monomer include “ZEONOR” manufactured by Nippon Zeon Co., Ltd.
  • examples of the copolymer (COC) include “Appel” manufactured by Mitsui Chemicals, Inc. and “TOPAS” manufactured by Polyplastics.
  • the ethylene resin (b1) used for the layer (I) is an ethylene resin that satisfies the above conditions (i) and (ii).
  • ⁇ Condition (i) The density of the ethylene-based resin (b1), the film rigidity, in view of heat sealability, 880 ⁇ 970kg / m 3, preferably of 885 ⁇ 950kg / m 3, more preferably 900 ⁇ 930kg / m 3 range.
  • the density is a value measured according to JIS K7112 (density gradient tube method).
  • the MFR (190 ° C., 2.16 kg load, JIS K7210 compliant) of the ethylene-based resin (b1) is 0.1 to 50 g / 10 min from the viewpoint of bubble stability, film strength, moldability (fluidity), etc.
  • the range is preferably 0.5 to 30 g / 10 min, more preferably 0.7 to 15 g / 10 min.
  • Examples of the ethylene resin (b1) include linear low density polyethylene.
  • the linear low-density polyethylene contains a copolymer of ethylene and ⁇ -olefin, and such a copolymer can be obtained using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. It is also possible to add other low density polyethylene.
  • a polyethylene resin satisfying each of the above properties can be selected and used from commercially available polyethylene resins. Further, the ethylene resin (b1) may be used alone or in combination of two or more.
  • ком ⁇ онен ingredients ⁇ Other ingredients> If the resin composition (I) is within a range that does not impair the object of the present invention, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a slip agent, a lubricant, Various additives that are usually added to polyolefins, such as pigments and droplets, may be contained.
  • the layer (II) in the multilayer film of the present invention comprises 10 to 70% by weight, preferably 20 to 65% by weight, more preferably 30 to 60% by weight of the cyclic olefin resin (a2), and the conditions (i) and A resin composition containing 30 to 90% by weight, preferably 35 to 80% by weight, more preferably 40 to 70% by weight of the ethylene-based resin (b2) satisfying (ii) (provided that the component (a2) and the component ( The total of b2) is 100% by weight and is hereinafter also referred to as “resin composition (II)”.
  • the layer (II) is an intermediate layer of the multilayer film of the present invention.
  • the multilayer film excellent in easy-cut property can be obtained by making the intermediate
  • Examples of the cyclic olefin resin (a2) used for the layer (II) include the same as those exemplified for the cyclic olefin resin (a1).
  • the cyclic olefin resin (a2) used in the layer (II) the same type as the cyclic olefin resin (a1) may be used, or a different type may be used.
  • examples of the ethylene resin (b2) used for the layer (II) include the same ones as exemplified for the ethylene resin (b1).
  • the same type as the ethylene resin (b1) may be used, or a different type may be used.
  • ethylene-type resin (b2) may be only 1 type, and may be used in combination of 2 or more type.
  • the resin composition (II) may contain the other components in the same manner as the resin composition (I).
  • the layer (III) in the multilayer film of the present invention contains the ethylene resin (b3) as a main component.
  • the ethylene resin (b3) is not particularly limited as long as it is an ethylene resin used for a sealant, and examples thereof include those similar to those exemplified for the ethylene resin (b1).
  • the ethylene resin (b3) used in the layer (III) the same type as the ethylene resin (b1) or (b2) may be used, or a different type may be used.
  • the layer (III) is an inner layer (seal layer) of the multilayer film of the present invention.
  • the inner layer of a multilayer film consists of ethylene-type resin (b3)
  • the multilayer film excellent in heat-sealability can be obtained.
  • the layer (III) may be a single layer or a multilayer including two or more layers. Moreover, only 1 type may be used for ethylene-type resin (b3), and it may use it in combination of 2 or more type.
  • the layer (III) may contain other components exemplified in the resin composition (I) as necessary as long as the object of the present invention is not impaired.
  • the layer (IV) optionally provided in the multilayer film of the present invention comprises 0 to 70% by weight, preferably 0 to 60% by weight, more preferably 1 to 55% by weight of the cyclic olefin resin (a3), A resin composition containing 30 to 100% by weight, preferably 40 to 100% by weight, more preferably 45 to 99% by weight of an ethylene-based resin (b4) satisfying (i) and (ii) (provided that component (a3 ) And component (b4) is 100% by weight, hereinafter also referred to as “resin composition (IV)”.
  • Examples of the cyclic olefin resin (a3) used for the layer (IV) include the same as those exemplified for the cyclic olefin resin (a1).
  • the cyclic olefin resin (a3) used for the layer (IV) the same type as the cyclic olefin resin (a1) or (a2) may be used, or a different type may be used.
  • examples of the ethylene resin (b4) used for the layer (IV) include the same ones as exemplified for the ethylene resin (b1).
  • the ethylene resin (b4) used for the layer (IV) may be the same type as the ethylene resin (b1), (b2) or (b3), or may be a different type. Good.
  • only 1 type may be used for ethylene-type resin (b4), and it may use it in combination of 2 or more type.
  • the resin composition (II) may contain the other components in the same manner as the resin composition (I).
  • the multilayer film of the present invention includes the above-described layer (I), layer (II), and layer (III), and includes the above-described layer (IV) as necessary.
  • the total use ratio of the cyclic olefin resins (a1), (a2) and (a3) to the whole film is preferably 0.1 to 60% by weight, more preferably 1 to 55% by weight. %, More preferably 5 to 50% by weight.
  • the total use ratio of the cyclic olefin-based resins (a1), (a2) and (a3) in the entire multilayer film of the present invention is within the above range, the film can be stably formed and easily cut. Can be granted.
  • the thickness of the multilayer film of the present invention may be appropriately set according to various uses, but the thickness of the layer (I) is usually in the range of 2 to 100 ⁇ m, preferably 4 to 80 ⁇ m.
  • the thickness of II) is usually in the range of 2 to 100 ⁇ m, preferably 4 to 80 ⁇ m, and the thickness of the layer (III) is usually in the range of 4 to 150 ⁇ m, preferably 8 to 120 ⁇ m.
  • the thickness of the layer (IV) is usually in the range of 2 to 100 ⁇ m, preferably 4 to 80 ⁇ m.
  • the multilayer film of the present invention has a haze of preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less as a 90 ⁇ m thick multilayer film.
  • a haze preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less as a 90 ⁇ m thick multilayer film.
  • the multilayer film of the present invention has a dart impact strength of preferably 600 g or more, more preferably 700 g or more as a 90 ⁇ m thick multilayer film.
  • the dart impact strength is 600 g or more
  • the bag has sufficient strength, and when applied as a food packaging bag, the bag can be prevented from being torn during transportation or dropping.
  • the upper limit is not particularly limited.
  • the multilayer film of the present invention is an Elmendorf tear strength in the TD direction as a multilayer film having a thickness of 90 ⁇ m, preferably 0.1 to 6N, more preferably 0.1 to 4N, and more preferably 0.1 to 3N. Is more preferable.
  • TD direction Transverse Direction
  • MD direction Machine Direction
  • the multilayer film of the present invention is a 90 ⁇ m-thick multilayer film, and preferably has a tensile modulus in the MD direction of 10 to 2500 MPa, more preferably 50 to 2000 MPa, and even more preferably 100 to 2000 MPa.
  • a tensile modulus in the MD direction 10 MPa or more
  • the strength of the film is further improved.
  • the tensile modulus in the MD direction is 2500 MPa or less
  • the film has excellent mechanical strength such as tensile strength.
  • the multilayer film of the present invention is a 90 ⁇ m thick multilayer film having a microhardness of preferably 250 to 1000 MPa, more preferably 300 to 900 MPa, and further preferably 350 to 800 MPa.
  • a microhardness preferably 250 to 1000 MPa, more preferably 300 to 900 MPa, and further preferably 350 to 800 MPa.
  • the microhardness is within the above range, a multilayer film having appropriate rigidity is obtained.
  • the microhardness of the multilayer film of the present invention can be improved by 10% or more compared to the microhardness of the multilayer film produced under the same conditions except that the layer (I) does not contain a cyclic olefin resin. preferable.
  • the method for producing the multilayer film of the present invention is not particularly limited.
  • the resin composition used for each layer is laminated by coextrusion molding in a molten state using a multilayer die, and then formed into a film by an inflation method or the like.
  • a coextrusion method may be mentioned.
  • the film thus obtained can be processed into a film for producing a food packaging bag or the like as it is, as an unstretched film, or as a stretched film by further stretching.
  • the thickness of the melt-extruded film (referred to as a stretched original fabric, including a thick molded body called a sheet depending on the thickness) varies depending on the molding method.
  • the stretched original fabric has a thickness of preferably 50 ⁇ m to 2000 ⁇ m, and more preferably 100 ⁇ m to 1500 ⁇ m.
  • the method for cooling the molten resin may be either air cooling or water cooling.
  • a method of stretching the stretched raw fabric a method of simultaneously or sequentially biaxially stretching longitudinally and laterally by a tenter method, a method of simultaneously biaxially stretching longitudinally and laterally by a tubular method, or a difference in rotational speed ratio of two or more rolls
  • Examples of the method include uniaxial stretching in the film flow direction.
  • the multilayer film of the present invention is a water packaging bag, liquid soup bag, liquid paper container, lami raw fabric, special shape liquid packaging bag (such as standing pouch), standard bag, heavy bag, wrap film, sugar bag, oil packaging Suitable for various packaging films such as bags and food packaging, protective films, infusion bags, agricultural materials, back-in boxes, semiconductor materials, pharmaceuticals, clean films used for packaging foods, and the like.
  • Test piece (90 ⁇ m thickness) is clamped by air clamp method, hemispherical dart is dropped from a certain height, and the load [g] at which the test piece breaks 50% is read from the graph.
  • the number of drops at one level is 10 times, and method A is used.
  • ⁇ Tensile modulus (MD direction)> A specimen cut into a shape for a tensile cutting load according to JIS K6781 was used as a test piece (90 ⁇ m thickness). Using a tensile tester (Instron “Universal Tensile Tester 3380”), the tensile modulus of elasticity of the test piece (MD method) (unit: MD) under the conditions of a chuck distance of 80 mm, a tensile speed of 500 mm / min, and a temperature of 23 ° C. : MPa).
  • ⁇ Micro hardness> Using a “dynamic ultra-micro hardness tester DUH-W201S” manufactured by Shimadzu Corporation, measurement was performed under conditions of a temperature of 23 ° C. and a humidity of 50%, and the hardness was calculated from the indentation depth when a test load was applied.
  • ⁇ Curl> As a test piece, a film having a size of 30 mm in length and 200 mm in width was cut out. As the cutting direction, a sample cut 200 mm along the MD direction was an MD sample, and a shape along the TD direction was a TD sample. The left end of the cut film sample was fixed with tape, the right end was held by hand so that it was in close contact with the table, and the lateral length not touching the table when the hand was released was measured. If each sample in the MD direction and the TD direction was less than 35 mm, it was “pass”, and if either one was 35 mm or more, it was “bad”.
  • LL1 “Evolue SP2510” manufactured by Prime Polymer Co., Ltd. (density: 923 kg / m 3 , MFR: 1.4 g / 10 min)
  • LL2 “Evolue SP1022” manufactured by Prime Polymer Co., Ltd. (density: 908 kg / m 3 , MFR: 2.0 g / 10 min)
  • LL3 “Evolue SP2520” manufactured by Prime Polymer Co., Ltd. (density: 925 kg / m 3 , MFR: 1.9 g / 10 min)
  • LL4 “Evolue SP1520” manufactured by Prime Polymer Co., Ltd.
  • Example 1 when Examples 1 and 2 are compared with Comparative Example 2, transparency, easy cutability, impact strength, and tensile modulus are obtained by blending the layer (I) with a cyclic olefin resin. It was found that the surface hardness (microhardness) was improved without curling while maintaining the above. In particular, it was found that the surface hardness of Example 2 was improved by 10% or more compared with Comparative Example 2. Similarly, when Example 3 and Comparative Example 3 were compared, it was found that in Example 3, the surface hardness was improved by 10% or more and other characteristics were maintained.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention addresses the problem of providing a multilayer film that has a suitable stiffness without the occurrence of curling, since the surface hardness of the film is improved while maintaining transparency, heat sealing properties, impact strength, and tensile elastic modulus. The multilayer film according to the present invention contains (I) a layer made of a resin composition containing 0.1-10 wt% of a cyclic olefin resin (a1) and 90-99.9 wt% of an ethylene resin (b1) satisfying conditions (i) and (ii), (II) a layer made of a resin composition containing 10-70 wt% of a cyclic olefin resin (a2) and 30-90 wt% of an ethylene resin (b2) satisfying (i) and (ii), and (III) a layer containing an ethylene resin (b3). (i) The density is 880-970 kg/m3. (ii) The melt mass-flow rate (MFR) at 190°C and a load of 2.16 kg is 0.1-50 g/10 min.

Description

表面硬度が高い易カット性多層フィルムEasy-cut multilayer film with high surface hardness
　本発明は、易カット性を有し、表面硬度が高く、包装用途に適した多層フィルムに関する。 The present invention relates to a multilayer film having easy cutting properties, high surface hardness, and suitable for packaging applications.
　ポリエチレン製のインフレーションフィルムは包装用途に広く使用され、包装袋を密閉するためにヒートシールが行われる。 Polyethylene blown film is widely used for packaging applications, and heat sealing is performed to seal the packaging bag.
　このような包装用フィルムには、用途に応じた特性が求められている。例えば、包装体を手で引き裂いて開封できるように易引裂き開封性（易カット性）が求められている（例えば特許文献１参照）。また、重量物包装袋の場合、数十キログラム単位の穀物や肥料を入れても破れない強度が求められるため、ダート衝撃強度が強いことが要求される（例えば特許文献２参照）。また、充填時にフィルム自身の剛性がないとフィルムが折れてシワになったり、装置に引っかかり傷がついたりするため、適度な剛性が要求される。しかしながら、剛性が高いとダート衝撃強度が弱くなり、フィルムが破れて中身がこぼれるといった問題や、透明性が悪化して中身が見えにくくなるといった問題が生じる。 Such a packaging film is required to have characteristics depending on the application. For example, an easy tear openability (easy cut property) is required so that the package can be opened and opened by hand (see, for example, Patent Document 1). Further, in the case of heavy weight packaging bags, strength that cannot be broken even when grains and fertilizers in the unit of several tens of kilograms are added is required, so that the dart impact strength is required to be strong (see, for example, Patent Document 2). In addition, if the film itself does not have rigidity at the time of filling, the film will be broken and wrinkled, or the apparatus may be caught and scratched, so that appropriate rigidity is required. However, if the rigidity is high, the dart impact strength is weakened, and there are problems that the film is torn and the contents are spilled, and the transparency is deteriorated and the contents are difficult to see.
　適度な剛性（表面硬度）を付与するために、包装用フィルムの表層に、中間層よりも剛性の高い高密度のポリエチレンまたはポリプロピレンを用いる方法が知られているが、この場合、カールが酷く、製袋が困難となる問題が発生する。 In order to give moderate rigidity (surface hardness), a method using high-density polyethylene or polypropylene having higher rigidity than the intermediate layer is known as the surface layer of the packaging film. In this case, curl is severe, The problem that bag making becomes difficult occurs.
　したがって、フィルムとしてカールが発生せずに充填時に必要十分な剛性（表面硬度）を持ち、かつ衝撃強度が強いフィルムが望まれていた。 Therefore, there has been a demand for a film having sufficient rigidity (surface hardness) at the time of filling without causing curling as a film and having high impact strength.
特開平１０－２３７２３４号公報JP-A-10-237234 特開２０１６－０４９７７５号公報JP 2016-049775 A
　本発明の目的は、上述した従来技術の問題点に鑑み、透明性、ヒートシール性、衝撃強度および引張弾性率を維持した状態で、フィルムの表面硬度を向上させることにより、カールが発生せずに適度な剛性を有する多層フィルムを提供することにある。 The object of the present invention is to prevent the occurrence of curling by improving the surface hardness of the film while maintaining transparency, heat sealability, impact strength and tensile elastic modulus in view of the above-mentioned problems of the prior art. Another object of the present invention is to provide a multilayer film having moderate rigidity.
　本発明者らは、上記課題を解決すべく鋭意検討した。その結果、ポリエチレンの多層フィルムの表層に環状オレフィン系樹脂を特定の量で配合することで、衝撃強度や引張弾性率に優れた特性を維持しつつ、表面硬度を上げることができることを見出し、本発明を完成するに至った。なお、特許文献１，２等の従来技術では、多層フィルムの中間層に環状オレフィン系樹脂を配合して易カット性を得るという技術的思想は存在していたが、多層フィルムの表層に特定量の環状オレフィン系樹脂を配合して表面硬度を向上させるという技術的思想は存在しなかった。本発明の態様の例を以下に示す。 The present inventors diligently studied to solve the above problems. As a result, it was found that by adding a specific amount of cyclic olefin resin to the surface layer of the polyethylene multilayer film, the surface hardness can be increased while maintaining excellent properties in impact strength and tensile modulus. The invention has been completed. In addition, in the prior arts such as Patent Documents 1 and 2, the technical idea of blending a cyclic olefin-based resin in the intermediate layer of the multilayer film to obtain easy cutting properties, a specific amount is present on the surface layer of the multilayer film. There was no technical idea to improve the surface hardness by blending the cyclic olefin-based resin. Examples of embodiments of the present invention are shown below.
　［１］　環状オレフィン系樹脂（ａ１）０．１～１０重量％と、下記条件（i）および（ii）を満たすエチレン系樹脂（ｂ１）９０～９９．９重量％とを含有する樹脂組成物（ただし、成分（ａ１）と成分（ｂ１）の合計を１００重量％とする。）からなる層（Ｉ）と、
　環状オレフィン系樹脂（ａ２）１０～７０重量％と、下記条件（i）および（ii）を満たすエチレン系樹脂（ｂ２）３０～９０重量％とを含有する樹脂組成物（ただし、成分（ａ２）と成分（ｂ２）の合計を１００重量％とする。）からなる層（ＩＩ）と、
　エチレン系樹脂（ｂ３）を含有する層（III）と
を含む多層フィルム：
（i）密度が８８０～９７０ｋｇ／ｍ3である；
（ii）１９０℃、２．１６ｋｇ荷重におけるメルトマスフローレイト（ＭＦＲ）が、０．１～５０ｇ／１０分である。 [1] A resin composition containing 0.1 to 10% by weight of a cyclic olefin resin (a1) and 90 to 99.9% by weight of an ethylene resin (b1) satisfying the following conditions (i) and (ii) (However, the total of component (a1) and component (b1) is 100% by weight) layer (I),
A resin composition containing 10 to 70% by weight of a cyclic olefin resin (a2) and 30 to 90% by weight of an ethylene resin (b2) satisfying the following conditions (i) and (ii) (provided that the component (a2) And the component (b2) is 100% by weight.)
A multilayer film comprising an ethylene resin (b3) -containing layer (III):
(I) the density is from 880 to 970 kg / m 3 ;
(Ii) Melt mass flow rate (MFR) at 190 ° C. and a load of 2.16 kg is 0.1 to 50 g / 10 min.
　［２］　前記環状オレフィン系樹脂（ａ１）および（ａ２）が、エチレン・環状オレフィン共重合体であることを特徴とする項［１］に記載の多層フィルム。 [2] The multilayer film according to item [1], wherein the cyclic olefin resins (a1) and (a2) are ethylene / cyclic olefin copolymers.
　［３］　前記層（Ｉ）と前記層（ＩＩ）の間、および、前記層（ＩＩ）と前記層（III）の間の少なくとも一方に、環状オレフィン系樹脂（ａ３）０～７０重量％と、前記条件（i）および（ii）を満たすエチレン系樹脂（ｂ４）３０～１００重量％とを含有する樹脂組成物（ただし、成分（ａ３）と成分（ｂ４）の合計を１００重量％とする。）からなる層（ＩＶ）をさらに含むことを特徴とする項［１］または［２］に記載の多層フィルム。 [3] Between at least one of the layer (I) and the layer (II), and between the layer (II) and the layer (III), 0 to 70% by weight of the cyclic olefin resin (a3) A resin composition containing ethylene resin (b4) 30 to 100% by weight satisfying the above conditions (i) and (ii) (provided that the total of component (a3) and component (b4) is 100% by weight) The multilayer film according to item [1] or [2], further comprising a layer (IV) comprising:
　［４］　前記環状オレフィン系樹脂（ａ１）、（ａ２）および（ａ３）のフィルム全体に対する使用割合の合計が０．１～６０重量％であることを特徴とする項［３］に記載の多層フィルム。 [4] The multilayer according to item [3], wherein the total use ratio of the cyclic olefin resins (a1), (a2) and (a3) to the whole film is 0.1 to 60% by weight. the film.
　本発明によれば、透明性、ヒートシール性、衝撃強度および引張弾性率を維持しつつ、カールを発生させずにフィルムの表面硬度を向上させた包装用多層フィルムを提供することができる。 According to the present invention, it is possible to provide a multilayer film for packaging in which the surface hardness of the film is improved without curling while maintaining transparency, heat sealability, impact strength and tensile elastic modulus.
　以下、本発明に係る多層フィルムについて詳細に説明する。 Hereinafter, the multilayer film according to the present invention will be described in detail.
　本発明に係る多層フィルムは、
　環状オレフィン系樹脂（ａ１）０．１～１０重量％と、下記条件（i）および（ii）を満たすエチレン系樹脂（ｂ１）９０～９９．９重量％とを含有する樹脂組成物（ただし、成分（ａ１）と成分（ｂ１）の合計を１００重量％とする。）からなる層（Ｉ）と、
　環状オレフィン系樹脂（ａ２）１０～７０重量％と、下記条件（i）および（ii）を満たすエチレン系樹脂（ｂ２）３０～９０重量％とを含有する樹脂組成物（ただし、成分（ａ２）と成分（ｂ２）の合計を１００重量％とする。）からなる層（ＩＩ）と、
　エチレン系樹脂（ｂ３）を含有する層（III）と
を含むことを特徴とする。
（i）密度が８８０～９７０ｋｇ／ｍ3である。
（ii）１９０℃、２．１６ｋｇ荷重におけるメルトマスフローレイト（ＭＦＲ）が、０．１～５０ｇ／１０分である。 The multilayer film according to the present invention is
Resin composition containing cyclic olefin-based resin (a1) 0.1 to 10% by weight and ethylene-based resin (b1) 90 to 99.9% by weight satisfying the following conditions (i) and (ii) (however, A layer (I) comprising a total of 100% by weight of component (a1) and component (b1);
A resin composition containing 10 to 70% by weight of a cyclic olefin resin (a2) and 30 to 90% by weight of an ethylene resin (b2) satisfying the following conditions (i) and (ii) (provided that the component (a2) And the component (b2) is 100% by weight.)
And a layer (III) containing an ethylene-based resin (b3).
(I) The density is 880 to 970 kg / m 3 .
(Ii) Melt mass flow rate (MFR) at 190 ° C. and a load of 2.16 kg is 0.1 to 50 g / 10 min.
　また、本発明に係る多層フィルムは、前記層（Ｉ）と前記層（ＩＩ）の間、および、前記層（ＩＩ）と前記層（III）の間の少なくとも一方に、環状オレフィン系樹脂（ａ３）０～７０重量％と、前記条件（i）および（ii）を満たすエチレン系樹脂（ｂ４）３０～１００重量％とを含有する樹脂組成物（ただし、成分（ａ３）と成分（ｂ４）の合計を１００重量％とする。）からなる層（ＩＶ）をさらに含んでもよい。 In addition, the multilayer film according to the present invention comprises a cyclic olefin resin (a3) between at least one of the layer (I) and the layer (II) and between the layer (II) and the layer (III). ) A resin composition containing 0 to 70 wt% and an ethylene resin (b4) satisfying the above conditions (i) and (ii) (30 to 100 wt%) (provided that the components (a3) and (b4) It may further comprise a layer (IV) consisting of 100% by weight in total.
　［層（Ｉ）］
　本発明の多層フィルム中の層（Ｉ）は、環状オレフィン系樹脂（ａ１）０．１～１０重量％、好ましくは０．５～９重量％、より好ましくは０．８～８重量％と、前記条件（i）および（ii）を満たすエチレン系樹脂（ｂ１）９０～９９．９重量％、好ましくは９１～９９．５重量％、より好ましくは９２～９９．２重量％とを含有する樹脂組成物（ただし、成分（ａ１）と成分（ｂ１）の合計を１００重量％とする。以下「樹脂組成物（Ｉ）」ともいう。）からなる。 [Layer (I)]
The layer (I) in the multilayer film of the present invention has a cyclic olefin resin (a1) of 0.1 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 0.8 to 8% by weight, Resin containing 90 to 99.9 wt%, preferably 91 to 99.5 wt%, more preferably 92 to 99.2 wt% of ethylene-based resin (b1) satisfying the above conditions (i) and (ii) It consists of a composition (however, the total of component (a1) and component (b1) is 100% by weight. Hereinafter also referred to as “resin composition (I)”).
　前記層（Ｉ）は、本発明の多層フィルムの表層となる。このように、多層フィルムの表層に環状オレフィン系樹脂（ａ１）を前記範囲で含有させることにより、透明性、ヒートシール性、衝撃強度および引張弾性率を維持しつつ、カールを発生させずにフィルムの表面硬度を向上させることができる。 The layer (I) is a surface layer of the multilayer film of the present invention. Thus, by including the cyclic olefin-based resin (a1) in the above-mentioned range in the surface layer of the multilayer film, the film can be produced without curling while maintaining transparency, heat sealability, impact strength and tensile elastic modulus. The surface hardness of can be improved.
　＜環状オレフィン系樹脂（ａ１）＞
　前記層（Ｉ）に用いられる環状オレフィン系樹脂（ａ１）としては、例えば、ノルボルネン系重合体、ビニル脂環式炭化水素重合体、環状共役ジエン重合体等が挙げられる。これらの中でも、ノルボルネン系重合体が好ましい。また、ノルボルネン系重合体としては、ノルボルネン系単量体の開環重合体（以下「ＣＯＰ」ともいう。）、ノルボルネン系単量体とエチレン等のα－オレフィンを共重合したノルボルネン系共重合体（以下「ＣＯＣ」ともいう。）等が挙げられる。また、ＣＯＰ及びＣＯＣの水素添加物も用いることができる。本発明では、ポリエチレンに対する分散性の理由により、環状オレフィン系樹脂（ａ１）はＣＯＣであることが好ましい。 <Cyclic olefin resin (a1)>
Examples of the cyclic olefin resin (a1) used for the layer (I) include a norbornene polymer, a vinyl alicyclic hydrocarbon polymer, a cyclic conjugated diene polymer, and the like. Among these, norbornene-based polymers are preferable. The norbornene polymer includes a ring-opening polymer of a norbornene monomer (hereinafter also referred to as “COP”), and a norbornene copolymer obtained by copolymerizing a norbornene monomer and an α-olefin such as ethylene. (Hereinafter also referred to as “COC”). COP and COC hydrogenated products can also be used. In the present invention, the cyclic olefin-based resin (a1) is preferably COC for reasons of dispersibility with respect to polyethylene.
　ＣＯＣとしては、例えば、エチレンと、下記一般式（１）で表わされる環状オレフィンとの共重合体が挙げられる。 Examples of COC include a copolymer of ethylene and a cyclic olefin represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000001
 　式（１）中、ｎは０または正の整数であり、Ｒ1～Ｒ12は、それぞれ独立に、水素原子、ハロゲン原子または炭化水素基である。前記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子またはヨウ素原子が挙げられる。
Figure JPOXMLDOC01-appb-C000001
 In the formula (1), n is 0 or a positive integer, and R 1 to R 12 are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.
  前記炭化水素基としては、炭素原子数１～２０のアルキル基、炭素原子数３～１５のシクロアルキル基および芳香族炭化水素基が挙げられる。前記アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基およびオクタデシル基が挙げられ、前記シクロアルキル基としては、例えば、シクロヘキシル基が挙げられ、前記芳香族炭化水素基としては、例えば、フェニル基およびナフチル基などが挙げられる。これらの炭化水素基は、ハロゲン原子で置換されていてもよい。 Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. These hydrocarbon groups may be substituted with a halogen atom.
　また、Ｒ9とＲ10、Ｒ11とＲ12とが一体化して２価の炭化水素基を形成してもよく、Ｒ9またはＲ10とＲ11またはＲ12とが互いに環を形成してもよい。前記２価の炭化水素基としては、例えば、エチリデン基、プロピリデン基、イソプロピリデン基等のアルキリデン基などが挙げられる。Ｒ9またはＲ10とＲ11またはＲ12とから形成される環は単環でも縮合多環であってもよく、架橋を有する多環であってもよく、不飽和結合を有する環であってもよく、またこれらの環の組み合わせからなる環であってもよい。 R 9 and R 10 , R 11 and R 12 may be integrated to form a divalent hydrocarbon group, and R 9 or R 10 and R 11 or R 12 may form a ring with each other. Also good. Examples of the divalent hydrocarbon group include alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group. The ring formed from R 9 or R 10 and R 11 or R 12 may be monocyclic or condensed polycyclic, may be a polycyclic ring having a bridge, and is a ring having an unsaturated bond. It may also be a ring composed of a combination of these rings.
　前記式（１）で表される環状オレフィンは、シクロペンタジエン類と、相応するオレフィン類または環状オレフィン類とをディールス・アルダー反応によって縮合させることにより、容易に製造することができる。 The cyclic olefin represented by the above formula (1) can be easily produced by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by Diels-Alder reaction.
　前記式（１）で表される環状オレフィンの具体例としては、ビシクロ［２．２．１］ヘプト－２－エン、６－メチルビシクロ［２．２．１］ヘプト－２－エン、５，６－ジメチルビシクロ［２．２．１］ヘプト－２－エン、１－メチルビシクロ［２．２．１］ヘプト－２－エン、６－エチルビシクロ［２．２．１］ヘプト－２－エン、６―ブチルビシクロ［２．２．１］ヘプト－２－エン、６－イソブチルビシクロ［２．２．１］ヘプト－２－エン、７―メチルビシクロ［２．２．１］ヘプト－２－エン、テトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－メチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－エチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－プロピルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８―ヘキシルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－ステアリルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８，９－ジメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－メチル－９－エチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－クロロテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－プロモテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－フルオロテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８，９－ジクロロテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－シクロヘキシルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－イソブチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－ブチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－エチリデンテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－エチリデン－９－メチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－エチリデン－９－エチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－エチリデン－９－イソプロピルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－エチリデン－９－ブチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－ｎ－プロピリデンテトラシクリ［４．４．０．１2,5．１7,10］－３－ドデセン、８－ｎ－プロピリデン－９－メチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－ｎ－プロピリデン－９－エチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－ｎ－プロピリデン－９－イソプロピルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－ｎ－プロピリデン－９－ブチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－イソプロピリデンテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－イソプロピリデン－９－メチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－イソプロピリデン－９－エチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－イソプロピリデン－９－イソプロピルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、８－イソプロピデン－９－ブチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、５，１０－ジメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、２，１０－ジメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、１１，１２－ジメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、２，７，９－トリメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、９－エチル－２，７－ジメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、９－イソブチル－２，７－ジメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、９，１１，１２－トリメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、９－エチル－１１，１２－ジメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、９－イソブチル－１１，１２－ジメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、５，８，９，１０－テトラメチルテトラシクロ［４．４．０．１2,5．１7,10］－３－ドデセン、ヘキサシクロ［６．６．１．１3,6．１10,13．０2,7．０9,14］－４－ペプタデセン、１２－メチルヘキサシクロ［６．６．１．１3,6．１10,13．０2,7．０9,14］－４－ヘプタデセン、１２－エチルヘキサシクロ［６．６．１．１3,6．１10,13．０2,7．０9,14］－４－ヘプタデセン、１２－イソブチルヘキサシクロ［６．６．１．１3,6．１10,13．０2,7．０9,14］－４－ヘプタデセン、１，６，１０－トリメチル－１２－イソブチルヘキサシクロ［６．６．１．１3,6．１10,13．０2,7．０9,14］－４－ヘプタデセン、オクタシクロ［８．８．０．１2,9．１4,7．１11,18．１13,16．０3,8．０12,17］－５－ドコセン、１５－メチルオクタシクロ［８．８．０．１2,9．１4,7．１11,18．１13,16．０3,8．０12,17］－５－ドコセン、１５－エチルオクタシクロ［８．８．０．１2,9．１4,7．１11,18．１13,16．０3,8．０12,17］－５－ドコセン、ペンタシクロ［６．６．１．１3,6．０2,7．０9,14］－４－ヘキサデセン、１，３－ジメチルペンタシクロ［６．６．１．１3,6．０2,7．０9,14］－４－ヘキサデセン、１，６－ジメチルペンタシクロ［６．６．１．１3,6．０2,7．０9,14］－４－ヘキサデセン、１５，１６－ジメチルペンタシクロ［６．６．１．１3,6．０2,7．０9,14］－４－ヘキサデセン、ペンタシクロ［６．５．１．１3,6．０2,7．０9,13］－４－ペンタデセン、１，３－ジメチルペンタシクロ［６．５．１．１3,6．０2,7．０9,13］－４－ペンタデセン、１，６－ジメチルペンタシクロ［６．５．１．１3,6．０2,7．０9,13］－４－ペンタデセン、１４，１５－ジメチルペンタシクロ［６．５．１．１3,6．０2,7．０9,13］－４－ペンタデセン、ペンタシクロ［８．７．０．１2,9．１4,7．１11,17．０3,8．０12,16］－５－エイコセン、ヘプタシクロ［８．８．０．１2,9．１4,7．１11,18．０3,8．０12,17］－５－ヘンエイコセン、トリシクロ［４．３．０．１2,5］－３，７－デカジエン、トリシクロ［４．３．０．１2,5］－３－デセン、２－メチルトリシクロ［４．３．０．１2,5］－３－デセン、５－メチルトリシクロ［４．３．０．１2,5］－３－デセン、トリシクロ［４．４．０．１2,5］－３－ウンデセン、１０－メチルトリシクロ［４．４．０．１2,5］－３－ウンデセン、テトラシクロ［６．５．１2,5．０1,6．０8,13］－３，８，１０，１２－トリデカテトラエン、テトラシクロ［６．６．１2,5．０1,6．０8,13］－３，８，１０，１２－テトラデカテトラエン、ペンタシクロ［６．５．１．１3,6．０2,7．０9,13］－４，１０－ペンタデカジエン、ペンタシクロ［４．７．０．１2,5．０8,13．１9,12］－３－ペンタデセン、メチル置換ペンタシクロ［４．７．０．１2,5．０8,13．１9,12］－３－ペンタデセン、ヘプタシクロ［７．８．０．１3,6．０2,7．１10,17．０11,16．１12,15］－４－エイコセン、ジメチル置換ヘプタシクロ［７．８．０．１3,6．０2,7．１10,17．０11,16．１12,15］－４－エイコセン、ノナシクロ［９．１０．１．１4,7．０3,8．０2,10．０12,21．１13,20．０14,19．１15,18］－５－ペンタコセン、トリメチル置換ノナシクロ［９．１．１．１4,7．０3,8．０2,10．０12,21．１13,20．０14,19．１15,18］－５－ペンタコセンなどが挙げられる。 Specific examples of the cyclic olefin represented by the formula (1) include bicyclo [2.2.1] hept-2-ene, 6-methylbicyclo [2.2.1] hept-2-ene, 5, 6-dimethylbicyclo [2.2.1] hept-2-ene, 1-methylbicyclo [2.2.1] hept-2-ene, 6-ethylbicyclo [2.2.1] hept-2-ene 6-butylbicyclo [2.2.1] hept-2-ene, 6-isobutylbicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] hept-2-ene Ene, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-propyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-hexyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-stearyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8,9-dimethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-methyl-9-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-chlorotetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-promotetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-fluorotetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8,9-dichlorotetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-cyclohexyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-isobutyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-butyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-ethylidenetetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-ethylidene-9-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-ethylidene-9-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-ethylidene-9-isopropyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-ethylidene-9-butyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-n-propylidenetetracyclyl [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-n-propylidene-9-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-n-propylidene-9-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-n-propylidene-9-isopropyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-n-propylidene-9-butyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-isopropylidenetetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-isopropylidene-9-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-isopropylidene-9-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-isopropylidene-9-isopropyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 8-isopropylidene-9-butyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 5,10-dimethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 2,10-dimethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 11,12-dimethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 2,7,9-trimethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 9-ethyl-2,7-dimethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 9-isobutyl-2,7-dimethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 9,11,12-trimethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 9-ethyl-11,12-dimethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 9-isobutyl-11,12-dimethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, 5,8,9,10-tetramethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene, hexacyclo [6.6.1.1 3,6 . 1 10,13 . 0 2,7 . 0 9,14] -4 Peputadesen, 12-methyl hexa cyclo [6.6.1.1 3, 6. 1 10,13 . 0 2,7 . 0 9,14] -4-heptadecene, 12-ethylhexanoate cyclo [6.6.1.1 3, 6. 1 10,13 . 0 2,7 . 0 9,14] -4-heptadecene, 12-isobutyl hexamethylene cyclo [6.6.1.1 3, 6. 1 10,13 . 0 2,7 . 0 9,14] -4-heptadecene, 1,6,10- trimethyl-12-isobutyl hexamethylene cyclo [6.6.1.1 3, 6. 1 10,13 . 0 2,7 . 0 9,14] -4-heptadecene, octacyclo [8.8.0.1 2,9. 1 4,7 . 1 11,18 . 1 13,16 . 0 3,8 . 0 12,17 ] -5-docosene, 15-methyloctacyclo [8.8.0.1 2,9 . 1 4,7 . 1 11,18 . 1 13,16 . 0 3,8 . 0 12,17 ] -5-docosene, 15-ethyloctacyclo [8.8.0.1 2,9 . 1 4,7 . 1 11,18 . 1 13,16 . 0 3,8 . 0 12,17 ] -5-docosene, pentacyclo [6.6.1.1 3,6 . 0 2,7 . 0 9,14 ] -4-hexadecene, 1,3-dimethylpentacyclo [6.6.1.1 3,6 . 0 2,7 . 0 9,14 ] -4-hexadecene, 1,6-dimethylpentacyclo [6.6.1.1 3,6 . 0 2,7 . 0 9,14 ] -4-hexadecene, 15,16-dimethylpentacyclo [6.6.1.1 3,6 . 0 2,7 . 0 9,14 ] -4-hexadecene, pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ] -4-pentadecene, 1,3-dimethylpentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ] -4-pentadecene, 1,6-dimethylpentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ] -4-pentadecene, 14,15-dimethylpentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13] -4-pentadecene, pentacyclo [8.7.0.1 2,9. 1 4,7 . 1 11,17 . 0 3,8 . 0 12,16 ] -5-eicosene, heptacyclo [8.8.0.1 2,9 . 1 4,7 . 1 11,18 . 0 3,8 . 0 12,17 ] -5- heneicosene , tricyclo [4.3.0.1 2,5 ] -3,7-decadiene, tricyclo [4.3.0.1 2,5 ] -3-decene, 2- Methyltricyclo [4.3.0.1 2,5 ] -3-decene, 5-methyltricyclo [4.3.0.1 2,5 ] -3-decene, tricyclo [4.4.0. 1 2,5] -3-undecene, 10-methyltricyclo [4.4.0.1 2,5] -3-undecene, tetracyclo [6.5.1 2,5. 0 1,6 . 0 8,13] -3,8,10,12- tridecafluoro tetra-ene, tetracyclo [6.6.1 2,5. 0 1,6 . 0 8,13] -3,8,10,12- tetradecanol tetra-ene, pentacyclo [6.5.1.1 3,6. 0 2,7 . 0 9,13] 4,10 penta octadecadienoic, pentacyclo [4.7.0.1 2,5. 0 8,13 . 1 9,12] -3-pentadecene, methyl-substituted pentacyclo [4.7.0.1 2,5. 0 8,13 . 1 9,12 ] -3-pentadecene, heptacyclo [7.8.0.1 3,6 . 0 2,7 . 1 10,17 . 0 11,16 . 1 12,15] -4-eicosene, dimethyl-substituted heptacyclo [7.8.0.1 3,6. 0 2,7 . 1 10,17 . 0 11,16 . 1 12, 15] -4-eicosene, Nonashikuro [9.10.1.1 4,7. 0 3,8 . 0 2,10 . 0 12,21 . 1 13,20 . 0 14,19 . 1 15,18] -5-pentacosene, trimethyl-substituted Nonashikuro [9.1.1.1 4, 7. 0 3,8 . 0 2,10 . 0 12,21 . 1 13,20 . 0 14,19 . 1 15,18] -5-pentacosene and the like.
　前記ＣＯＣは、エチレン成分および上記式（１）で表わされる環状オレフィン成分の他に、本発明の目的に損なわない範囲内で、他の共重合可能な不飽和単量体成分、例えば、プロピレン、１－ブテン、４－メチル－１－ペンテン、１－ヘキセン、１－オクテン、１－デセン、１－ドデセン、１－テトラデセン、１－ヘキサデセン、１－オクタデセン、１－エイコセンなどの炭素数３～２０のα－オレフィン、ノルボルネン、エチリデンノルボルネン、ジシクロペンタジエン等の環状オレフィン、環状ジエンなどを含有してもよい。 The COC is, in addition to the ethylene component and the cyclic olefin component represented by the above formula (1), other copolymerizable unsaturated monomer components such as propylene, within a range not impairing the object of the present invention. 3 to 20 carbon atoms such as 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene A cyclic olefin such as α-olefin, norbornene, ethylidene norbornene, and dicyclopentadiene, and cyclic diene.
　前記ＣＯＣにおいて、エチレンに由来する構造単位は、好ましくは４０～８５モル％、より好ましくは５０～７５モル％の範囲であり、環状オレフィンに由来する構造単位は、好ましくは１５～６０モル％、より好ましくは２５～５０モル％の範囲である。エチレン由来の構造単位が前記範囲内で含有されていることにより、フィルムの剛性、引き裂き性、加工安定性、衝撃強度に優れる。 In the COC, the structural unit derived from ethylene is preferably in the range of 40 to 85 mol%, more preferably 50 to 75 mol%, and the structural unit derived from the cyclic olefin is preferably 15 to 60 mol%, More preferably, it is in the range of 25-50 mol%. When the structural unit derived from ethylene is contained within the above range, the film has excellent rigidity, tearability, processing stability, and impact strength.
　環状オレフィン系樹脂（ａ１）として用いることができる市販品として、ノルボルネン系モノマーの開環重合体（ＣＯＰ）としては、例えば、日本ゼオン株式会社製「ゼオノア（ＺＥＯＮＯＲ）」等が挙げられ、ノルボルネン系共重合体（ＣＯＣ）としては、例えば、三井化学株式会社製「アペル」、ポリプラスチックス社製「トパス（ＴＯＰＡＳ）」等が挙げられる。 As a commercial product that can be used as the cyclic olefin resin (a1), examples of the ring-opening polymer (COP) of the norbornene monomer include “ZEONOR” manufactured by Nippon Zeon Co., Ltd. Examples of the copolymer (COC) include “Appel” manufactured by Mitsui Chemicals, Inc. and “TOPAS” manufactured by Polyplastics.
　＜エチレン系樹脂（ｂ１）＞
　前記層（Ｉ）に用いられるエチレン系樹脂（ｂ１）は、上記条件（i）および（ii）を満たすエチレン系樹脂である。 <Ethylene resin (b1)>
The ethylene resin (b1) used for the layer (I) is an ethylene resin that satisfies the above conditions (i) and (ii).
　≪条件（i）≫
　エチレン系樹脂（ｂ１）の密度は、フィルム剛性、ヒートシール性の観点から、８８０～９７０ｋｇ／ｍ3、好ましくは８８５～９５０ｋｇ／ｍ3、より好ましくは９００～９３０ｋｇ／ｍ3の範囲である。前記密度は、ＪＩＳ　Ｋ７１１２（密度勾配管法）に準拠して測定される値である。 ≪Condition (i) ≫
The density of the ethylene-based resin (b1), the film rigidity, in view of heat sealability, 880 ~ 970kg / m 3, preferably of 885 ~ 950kg / m 3, more preferably 900 ~ 930kg / m 3 range. The density is a value measured according to JIS K7112 (density gradient tube method).
　≪条件（ii）≫
　エチレン系樹脂（ｂ１）のＭＦＲ（１９０℃、２．１６ｋｇ荷重、ＪＩＳ　Ｋ７２１０準拠）は、バブル安定性、フィルム強度、成形加工性（流動性）などの観点から、０．１～５０ｇ／１０分、好ましくは０．５～３０ｇ／１０分、より好ましくは０．７～１５ｇ／１０分の範囲である。 ≪Condition (ii) ≫
The MFR (190 ° C., 2.16 kg load, JIS K7210 compliant) of the ethylene-based resin (b1) is 0.1 to 50 g / 10 min from the viewpoint of bubble stability, film strength, moldability (fluidity), etc. The range is preferably 0.5 to 30 g / 10 min, more preferably 0.7 to 15 g / 10 min.
　エチレン系樹脂（ｂ１）としては、例えば、直鎖状低密度ポリエチレンなどが挙げられる。直鎖状低密度ポリエチレンは、エチレンとα－オレフィンの共重合体を含み、このような共重合体は、チーグラーナッタ触媒やメタロセン触媒といった公知の触媒を用いて得ることができる。また、他の低密度ポリエチレンを添加することも可能である。本発明では、市販のポリエチレン系樹脂から、上記各特性を満足するポリエチレン系樹脂を選択して使用することができる。また、エチレン系樹脂（ｂ１）は、１種のみでもよく、２種以上を組み合わせて用いてもよい。 Examples of the ethylene resin (b1) include linear low density polyethylene. The linear low-density polyethylene contains a copolymer of ethylene and α-olefin, and such a copolymer can be obtained using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. It is also possible to add other low density polyethylene. In the present invention, a polyethylene resin satisfying each of the above properties can be selected and used from commercially available polyethylene resins. Further, the ethylene resin (b1) may be used alone or in combination of two or more.
　＜他の成分＞
　前記樹脂組成物（Ｉ）は、本発明の目的を損なわない範囲であれば、必要に応じて耐候安定剤、耐熱安定剤、帯電防止剤、防曇剤、アンチブロッキング剤、スリップ剤、滑剤、顔料、流滴剤などの通常ポリオレフィンに添加される各種添加剤を含有してもよい。 <Other ingredients>
If the resin composition (I) is within a range that does not impair the object of the present invention, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a slip agent, a lubricant, Various additives that are usually added to polyolefins, such as pigments and droplets, may be contained.
　［層（ＩＩ）］
　本発明の多層フィルム中の層（ＩＩ）は、環状オレフィン系樹脂（ａ２）１０～７０重量％、好ましくは２０～６５重量％、より好ましくは３０～６０重量％と、前記条件（i）および（ii）を満たすエチレン系樹脂（ｂ２）３０～９０重量％、好ましくは３５～８０重量％、より好ましくは４０～７０重量％とを含有する樹脂組成物（ただし、成分（ａ２）と成分（ｂ２）の合計を１００重量％とする。以下「樹脂組成物（ＩＩ）」ともいう。）からなる。 [Layer (II)]
The layer (II) in the multilayer film of the present invention comprises 10 to 70% by weight, preferably 20 to 65% by weight, more preferably 30 to 60% by weight of the cyclic olefin resin (a2), and the conditions (i) and A resin composition containing 30 to 90% by weight, preferably 35 to 80% by weight, more preferably 40 to 70% by weight of the ethylene-based resin (b2) satisfying (ii) (provided that the component (a2) and the component ( The total of b2) is 100% by weight and is hereinafter also referred to as “resin composition (II)”.
　前記層（ＩＩ）は、本発明の多層フィルムの中間層となる。このように、多層フィルムの中間層に環状オレフィン系樹脂（ａ２）を前記範囲で含有させることにより、易カット性に優れた多層フィルムを得ることができる。 The layer (II) is an intermediate layer of the multilayer film of the present invention. Thus, the multilayer film excellent in easy-cut property can be obtained by making the intermediate | middle layer of a multilayer film contain cyclic olefin resin (a2) in the said range.
　前記層（ＩＩ）に用いられる環状オレフィン系樹脂（ａ２）の例としては、前記環状オレフィン系樹脂（ａ１）で例示したものと同様のものが挙げられる。前記層（ＩＩ）に用いられる環状オレフィン系樹脂（ａ２）は、前記環状オレフィン系樹脂（ａ１）と同じ種類のものを用いてもよく、異なる種類のものを用いてもよい。 Examples of the cyclic olefin resin (a2) used for the layer (II) include the same as those exemplified for the cyclic olefin resin (a1). As the cyclic olefin resin (a2) used in the layer (II), the same type as the cyclic olefin resin (a1) may be used, or a different type may be used.
　また、前記層（ＩＩ）に用いられるエチレン系樹脂（ｂ２）の例としては、前記エチレン系樹脂（ｂ１）で例示したものと同様のものが挙げられる。前記層（ＩＩ）に用いられるエチレン系樹脂（ｂ２）は、前記エチレン系樹脂（ｂ１）と同じ種類のものを用いてもよく、異なる種類のものを用いてもよい。なお、エチレン系樹脂（ｂ２）は、１種のみでもよく、２種以上を組み合わせて用いてもよい。 Further, examples of the ethylene resin (b2) used for the layer (II) include the same ones as exemplified for the ethylene resin (b1). As the ethylene resin (b2) used for the layer (II), the same type as the ethylene resin (b1) may be used, or a different type may be used. In addition, ethylene-type resin (b2) may be only 1 type, and may be used in combination of 2 or more type.
　また、前記樹脂組成物（ＩＩ）は、前記樹脂組成物（Ｉ）と同様に、前記他の成分を含有してもよい。 In addition, the resin composition (II) may contain the other components in the same manner as the resin composition (I).
　［層（III）］
　本発明の多層フィルム中の層（III）は、エチレン系樹脂（ｂ３）を主成分として含有する。前記エチレン系樹脂（ｂ３）としては、シーラントに用いられるエチレン系樹脂であれば特に限定されず、例えば、前記エチレン系樹脂（ｂ１）で例示したものと同様のものが挙げられる。前記層（III）に用いられるエチレン系樹脂（ｂ３）は、前記エチレン系樹脂（ｂ１）または（ｂ２）と同じ種類のものを用いてもよく、異なる種類のものを用いてもよい。 [Layer (III)]
The layer (III) in the multilayer film of the present invention contains the ethylene resin (b3) as a main component. The ethylene resin (b3) is not particularly limited as long as it is an ethylene resin used for a sealant, and examples thereof include those similar to those exemplified for the ethylene resin (b1). As the ethylene resin (b3) used in the layer (III), the same type as the ethylene resin (b1) or (b2) may be used, or a different type may be used.
　前記層（III）は、本発明の多層フィルムの内層（シール層）となる。このように、多層フィルムの内層がエチレン系樹脂（ｂ３）からなることにより、ヒートシール性に優れた多層フィルムを得ることができる。前記層（III）は、単層でもよく、２以上の層を含む多層であってもよい。また、エチレン系樹脂（ｂ３）は、１種のみでもよく、２種以上を組み合わせて用いてもよい。 The layer (III) is an inner layer (seal layer) of the multilayer film of the present invention. Thus, when the inner layer of a multilayer film consists of ethylene-type resin (b3), the multilayer film excellent in heat-sealability can be obtained. The layer (III) may be a single layer or a multilayer including two or more layers. Moreover, only 1 type may be used for ethylene-type resin (b3), and it may use it in combination of 2 or more type.
　前記層（III）は、本発明の目的を損なわない範囲であれば、必要に応じて、前記樹脂組成物（Ｉ）で例示した他の成分を含有してもよい。 The layer (III) may contain other components exemplified in the resin composition (I) as necessary as long as the object of the present invention is not impaired.
　［層（ＩＶ）］
　本発明の多層フィルム中に任意に設けられる層（ＩＶ）は、環状オレフィン系樹脂（ａ３）０～７０重量％、好ましくは０～６０重量％、より好ましくは１～５５重量％と、前記条件（i）および（ii）を満たすエチレン系樹脂（ｂ４）３０～１００重量％、好ましくは４０～１００重量％、より好ましくは４５～９９重量％とを含有する樹脂組成物（ただし、成分（ａ３）と成分（ｂ４）の合計を１００重量％とする。以下「樹脂組成物（ＩＶ）」ともいう。）からなる。 [Layer (IV)]
The layer (IV) optionally provided in the multilayer film of the present invention comprises 0 to 70% by weight, preferably 0 to 60% by weight, more preferably 1 to 55% by weight of the cyclic olefin resin (a3), A resin composition containing 30 to 100% by weight, preferably 40 to 100% by weight, more preferably 45 to 99% by weight of an ethylene-based resin (b4) satisfying (i) and (ii) (provided that component (a3 ) And component (b4) is 100% by weight, hereinafter also referred to as “resin composition (IV)”.
　前記層（Ｉ）と前記層（ＩＩ）の間、および、前記層（ＩＩ）と前記層（III）の間の少なくとも一方に、前記層（ＩＶ）を設けることにより、引裂強度、衝撃強度、剛性などの物性を制御できるようになる。 By providing the layer (IV) between the layer (I) and the layer (II) and at least one of the layer (II) and the layer (III), tear strength, impact strength, It becomes possible to control physical properties such as rigidity.
　前記層（ＩＶ）に用いられる環状オレフィン系樹脂（ａ３）の例としては、前記環状オレフィン系樹脂（ａ１）で例示したものと同様のものが挙げられる。前記層（ＩＶ）に用いられる環状オレフィン系樹脂（ａ３）は、前記環状オレフィン系樹脂（ａ１）または（ａ２）と同じ種類のものを用いてもよく、異なる種類のものを用いてもよい。 Examples of the cyclic olefin resin (a3) used for the layer (IV) include the same as those exemplified for the cyclic olefin resin (a1). As the cyclic olefin resin (a3) used for the layer (IV), the same type as the cyclic olefin resin (a1) or (a2) may be used, or a different type may be used.
　また、前記層（ＩＶ）に用いられるエチレン系樹脂（ｂ４）の例としては、前記エチレン系樹脂（ｂ１）で例示したものと同様のものが挙げられる。前記層（ＩＶ）に用いられるエチレン系樹脂（ｂ４）は、前記エチレン系樹脂（ｂ１）、（ｂ２）または（ｂ３）と同じ種類のものを用いてもよく、異なる種類のものを用いてもよい。また、エチレン系樹脂（ｂ４）は、１種のみでもよく、２種以上を組み合わせて用いてもよい。 Moreover, examples of the ethylene resin (b4) used for the layer (IV) include the same ones as exemplified for the ethylene resin (b1). The ethylene resin (b4) used for the layer (IV) may be the same type as the ethylene resin (b1), (b2) or (b3), or may be a different type. Good. Moreover, only 1 type may be used for ethylene-type resin (b4), and it may use it in combination of 2 or more type.
　また、前記樹脂組成物（ＩＩ）は、前記樹脂組成物（Ｉ）と同様に、前記他の成分を含有してもよい。 In addition, the resin composition (II) may contain the other components in the same manner as the resin composition (I).
　［多層フィルム］
　本発明の多層フィルムは、上述した層（Ｉ）、層（ＩＩ）および層（III）を含み、必要に応じて上述した層（ＩＶ）を含む。 [Multilayer film]
The multilayer film of the present invention includes the above-described layer (I), layer (II), and layer (III), and includes the above-described layer (IV) as necessary.
　本発明の多層フィルムにおいて、前記環状オレフィン系樹脂（ａ１）、（ａ２）および（ａ３）のフィルム全体に対する使用割合の合計は、好ましくは０．１～６０重量％、より好ましくは１～５５重量％、さらに好ましくは５～５０重量％である。本発明の多層フィルム全体における前記環状オレフィン系樹脂（ａ１）、（ａ２）および（ａ３）の合計の使用割合が前記範囲内であることにより、安定的に製膜が可能であり、易カット性を付与することができる。 In the multilayer film of the present invention, the total use ratio of the cyclic olefin resins (a1), (a2) and (a3) to the whole film is preferably 0.1 to 60% by weight, more preferably 1 to 55% by weight. %, More preferably 5 to 50% by weight. When the total use ratio of the cyclic olefin-based resins (a1), (a2) and (a3) in the entire multilayer film of the present invention is within the above range, the film can be stably formed and easily cut. Can be granted.
　本発明の多層フィルムの厚みは、種々用途に応じて適宜設定すればよいが、前記層（Ｉ）の厚みとしては、通常、２～１００μｍ、好ましくは４～８０μｍの範囲であり、前記層（ＩＩ）の厚みとしては、通常、２～１００μｍ、好ましくは４～８０μｍの範囲であり、前記層（III）の厚みとしては、通常、４～１５０μｍ、好ましくは８～１２０μｍの範囲であり、前記層（ＩＶ）の厚みとしては、通常、２～１００μｍ、好ましくは４～８０μｍの範囲である。 The thickness of the multilayer film of the present invention may be appropriately set according to various uses, but the thickness of the layer (I) is usually in the range of 2 to 100 μm, preferably 4 to 80 μm. The thickness of II) is usually in the range of 2 to 100 μm, preferably 4 to 80 μm, and the thickness of the layer (III) is usually in the range of 4 to 150 μm, preferably 8 to 120 μm. The thickness of the layer (IV) is usually in the range of 2 to 100 μm, preferably 4 to 80 μm.
　本発明の多層フィルムは、９０μｍ厚の多層フィルムとしてヘイズが５０％以下であることが好ましく、３０％以下であることがより好ましく、２０％以下であることがさらに好ましい。ヘイズが５０％以下であることによりフィルムの透明性が優れる。 The multilayer film of the present invention has a haze of preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less as a 90 μm thick multilayer film. When the haze is 50% or less, the transparency of the film is excellent.
　本発明の多層フィルムは、９０μｍ厚の多層フィルムとしてダート衝撃強度が６００ｇ以上であることが好ましく、７００ｇ以上であることがより好ましい。ダート衝撃強度が６００ｇ以上であることで、十分な強度を有し、食品包装袋として適用した際、輸送時や落下時に袋が破れることを防止することができる。一方、上限については特に制限されない。 The multilayer film of the present invention has a dart impact strength of preferably 600 g or more, more preferably 700 g or more as a 90 μm thick multilayer film. When the dart impact strength is 600 g or more, the bag has sufficient strength, and when applied as a food packaging bag, the bag can be prevented from being torn during transportation or dropping. On the other hand, the upper limit is not particularly limited.
　本発明の多層フィルムは、９０μｍ厚の多層フィルムとしてＴＤ方向のエルメンドルフ引裂き強度が０．１～６Ｎであることが好ましく、０．１～４Ｎであることがより好ましく、０．１～３Ｎあることがさらに好ましい。 The multilayer film of the present invention is an Elmendorf tear strength in the TD direction as a multilayer film having a thickness of 90 μm, preferably 0.1 to 6N, more preferably 0.1 to 4N, and more preferably 0.1 to 3N. Is more preferable.
　なお、本明細書において、「ＴＤ方向」（Transverse Direction）とは、ＭＤ方向と直交し、フィルムの主面と平行な方向を指し、「ＭＤ方向」（Machine Direction）とは、フィルムの流れ方向を指す。 In this specification, “TD direction” (Transverse Direction) means a direction perpendicular to the MD direction and parallel to the main surface of the film, and “MD direction” (Machine Direction) means the flow direction of the film. Point to.
　本発明の多層フィルムは、９０μｍ厚の多層フィルムとしてＭＤ方向の引張弾性率が１０～２５００ＭＰａであることが好ましく、５０～２０００ＭＰａであることがより好ましく、１００～２０００ＭＰａであることがさらに好ましい。ＭＤ方向の引張弾性率が１０ＭＰａ以上であると、フィルムの強度がより向上する。また、ＭＤ方向の引張弾性率が２５００ＭＰａ以下であると、引張強度等、機械強度に優れたフィルムとなる。 The multilayer film of the present invention is a 90 μm-thick multilayer film, and preferably has a tensile modulus in the MD direction of 10 to 2500 MPa, more preferably 50 to 2000 MPa, and even more preferably 100 to 2000 MPa. When the tensile modulus in the MD direction is 10 MPa or more, the strength of the film is further improved. Moreover, when the tensile modulus in the MD direction is 2500 MPa or less, the film has excellent mechanical strength such as tensile strength.
　本発明の多層フィルムは、９０μｍ厚の多層フィルムとして微小硬度が２５０～１０００ＭＰａであることが好ましく、３００～９００ＭＰａであることがより好ましく、３５０～８００ＭＰａであることがさらに好ましい。微小硬度が前記範囲内であることにより、適度な剛性を有する多層フィルムとなる。また、本発明の多層フィルムの微小硬度は、層（Ｉ）に環状オレフィン系樹脂を配合しないこと以外は同様の条件で製造した多層フィルムの微小硬度と比較して、１０％以上向上することが好ましい。 The multilayer film of the present invention is a 90 μm thick multilayer film having a microhardness of preferably 250 to 1000 MPa, more preferably 300 to 900 MPa, and further preferably 350 to 800 MPa. When the microhardness is within the above range, a multilayer film having appropriate rigidity is obtained. Further, the microhardness of the multilayer film of the present invention can be improved by 10% or more compared to the microhardness of the multilayer film produced under the same conditions except that the layer (I) does not contain a cyclic olefin resin. preferable.
　＜多層フィルムの製造方法＞
　本発明の多層フィルムの製造方法としては、特に限定されないが、例えば、各層に用いる樹脂組成物を、多層ダイを用いて溶融状態で共押出し成形して積層した後、インフレーション法等によりフィルム化する共押出法が挙げられる。このようにして得られたフィルムは、そのまま無延伸フィルムとして、あるいは、さらに延伸して延伸フィルムとして、食品包装用袋などを製造するためのフィルムに加工することができる。その場合、溶融押出成形されたフィルム（延伸原反といい、厚さによってはシートと称される厚手の成形体を含む）の厚みは、成形法によって異なる。インフレーション成形で作成する場合の延伸原反は、５０μｍ～２０００μｍの厚みが好ましく、１００μｍ～１５００μｍがより好ましい。溶融樹脂の冷却方法は空冷、水冷のどちらであってもよい。 <Method for producing multilayer film>
The method for producing the multilayer film of the present invention is not particularly limited. For example, the resin composition used for each layer is laminated by coextrusion molding in a molten state using a multilayer die, and then formed into a film by an inflation method or the like. A coextrusion method may be mentioned. The film thus obtained can be processed into a film for producing a food packaging bag or the like as it is, as an unstretched film, or as a stretched film by further stretching. In that case, the thickness of the melt-extruded film (referred to as a stretched original fabric, including a thick molded body called a sheet depending on the thickness) varies depending on the molding method. In the case of forming by inflation molding, the stretched original fabric has a thickness of preferably 50 μm to 2000 μm, and more preferably 100 μm to 1500 μm. The method for cooling the molten resin may be either air cooling or water cooling.
　延伸原反を延伸する方法としては、テンター法により縦横に同時又は逐次２軸延伸する方法、チューブラー法により縦横方法に同時２軸延伸する方法、または２つ以上のロールの回転速度比の違いによりフィルムの流れ方向に１軸延伸する方法などを例示できる。 As a method of stretching the stretched raw fabric, a method of simultaneously or sequentially biaxially stretching longitudinally and laterally by a tenter method, a method of simultaneously biaxially stretching longitudinally and laterally by a tubular method, or a difference in rotational speed ratio of two or more rolls Examples of the method include uniaxial stretching in the film flow direction.
　＜多層フィルムの用途＞
　本発明の多層フィルムは、水物包装袋、液体スープ包袋、液体紙器、ラミ原反、特殊形状液体包装袋（スタンディングパウチなど）、規格袋、重袋、ラップフィルム、砂糖袋、油物包装袋、食品包装用などの各種包装用フィルム、プロテクトフィルム、輸液バック、農業用資材、バックインボックス、半導体材料、医薬品、食品などの包装に用いられるクリーンフィルムなどに好適である。 <Use of multilayer film>
The multilayer film of the present invention is a water packaging bag, liquid soup bag, liquid paper container, lami raw fabric, special shape liquid packaging bag (such as standing pouch), standard bag, heavy bag, wrap film, sugar bag, oil packaging Suitable for various packaging films such as bags and food packaging, protective films, infusion bags, agricultural materials, back-in boxes, semiconductor materials, pharmaceuticals, clean films used for packaging foods, and the like.
　以下、実施例に基づいて本発明をより具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
　以下の実施例において、各種物性の測定および評価は、下記のようにして行った。 In the following examples, various physical properties were measured and evaluated as follows.
　＜メルトマスフローレイト（ＭＦＲ：［ｇ／１０ｍｉｎ］）＞
　ＪＩＳ　Ｋ７２１０に準拠し、１９０℃、２．１６ｋｇ荷重（ｋｇｆ）の条件下で測定した。 <Melt Mass Flow Rate (MFR: [g / 10 min])>
Based on JIS K7210, the measurement was performed under the conditions of 190 ° C. and 2.16 kg load (kgf).
　＜密度［ｋｇ／ｍ3］＞
　ＪＩＳ　Ｋ７１１２に準拠し、ＭＦＲ測定時に得られるストランドを１００℃で１時間熱処理し、更に室温で１時間放置した後に密度勾配管法で測定した。 <Density [kg / m 3 ]>
Based on JIS K7112, the strand obtained at the time of MFR measurement was heat-treated at 100 ° C. for 1 hour, and further allowed to stand at room temperature for 1 hour, and then measured by a density gradient tube method.
　＜ヘイズ＞
　ＪＩＳ　Ｋ７１３６に準拠し、試験片（９０μｍ厚）を用いて、日本電色工業（株）製のデジタル濁度計「ＮＤＨ‐２０Ｄ」にて測定した。 <Haze>
Based on JIS K7136, it measured with the digital turbidity meter "NDH-20D" by Nippon Denshoku Industries Co., Ltd. using the test piece (90 micrometers thickness).
　＜エルメンドルフ引裂強度（ＴＤ方向）＞
　ＪＩＳ  Ｋ７１２８－２（１９９８）に準拠し、下記の条件で測定した。
測定装置：引裂き試験機（ＳＡ－ＷＰ、（株）東洋精機製作所製）
試験片サイズ：幅７５ｍｍ×長さ６３ｍｍ×厚み９０μｍ（短冊状）
測定温度：２３℃
　＜ダート衝撃強度［ｇ］＞
　ダート衝撃強度は、ＡＳＴＭ　Ｄ１７０９に従って、以下の条件および方法にて測定した。 <Elmendorf tear strength (TD direction)>
Based on JIS K7128-2 (1998), the measurement was performed under the following conditions.
Measuring device: Tear tester (SA-WP, manufactured by Toyo Seiki Seisakusho)
Test piece size: width 75 mm x length 63 mm x thickness 90 μm (strip shape)
Measurement temperature: 23 ° C
<Dirt impact strength [g]>
Dirt impact strength was measured according to ASTM D1709 under the following conditions and method.
　試験片（９０μｍ厚）をエアークランプ方式で締め付け、半球形のダートを一定の高さから落下させ、試験片が５０％破壊する荷重［ｇ］をグラフから読み取る。一水準の落下回数は１０回として、Ａ法を用いる。 Test piece (90 μm thickness) is clamped by air clamp method, hemispherical dart is dropped from a certain height, and the load [g] at which the test piece breaks 50% is read from the graph. The number of drops at one level is 10 times, and method A is used.
　＜引張弾性率（ＭＤ方向）＞
　ＪＩＳ  Ｋ６７８１に準拠して、引張切断荷重用の形状に切断したものを試験片（９０μｍ厚）として用いた。引張試験機（インストロン製「万能引張試験機３３８０」）を用いて、チャック間距離８０ｍｍ、引張速度５００ｍｍ／ｍｉｎ、及び温度２３℃の条件で、試験片の引張弾性率（ＭＤ方法）（単位：ＭＰａ）を測定した。 <Tensile modulus (MD direction)>
A specimen cut into a shape for a tensile cutting load according to JIS K6781 was used as a test piece (90 μm thickness). Using a tensile tester (Instron “Universal Tensile Tester 3380”), the tensile modulus of elasticity of the test piece (MD method) (unit: MD) under the conditions of a chuck distance of 80 mm, a tensile speed of 500 mm / min, and a temperature of 23 ° C. : MPa).
　＜微小硬度＞
　島津製作所製「ダイナミック超微小硬度計DUH-W201S」を用いて、温度２３℃および湿度５０％の条件で測定し、試験荷重を負荷したときの押し込み深さより求められる硬さで計算した。 <Micro hardness>
Using a “dynamic ultra-micro hardness tester DUH-W201S” manufactured by Shimadzu Corporation, measurement was performed under conditions of a temperature of 23 ° C. and a humidity of 50%, and the hardness was calculated from the indentation depth when a test load was applied.
　＜カール＞
　試験片として、縦３０ｍｍ、横２００ｍｍのサイズでフィルムを切り出した。切り出す方向は、ＭＤ方向に沿った形で２００ｍｍ切ったサンプルをＭＤサンプル、ＴＤ方向に沿った形をＴＤサンプルとした。カットしたフィルムサンプルの左端をテープで固定し、テーブルに密着するように右端を手で押さえ、手を離したときにテーブルに接触していない横方向の長さを測定した。ＭＤ方向とＴＤ方向それぞれのサンプルが３５ｍｍ未満であれば「合格」とし、どちらか一方でも３５ｍｍ以上となった場合は「不良」とした。 <Curl>
As a test piece, a film having a size of 30 mm in length and 200 mm in width was cut out. As the cutting direction, a sample cut 200 mm along the MD direction was an MD sample, and a shape along the TD direction was a TD sample. The left end of the cut film sample was fixed with tape, the right end was held by hand so that it was in close contact with the table, and the lateral length not touching the table when the hand was released was measured. If each sample in the MD direction and the TD direction was less than 35 mm, it was “pass”, and if either one was 35 mm or more, it was “bad”.
　［使用した材料］
  実施例および比較例で用いた各種原料は以下のとおりである。 [Materials used]
Various raw materials used in Examples and Comparative Examples are as follows.
　＜エチレン・α－オレフィン共重合体＞
ＬＬ１：（株）プライムポリマー製「エボリュー　ＳＰ２５１０」（密度：９２３ｋｇ／ｍ3、ＭＦＲ:１．４ｇ／１０分）
ＬＬ２：（株）プライムポリマー製「エボリュー　ＳＰ１０２２」（密度：９０８ｋｇ／ｍ3、ＭＦＲ:２．０ｇ／１０分）
ＬＬ３：（株）プライムポリマー製「エボリュー　ＳＰ２５２０」（密度：９２５ｋｇ／ｍ3、ＭＦＲ:１．９ｇ／１０分）
ＬＬ４：（株）プライムポリマー製「エボリュー　ＳＰ１５２０」（密度：９１３ｋｇ／ｍ3、ＭＦＲ:２．０ｇ／１０分）
　＜高密度ポリエチレン＞
ＨＤ：（株）プライムポリマー製「ハイゼックス　３６００Ｆ」（密度：９５８ｋｇ／ｍ3、ＭＦＲ:１．０ｇ／１０分）
　＜ポリプロピレン＞
ＰＰ：(株)プライムポリマー製「プライムポリプロ　Ｆ－３００ＳＰ」
　＜環状オレフィン系樹脂＞
ＣＯＣ１：ポリプラスチック社製「ＴＯＰＡＳ　８００７Ｆ－０４」
ＣＯＣ２：三井化学株式会社製「アペル　ＡＰＬ６５０９Ｔ」
　［実施例１～３および比較例１～５］
　表１に示す層構成を有するインフレーションフィルム（厚み９０μｍ、層比１：１：１）を、以下の条件で製造した。 <Ethylene / α-olefin copolymer>
LL1: “Evolue SP2510” manufactured by Prime Polymer Co., Ltd. (density: 923 kg / m 3 , MFR: 1.4 g / 10 min)
LL2: “Evolue SP1022” manufactured by Prime Polymer Co., Ltd. (density: 908 kg / m 3 , MFR: 2.0 g / 10 min)
LL3: “Evolue SP2520” manufactured by Prime Polymer Co., Ltd. (density: 925 kg / m 3 , MFR: 1.9 g / 10 min)
LL4: “Evolue SP1520” manufactured by Prime Polymer Co., Ltd. (density: 913 kg / m 3 , MFR: 2.0 g / 10 min)
<High density polyethylene>
HD: “Hi-Zex 3600F” manufactured by Prime Polymer Co., Ltd. (density: 958 kg / m 3 , MFR: 1.0 g / 10 min)
<Polypropylene>
PP: “Prime Polypro F-300SP” manufactured by Prime Polymer Co., Ltd.
<Cyclic olefin resin>
COC1: "TOPAS 8007F-04" manufactured by Polyplastics
COC2: “Appel APL6509T” manufactured by Mitsui Chemicals, Inc.
[Examples 1 to 3 and Comparative Examples 1 to 5]
An inflation film (thickness 90 μm, layer ratio 1: 1: 1) having the layer configuration shown in Table 1 was produced under the following conditions.
　＜フィルム成形条件＞
成形機：アルピネ製３層インフレーションフィルム成形機
押出機スクリュー径：５０ｍｍφ×３台
ダイ径：２２５ｍｍφ
ダイリップギャップ：３．０ｍｍ
押出量：１１１ｋｇ／ｈ（各３７ｋｇ／ｈ）
引取速度：１５ｍ／分
膨比：２．０
成形温度：１９０℃
冷却リング：トリプルタイプ
　得られたフィルムを用いて上記物性の測定および評価を行った。結果を表１に示す。 <Film forming conditions>
Molding machine: Alpine 3 layer inflation film molding machine Extruder screw diameter: 50mmφ x 3 die diameter: 225mmφ
Die lip gap: 3.0mm
Extrusion rate: 111kg / h (each 37kg / h)
Take-up speed: 15 m / minute expansion ratio: 2.0
Molding temperature: 190 ° C
Cooling ring: Triple type The physical properties were measured and evaluated using the obtained film. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000002
 　上記表１に示すように、実施例１および２と比較例２とを対比すると、層（Ｉ）に環状オレフィン系樹脂を配合することにより、透明性、易カット性、衝撃強度および引張弾性率を維持しつつ、カールを発生させずに表面硬度（微小硬度）が向上したことが判明した。特に実施例２の表面硬度は比較例２よりも１０％以上向上していることが判明した。同様に実施例３と比較例３とを対比すると、実施例３では表面硬度が１０％以上向上し、かつ他の特性は維持されていることが判明した。
Figure JPOXMLDOC01-appb-T000002
 As shown in Table 1 above, when Examples 1 and 2 are compared with Comparative Example 2, transparency, easy cutability, impact strength, and tensile modulus are obtained by blending the layer (I) with a cyclic olefin resin. It was found that the surface hardness (microhardness) was improved without curling while maintaining the above. In particular, it was found that the surface hardness of Example 2 was improved by 10% or more compared with Comparative Example 2. Similarly, when Example 3 and Comparative Example 3 were compared, it was found that in Example 3, the surface hardness was improved by 10% or more and other characteristics were maintained.

Claims (4)

  1. 　環状オレフィン系樹脂（ａ１）０．１～１０重量％と、下記条件（i）および（ii）を満たすエチレン系樹脂（ｂ１）９０～９９．９重量％とを含有する樹脂組成物（ただし、成分（ａ１）と成分（ｂ１）の合計を１００重量％とする。）からなる層（Ｉ）と、
    　環状オレフィン系樹脂（ａ２）１０～７０重量％と、下記条件（i）および（ii）を満たすエチレン系樹脂（ｂ２）３０～９０重量％とを含有する樹脂組成物（ただし、成分（ａ２）と成分（ｂ２）の合計を１００重量％とする。）からなる層（ＩＩ）と、
    　エチレン系樹脂（ｂ３）を含有する層（III）と
    を含む多層フィルム：
    （i）密度が８８０～９７０ｋｇ／ｍ3である；
    （ii）１９０℃、２．１６ｋｇ荷重におけるメルトマスフローレイト（ＭＦＲ）が、０．１～５０ｇ／１０分である。     Resin composition containing cyclic olefin-based resin (a1) 0.1 to 10% by weight and ethylene-based resin (b1) 90 to 99.9% by weight satisfying the following conditions (i) and (ii) (however, A layer (I) comprising a total of 100% by weight of component (a1) and component (b1);
    A resin composition containing 10 to 70% by weight of a cyclic olefin resin (a2) and 30 to 90% by weight of an ethylene resin (b2) satisfying the following conditions (i) and (ii) (provided that the component (a2) And the component (b2) is 100% by weight.)
    A multilayer film comprising an ethylene resin (b3) -containing layer (III):
    (I) the density is from 880 to 970 kg / m 3 ;
    (Ii) Melt mass flow rate (MFR) at 190 ° C. and a load of 2.16 kg is 0.1 to 50 g / 10 min.
  2. 　前記環状オレフィン系樹脂（ａ１）および（ａ２）が、エチレン・環状オレフィン共重合体であることを特徴とする請求項１に記載の多層フィルム。 The multilayer film according to claim 1, wherein the cyclic olefin resins (a1) and (a2) are ethylene / cyclic olefin copolymers.
  3. 　前記層（Ｉ）と前記層（ＩＩ）の間、および、前記層（ＩＩ）と前記層（III）の間の少なくとも一方に、環状オレフィン系樹脂（ａ３）０～７０重量％と、前記条件（i）および（ii）を満たすエチレン系樹脂（ｂ４）３０～１００重量％とを含有する樹脂組成物（ただし、成分（ａ３）と成分（ｂ４）の合計を１００重量％とする。）からなる層（ＩＶ）をさらに含むことを特徴とする請求項１または２に記載の多層フィルム。 At least one of the layer (I) and the layer (II) and between the layer (II) and the layer (III) has a cyclic olefin resin (a3) of 0 to 70% by weight, and the above conditions From a resin composition containing 30 to 100% by weight of an ethylene resin (b4) satisfying (i) and (ii) (provided that the total of component (a3) and component (b4) is 100% by weight) The multilayer film according to claim 1, further comprising a layer (IV).
  4. 　前記環状オレフィン系樹脂（ａ１）、（ａ２）および（ａ３）のフィルム全体に対する使用割合の合計が０．１～６０重量％であることを特徴とする請求項３に記載の多層フィルム。 The multilayer film according to claim 3, wherein the total use ratio of the cyclic olefin resins (a1), (a2) and (a3) to the whole film is 0.1 to 60% by weight.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0873618A (en) * 1994-09-07 1996-03-19 Tousero Kk Opaque polyolefin film
JPH10237234A (en) * 1997-02-24 1998-09-08 Tamapori Kk Wrapping film
JP2005535481A (en) * 2002-08-21 2005-11-24 ティコナ　ゲゼルシャフト　ミット　ベシュレンクテル　ハフツング Multilayer polyolefin film, use thereof and method for producing the same
JP2007055234A (en) * 2005-07-27 2007-03-08 Dainippon Ink & Chem Inc Coextruded multilayered film and wrapper consisting of the film
JP2012011588A (en) * 2010-06-29 2012-01-19 Dainippon Printing Co Ltd Tearable packaging bag
JP2012011587A (en) * 2010-06-29 2012-01-19 Dainippon Printing Co Ltd Laminated film
JP2013166578A (en) * 2012-02-16 2013-08-29 Dic Corp Film for twist wrapping and twisting package
WO2014061403A1 (en) * 2012-10-17 2014-04-24 東レ株式会社 Laminated film
JP2015089619A (en) * 2013-11-05 2015-05-11 Dic株式会社 Multilayer film and packing material using the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5178582B2 (en) * 2009-02-27 2013-04-10 シーアイ化成株式会社 Multilayer film and container
JP5617059B1 (en) * 2012-11-22 2014-10-29 グンゼ株式会社 Heat shrinkable film
JP6552899B2 (en) * 2015-07-15 2019-07-31 住化積水フィルム株式会社 Laminated sheet having easy cutability in a specific direction and package using the same
JP2019171761A (en) * 2018-03-29 2019-10-10 株式会社プライムポリマー Multilayer film high in surface hardness

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0873618A (en) * 1994-09-07 1996-03-19 Tousero Kk Opaque polyolefin film
JPH10237234A (en) * 1997-02-24 1998-09-08 Tamapori Kk Wrapping film
JP2005535481A (en) * 2002-08-21 2005-11-24 ティコナ　ゲゼルシャフト　ミット　ベシュレンクテル　ハフツング Multilayer polyolefin film, use thereof and method for producing the same
JP2007055234A (en) * 2005-07-27 2007-03-08 Dainippon Ink & Chem Inc Coextruded multilayered film and wrapper consisting of the film
JP2012011588A (en) * 2010-06-29 2012-01-19 Dainippon Printing Co Ltd Tearable packaging bag
JP2012011587A (en) * 2010-06-29 2012-01-19 Dainippon Printing Co Ltd Laminated film
JP2013166578A (en) * 2012-02-16 2013-08-29 Dic Corp Film for twist wrapping and twisting package
WO2014061403A1 (en) * 2012-10-17 2014-04-24 東レ株式会社 Laminated film
JP2015089619A (en) * 2013-11-05 2015-05-11 Dic株式会社 Multilayer film and packing material using the same

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