WO2007032401A1 - Film multicouche pour un usage dans un joint supérieur - Google Patents

Film multicouche pour un usage dans un joint supérieur Download PDF

Info

Publication number
WO2007032401A1
WO2007032401A1 PCT/JP2006/318183 JP2006318183W WO2007032401A1 WO 2007032401 A1 WO2007032401 A1 WO 2007032401A1 JP 2006318183 W JP2006318183 W JP 2006318183W WO 2007032401 A1 WO2007032401 A1 WO 2007032401A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
ethylene
layer
multilayer film
weight
Prior art date
Application number
PCT/JP2006/318183
Other languages
English (en)
Japanese (ja)
Inventor
Eisuke Suzuki
Akinori Takeda
Original Assignee
Asahi Kasei Chemicals Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Chemicals Corporation filed Critical Asahi Kasei Chemicals Corporation
Priority to JP2007535516A priority Critical patent/JP4880608B2/ja
Publication of WO2007032401A1 publication Critical patent/WO2007032401A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber 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
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • 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
    • B32B27/06—Layered 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
    • B32B27/08—Layered 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0264—Polyamide particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/06—Vegetal particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • 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
    • B32B2435/00—Closures, end caps, stoppers
    • B32B2435/02—Closures, end caps, stoppers for containers
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Definitions

  • the present invention relates to a multilayer film used for a top seal.
  • the present invention particularly relates to a multi-layer film for top-seal packaging, a package using the multi-layer film, and a package using the multi-layer film, which are used together with a tray having a surface layer containing polystyrene-based resin for storing, transporting and selling foods.
  • the present invention relates to a method for producing a multilayer film.
  • Stretch wrapping is characterized by the ability to maintain a good packaging appearance because the film does not loosen even after transporting the resulting package, since the tray is packed with the pulling force S of the film.
  • shrink wrapping especially pillow shrink wrap
  • the packaged goods are generally packed by the following method. In other words, the food items and other items to be packaged in the tray are gently wrapped with a film with a margin regardless of the shape and size of the items to be packaged, and then heat-sealed with a rotating roller to the film on the back of the package.
  • the center seal is performed by the method, and the film before and after the tray is sealed by the seal and cut method, and then the film is shrunk by applying heat to the package in a very short time with a heat shrink tunnel.
  • the packaged body is packed tightly. Therefore, in pillow-shrink packaging, several types of trays can be packaged without changing the width of the film that wraps the tray. As a result, labor can be saved in the packaging process, and the packaging speed is higher than that of stretch packaging. It has the feature that it can be fast.
  • top seal wrapping is performed by adhering or fusing the tray and film at the upper peripheral edge of the tray and sealing it.
  • the edges around the upper surface of the tray are securely bonded or fused together, so that moisture and oil from the contents such as raw meat are transferred to the back of the tray and the moisture And no oil leaks.
  • the amount of film used is also an effective means for reducing waste because it allows for a reduction in the amount of packaging material compared to stretch packaging and shrink packaging.
  • Patent Document 1 discloses a layer mainly composed of ethylene-based resin and Z or ethylene a-olefin copolymer, and at least two polymer blocks mainly made of vinyl aromatic compounds. Further, there is disclosed a stretch film in which at least one polymer blocking force layer mainly made from conjugated gen is disposed on the surface layer.
  • Patent Document 1 JP-A-10-180951
  • the present invention can be sealed with a tray having a surface layer containing a polystyrene-based resin, in particular, a foamed tray made of polystyrene-based resin, and can be handled during transportation and storage after transportation. It is an object of the present invention to provide a film that does not tear or peel off the seal and satisfies a good packaging appearance at the same time, and a method for producing the film. In particular, it is an object of the present invention to provide a film that satisfies the sealing performance, tear resistance, and good packaging appearance at the same time when the height of the package is raised from the height of the tray, and a method for producing the same.
  • An object of the present invention is to provide a top seal film that exhibits good sealing properties even in the presence of these foreign substances and does not cause liquid leakage due to these foreign substances.
  • the present inventors have found that the above object can be achieved by a multilayer film and a method for producing a multilayer film described below, and to complete the present invention. It came. That is, the object of the present invention has been achieved by the following multilayer film and multilayer film production method.
  • a multilayer film for top seal used for a tray having a surface layer containing polystyrene-based resin, the multilayer film having at least a first layer and a second layer,
  • the first layer is composed of (a) a copolymer consisting of a conjugate gen and a bu aromatic compound, (b) a hydrogenated copolymer of a conjugated gen and a vinyl aromatic compound, and (c) a conjugated gel.
  • the second layer is made of high-density polyethylene, medium-density polyethylene, branched low-density polyethylene, ethylene. ⁇ -olefin copolymer, ethylene 'methacrylic acid copolymer, partially neutralized ethylene, vinyl acetate Item 2.
  • the multilayer film according to Item 1, comprising at least 50% by weight of at least one selected from the group consisting of a copolymer, a polypropylene-based polymer, and a polypropylene-based terpolymer.
  • a copolymer composed of conjugated gen and vinyl aromatic compound ethylene 'butyl acetate copolymer, ethylene' methyl methacrylic acid copolymer, ethylene ' Metal partial neutralized product of methacrylic acid copolymer, ethylene 'acrylic acid copolymer, ethylene' ethylacrylic acid copolymer, ethylene 'maleic anhydride copolymer, ethylene.
  • Ethylene acrylate / maleic anhydride copolymer Polymer ethylene'maleic acid-modified resin, at least one selected from the group consisting of ethylene' ⁇ -olefin copolymer having a Vicat softening temperature of 50-68 ° C, polypropylene-based polymer, and polypropylene-based terpolymer power Item 3.
  • the multilayer film according to Item 1 or 2 comprising at least one third layer containing 3% by weight or more.
  • Packaging body having a surface layer containing a polystyrene-based resin and the multilayer film according to any one of items 1 to 7, wherein the multilayer film top seals the tray.
  • First layer containing 50% by weight or more of at least one selected from the group consisting of a mixture force with, high density polyethylene, medium density polyethylene, branched low density polyethylene, ethylene ' ⁇ -olefin copolymer, ethylene' methacrylic acid Mutual weight
  • a second metal containing 50% by weight or more of at least one selected from the group consisting of a metal partial neutralized product, an ethylene / vinyl acetate copolymer, a polypropylene polymer, a polyethylene terpolymer, and a polypropylene terpolymer.
  • a copolymer composed of conjugation and a vinyl aromatic compound ethylene 'vinyl acetate copolymer, ethylene' methyl methacrylate copolymer, ethylene partial neutralized product of ethylene 'methacrylic acid copolymer, ethylene 'Atalyl acid copolymer, ethylene' ethyl acrylate copolymer, ethylene 'maleic anhydride copolymer, ethylene' ethylene acrylate / maleic anhydride copolymer, ethylene.maleic acid modified resin, Vicat soft ⁇ ⁇ ⁇ ⁇ Ethylene 'alpha-olefin copolymer, polypropylene polymer, and polypropylene
  • the step of co-extrusion to form a tubular parison the step of cooling the tubular parison, and the tubular parison with the first one so that the gel fraction of the tubular parison is 0.5 to 50% by weight.
  • a method for producing a multilayer film comprising the steps of: The invention's effect
  • the package using the multilayer film of the present invention has a good seal strength against impacts caused by cargo handling in the storage and transport processes after packaging. As a result, it is possible to obtain a package that suppresses the tearing of the film and can maintain a good appearance such that the film has very little looseness when the package is arranged at the storefront after transportation. it can.
  • the package using the multilayer film of the present invention exhibits a good sealing property when top-sealing an object to be packaged higher than the height of the tray, that is, when performing a top seal in a raised state. , Has a good packaging appearance.
  • the present invention relates to a top seal multilayer film used for a tray having a surface layer containing a polystyrene-based resin.
  • Examples of the tray having a surface layer containing polystyrene-based resin include a hard tray and a foamed tray having a surface layer containing polystyrene-based resin.
  • a hard tray or foamed tray made of polystyrene-based resin as a main raw material, or a single-layered or laminated hard body or foamed material raw material other than polystyrene-based resin is used.
  • top seal packaging is a packaging method in which the contents are sealed by sealing a film as a lid material to the peripheral edge of the tray by means of heat fusion, impulse sealing or the like.
  • polystyrene-based resin that is a material for trays include homopolymers of styrene compounds, copolymers of two or more styrene compounds, and styrene compounds.
  • Rubber-modified styrene resin or the like in which a rubber-like polymer is dispersed in a particle form in a matrix made of the above polymer may be used. These may be used alone, or a mixture of two or more of these is also suitable. Can be used.
  • recycled materials are materials that have been processed so that they can be used again after cutting or pelletizing the film loss that occurs in the film manufacturing process or in the packaging process. ⁇ ⁇ .
  • the multilayer film of the present invention has at least a first layer and a second layer.
  • first layer is referred to as “surface layer (1)”
  • second layer is referred to as “surface layer (2)”.
  • the specific fat component described above is used for the surface layer (1), and the gel fraction of the entire film is specified.
  • the surface layer (1) of the present invention comprises (a) a copolymer comprising a conjugated diene and a vinyl aromatic compound, and (b) a copolymer obtained by hydrogenating a copolymer comprising a conjugate gen and a vinyl aromatic compound.
  • the content of the vinyl aromatic compound in the copolymer is particularly limited.
  • the content of the copolymer (a) is preferably 95% by weight or less from the viewpoint of sealing properties in a raised state where 50% by weight or more of the surface layer (1) is preferred from the viewpoint of film forming property. More preferably, it is 60% by weight or more and 85% by weight or less.
  • Conjugation is a compound containing an olefinic unsaturated conjugated double bond.
  • the vinyl aromatic compound is a compound having a vinyl bond and having an aromatic group in the side chain.
  • styrene, o-methylol styrene, p-methylol styrene, m-methino examples include restyrene, ⁇ -methyl styrene, ethyl styrene, monomethyl- ⁇ -methyl styrene, 2,4-dimethylol styrene, monochlorostyrene, ⁇ -methylol styrene, p-tert-butyl styrene, ⁇ -ethyl styrene and the like. These may be used alone or in combination of two or more.
  • the copolymer (a) of the present invention includes 1) a random copolymer of a conjugated diene and a bull aromatic compound, and 2) a block copolymer comprising a block of the conjugated diene and a bull aromatic. 3) Block block of conjugated aromatic compound and conjugated genVinyl aromatic compound Blocking block block copolymer, 4) Block of vinyl aromatic compound and conjugated gen Gen 'Bull aromatic compound copolymer Examples include block copolymers composed of blocks and conjugated gen blocks.
  • the block copolymer of the above 3) includes a block copolymer in which a block of vinyl aromatic compound is present on both ends, a block copolymer in which a block of vinyl aromatic compound is present on one end. Can be mentioned.
  • Examples of the block copolymer 4) include a block copolymer having a bull aromatic block on one end and a conjugated gen block force on the other end.
  • Examples of the copolymer block of the conjugated gen 'vinyl aromatic compound include those in which conjugated gen and vinyl aromatic compounds are present at random, and those in which the bulu aromatic compounds are present in a tapered shape. Any of these structures can be used in the multilayer film of the present invention.
  • a block copolymer having a block power which is a copolymer of a block of a bulu aromatic compound and a conjugate conjugated vinyl aromatic compound.
  • the weight average molecular weight of the copolymer (a) used in the present invention is not particularly limited, but is preferably 20,000 to 600,000, more preferably 20,000 to 400,000, Preferably it is 80,000 to 300,000.
  • the weight average molecular weight of the copolymer (a) is preferably 600,000 or less from the viewpoint of extrusion performance, which is preferably 20,000 or more from the viewpoint of film forming performance.
  • the molecular weight distribution is preferably 10.0 or less, more preferably 1.1 to 5.0, and even more preferably 1.1 to 4.0 from the viewpoint of molding cache performance. All of the above characteristics are measured by gel permeation chromatography (hereinafter abbreviated as GPC).
  • a copolymer obtained by hydrogenating (b) a copolymer that also has conjugation power and a butyl aromatic compound power may be used. That is, the copolymer (a) composed of the conjugation gen and the butyl aromatic compound may be hydrogenated.
  • copolymer (b) examples include styrene 'ethylene' butadiene block hydrogenated copolymer, styrene 'ethylene' butadiene block / styrene hydrogenated copolymer, styrene 'isoprene' butadiene block hydrogenated copolymer, Styrene “isoprene” butadiene block “styrene hydrogenated copolymer” and the like.
  • (c) As a bonding resin between a hydrogenated copolymer of conjugation diene and a copolymer having a bulu aromatic force and an ⁇ -olefin copolymer used for the surface layer (1) of the present invention, for example, at one end Polystyrene, polyethylene crystal component structure on the opposite end, and polymer having ⁇ -olefin copolymer between them, DYNARON 4600 ⁇ of JSR Co., Ltd .: styrene “ethylenebutylene” olefin crystalline block copolymer and the like.
  • the binding resin (c) used for the surface layer (1) of the present invention includes an ethylene' ⁇ -olefin copolymer and a branched low-density polymer in order to raise the stiffness of the film and suppress the stickiness of the film.
  • Liethylene may be mixed.
  • the mixture is used by mixing it with the binding resin of (c) so that it becomes 50% by weight or less of the total amount of the binding resin of (c) and the mixture, but the mixing ratio is not particularly limited.
  • the surface layer (1) of the present invention comprises (d) a binding resin of a hydrogenated copolymer of conjugated diene and butyl aromatic and an OC olefin copolymer, an ethylene ′ ⁇ -olefin copolymer, And a mixture of ⁇ ⁇ or (e) a hydrogenated product of a copolymer of conjugation diene and bulu aromatic power and an oc-olefin copolymer, and a branched resin May contain a mixture with low density polyethylene.
  • the surface layer (1) used in the present invention contains a mixture of the binding resin (c) and (d), or a mixture of the binding resin (c) and (e).
  • the total amount of the combined resin of the hydrogenated copolymer of conjugated diene and beer aromatic force and the OC olefin copolymer is 50% by weight or more of the total amount of the mixture.
  • one of the surface layers (1) may be added with other rosin within a range of 50% by weight or less.
  • the resin to be added is not particularly limited, but a polystyrene resin is preferable from the viewpoint of sealing properties and film rigidity.
  • polystyrene-based resin a homopolymer of a styrene-based compound, a copolymer of two or more styrene-based compounds, and a rubber-like polymer particles in a matrix made of the polymers of the styrene-based compounds.
  • rubber-modified styrene resin dispersed in the form of a rubber may be used alone or as a mixture of two or more. Among these, it is preferable to use a homopolymer of styrene.
  • copolymers of two or more styrenic compounds include o-methylstyrene, p-methylstyrene, m-methylstyrene, ⁇ -methyl, as well as styrene, as well as co-polymerized resins.
  • examples include styrene, ethyl styrene, monomethyl- ⁇ -methyl styrene, 2,4-dimethylol styrene, monochlorostyrene, ⁇ -methylol styrene, p-tert-butyl styrene, ⁇ -ethyl styrene, and the like. These may be used alone or in combination of two or more thereof.
  • the method for producing the polystyrene-based resin is not limited. Examples include bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. Further, the three-dimensional structure of the polystyrene-based resin can be suitably used in any force including atactic, isotactic, syndiotactic and the like. From the viewpoint of extrudability, the polystyrene-based resin preferably has a melt flow rate (hereinafter referred to as MFR) of 2 to 50 gZlOmin., More preferably 3 to 20 g / 10 min.
  • MFR melt flow rate
  • the polymerization method of the rubber-modified styrene resin is not particularly limited, but in general, a rubber-like polymer is dissolved in a styrene-based compound monomer, and bulk polymerization or bulk suspension polymerization is performed with stirring. Alternatively, it can be obtained by performing solution polymerization to precipitate a rubbery polymer into particles. Also before Examples of the rubbery polymer include polybutadiene, styrene / butadiene copolymer, polyisoprene, butadiene / isoprene copolymer, and ethylene / propylene copolymer. Polybutadiene and styrene 'butadiene copolymers are preferred, and those obtained by partial hydrogenation are more preferred.
  • the rubber-modified styrene resin a copolymer of a styrene unit and a methacrylic acid ester unit, a copolymer of a styrene unit and an alkyl acrylate unit, a polybutadiene or a styrene / butadiene copolymer is dispersed phase, Examples thereof include a copolymer having a continuous phase mainly composed of styrene / methacrylic acid ester.
  • the rubber-modified styrene resin is not particularly limited, but the MFR is preferably 2 to 50 gZlOmin., More preferably 3 to 20 gZlOmin.
  • the total of styrene components in (1) is preferably 60% by weight or more, more preferably 65% by weight or more, and particularly preferably 75 to 93% by weight. If the styrene component in the surface layer (1) is within this range, the sealing property with the tray having the surface layer containing the polystyrene-based resin is improved. In addition, by adjusting the amount of the styrene component as described above, it is possible to improve the slipperiness with a mechanical device that does not cause a significant decrease in transparency during film formation, and to improve the film formation stability.
  • the multilayer film of the present invention requires the presence of a gel component.
  • the gel component refers to a component that is formed from a high molecular weight component of rosin, a cross-linking component, and the like and does not dissolve even when attempted to dissolve with a solvent.
  • the gel fraction of the multilayer film of the present invention needs to be 0.5 to 50% by weight from the viewpoint of sealing strength in the presence of interstitial materials and the stretchability during film formation. And preferably 1 to 45% by weight, more preferably 2 to 40% by weight. Especially during the packaging process When many foreign substances are attached and sealing is difficult, the gel fraction of the entire multilayer film is set within the above range, and the gel fraction of the surface layer (1) is preferably 0.5-15. By making the weight%, more preferably 1 to 12% by weight, and still more preferably 1.5 to 8% by weight, the sealing performance can be further improved. By setting the gel fraction of the surface layer (1) within this range, the viscosity of the sealing layer at high temperatures can be increased and the surface layer (1) can be prevented from being destroyed, so even in the presence of contaminants. Good sealability can be obtained.
  • the multilayer film of the present invention is required to have a thickness of 70 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less.
  • the thickness of the multilayer film is preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more.
  • the tensile elastic modulus in the present invention is a value quantified by a 2% elastic modulus (an elastic modulus calculated from a stress when the strain is 2%).
  • the tensile elasticity of the multilayer film of the present invention is from the viewpoint of the recoverability of the film after packaging, storage and transportation, and in particular from the viewpoint of the sealing property when packaging a swelled product that wraps the contents higher than the container.
  • the rate needs to be in the range of 40 to 300 MPa in any direction, preferably 45 to 250 MPa, more preferably 50 to 230 MPa.
  • the heat shrinkage rate of the multilayer film of the present invention at 200 ° F is the viewpoint of occurrence of wrinkles after packaging, and in particular, the sealing property when packaging uplifted products in which the content is higher than the container From this viewpoint, it is necessary to be 15 to 75% in an arbitrary direction, preferably 15 to 60%, more preferably 18 to 50%.
  • top-sealing using the multilayer film of the present invention for example, the film of the package is removed, and as a result, in order to improve the packaging appearance, heat is applied at around 200 ° F. after packaging. . For this reason, it is necessary to define the thermal shrinkage rate of the multilayer film at 200 ° F.
  • the state in which the film surface is raised when the top seal is applied refers to a top seal packaging form in which the height of an object to be packaged in the tray is higher than the inner height of the tray.
  • the multilayer film of the present invention can be usefully used even when the height of the package is higher than the inner height of the tray.
  • the multi-layer film of the present invention has a bulge of 5 mm or more. (Even when the height is 5 mm or more larger than the height inside the tray), it can also be used effectively in a raised state of 10 mm or more. When the contents are raw meat, it can be used effectively even in a raised state of 20 mm or more.
  • the resin used in the surface layer (2) is a high-density polyethylene, a medium-density polyethylene, a branched low-density polyethylene, or an ethylene / ⁇ -olefin composite weight from the viewpoint of film formation stability.
  • Copolymer, Ethylene 'methacrylic acid copolymer partially neutralized metal, Ethylene' vinyl acetate copolymer, Polypropylene polymer, Polyethylene terpolymer, and Polypropylene terpolymer 50% by weight or more is preferable.
  • both ethylene ' ⁇ -olefin copolymer, branched low-density polyethylene, and ethylene' ⁇ -olefin are used. More preferably, it includes a mixture of polymer and branched low density polyethylene.
  • ⁇ -olefin is a random copolymer of ethylene and at least one monomer selected from ⁇ -olefin having 3 to 18 carbon atoms.
  • A-olefin is composed of propylene and butene. 1, pentene 1, 4-methyl 1 pentene 1, hexene 1, otaten 1, decene 1, dodecene 1, and the like.
  • Ethylene content of [0049] ethylene 'alpha Orefuin copolymer is preferably 40 to 95 weight 0/0, more preferably 50 to 90 wt%, more preferably 60 to 85 wt%.
  • the polymerization method of ethylene with olefin is not particularly limited, and examples thereof include a polymerization method using a multi-site catalyst, a single-site catalyst, and the like.
  • a material polymerized with a single-site catalyst it is preferable to use one having a molecular weight distribution (MwZMn) measured by GPC of 3.5 or less because the transparency is particularly good.
  • high-density polyethylene used in the surface layer (2) of the present invention an ethylene homopolymer is also properly is a copolymer of ethylene and 5 mol 0/0 following 1 Orefuin monomer, and, density refers to a 0. 942gZcm 3 more ⁇ .
  • the medium density polyethylene used in the surface layer (2) of the present invention among the homopolymer or the copolymer, density 0. 930gZcm 3 or more, have a ⁇ less than 0. 942gZcm 3
  • the density of the ethylene / ⁇ -olefin copolymer used in the surface layer (2) of the present invention is preferably from 0.870 to 0.925 gZcm 3 .
  • the density is 0.970 gZcm 3 or more, the film becomes soft and the running property on the packaging machine is improved, and when the density is 0.925 gZcm 3 or less, the transparency is improved.
  • the density of the branched low-density polyethylene used in the surface layer (2) of the present invention is 0.908-0.
  • 925 gZcm 3 is preferred.
  • the density is 0.908 gZcm 3 or more, the film is stretched and the running property on the packaging machine is improved, and when the density is 0.925 gZcm 3 or less, the transparency is improved.
  • the MFR of the ethylene 'vinyl acetate copolymer used in the surface layer (2) is 0.3 to 5. Og / 10 min. From the viewpoint of extrusion characteristics. S is preferable, more preferably 0.5. ⁇ 3.5g / 10mi n.
  • the vinyl acetate content is preferably 5.5 to 20% by weight, more preferably 5.5 to 16.0% by weight from the viewpoints of preventing film tearing and preventing the smell of acetic acid. is there.
  • Examples of the polypropylene polymer used in the surface layer (2) include a homopolymer, a random copolymer with ethylene or butene, and the like. Among these, from the viewpoint of packaging appearance, a copolymer with ethylene or butene is preferable.
  • the polypropylene-based terpolymer means a terpolymer of ethylene-butene-propylene or ethylene-propylene-gen, in which propylene is a main component.
  • the ethylene part methacrylic acid copolymer metal neutralized product used in the surface layer (2) of the present invention is a part of a copolymer of ethylene and methacrylic acid with a polyvalent metal ion such as sodium or zinc.
  • a polyvalent metal ion such as sodium or zinc.
  • This is a neutralized thermoplastic resin, in which polymer chains are linked by ionic bonds.
  • the above-mentioned fat used in the surface layer (2) of the present invention is not particularly limited as long as it is contained in the surface layer (2) in an amount of 50% by weight or more and the remaining 50% by weight or less. Any rosin can be used.
  • the third layer is a copolymer consisting of conjugation and butyl aromatic compounds, Lene 'vinyl acetate copolymer, ethylene' methyl methacrylic acid copolymer, ethylene partial neutralized product of ethylene 'metatalic acid copolymer, ethylene / acrylic acid copolymer, ethylene' ethyl acrylic acid copolymer, ethylene 'Maleic anhydride copolymer, ethylene' ethylene acrylate 'maleic anhydride copolymer, ethylene' maleic acid modified resin, ethylene with Vicat softening temperature of 50-68 ° C.
  • the MFR of the third layer is preferably 0.3 to 5.0 g / 10 min., More preferably 0.5 to 3.5 g / 10 min.
  • the third layer contains 50% by weight or more of the above resin, the remaining 50% by weight or less of the resin is not particularly limited, and any resin can be used.
  • the multilayer film of the present invention has a good packaging appearance without film tearing, glycerin, fatty acid, polyhydric alcohol fatty acid ester, talc, oleate, amide-based lubricant, and number average molecular weight 250
  • it contains at least one additive selected from the group that also has a mineral oil strength of ⁇ 480.
  • the additive imparts lubricity to the film, and the packaging speed is high in the packaging process.
  • the film is pulled against a part of the packaging machine and prevents the film from being torn. effective.
  • it has the effect of improving the slipperiness between the film and the tray and preventing film tearing during transport.
  • it has the effect of improving the opening property when forming the tube-shaped parison, improving the sliding property with the mechanical device, and improving the stability of film formation. From such a viewpoint, it is preferable to add the above-mentioned additive at 10% by weight or less based on the entire surface layers (1) and Z or the surface layer (2).
  • Examples of the fatty acid used in the present invention include force puric acid, coconut oil fatty acid, oleic acid, castor oil fatty acid, and cabronic acid.
  • Examples of the polyhydric alcohol fatty acid ester include glycerin fatty acid ester, diglycerin fatty acid ester, polyglycerin fatty acid ester, and the like, all of which contribute to antifogging properties and film formation stability.
  • Polyhydric alcohol fat from the viewpoint of film-forming stability and anti-fogging property The addition amount of the acid ester is preferably 0.5 to 7% by weight, more preferably 0.7 to 5% by weight, based on the entire surface layer (1) and Z or surface layer (2). .
  • the content is preferably 0.8 to 3% by weight from the viewpoint of ink peeling.
  • Examples of the oleate include sodium oleate, calcium oleate, and potassium oleate.
  • Sodium oleate is particularly preferable from the viewpoint of film formation stability of the film.
  • the amide-based lubricant examples include erucic acid amide, oleic acid amide, stearic acid amide and the like.
  • the amount of the amide-based lubricant added is preferably 0.1 to 2% by weight based on the entire surface layer (1) and Z or surface layer (2).
  • mineral oil when used in the present invention, its number average molecular weight is preferably 250-480.
  • the number average molecular weight is 250 or more, the effect of contributing to the film forming stability is at most 480 or less, the film forming stability is good and the seal strength is improved.
  • additives have different optimum values depending on the film forming conditions, one or more additives selected from the above substances can be selected as necessary.
  • the multilayer film of the present invention is most suitable for a top seal packaging method in a state in which a packaged object rises from a tray. Therefore, for example, a surface layer containing polystyrene resin and containing raw poultry meat is used. It can be used satisfactorily for tray applications.
  • raw poultry meat is marketed in the form of overlapping packaging films or pillow shrink packaging on expanded polystyrene trays.
  • meat oil or moisture tends to adhere to the edges around the tray during the packaging process, so the sealing performance, particularly when the contents are raised, is improved. It becomes important. Since these problems can be solved by using the multilayer film of the present invention, the multilayer film of the present invention is most suitable for the above-mentioned use.
  • the package body in which the multilayer film of the present invention is top-sealed on a tray having a surface layer containing a polystyrene-based resin has a good sealing property, in particular, a foreign matter sealing property. It is possible to prevent the film from being torn even during refrigeration or freezing transport without leaks.
  • the liquid mainly contains blood that oozes from the meat.
  • the top seal package of the present invention it is possible to prevent liquid leakage to the outside of the package during storage, during transportation, and after transportation even if the impact generated during handling is strong.
  • the film of the present invention is formed into a film by a single bubble inflation method, a double bubble inflation method, a triple bubble inflation method, a tenter method, or the like. From the viewpoint of shrinkability, the single bubble inflation method, the double bubble inflation method, The double bubble inflation method is preferred, with the bubble inflation method and triple bubble inflation method being preferred.
  • the raw materials used are melted for each of the surface layer (1), the surface layer (2), and the third layer by using several types of extrusion machines, and each molten resin is screen changer, polymer pipe After passing the molten resin, each molten resin is guided to the annular die, and the molten resin forming each layer is sequentially or simultaneously laminated inside the annular die. An unstretched raw fabric (tubular parison) is obtained. Next, the tubular parison thus obtained is cooled by the following method.
  • Examples of the cooling method of the tubular parison include, for example, a method of cooling using an external force water of the parison as a cooling medium, a cooling using the external force water of the parison as a cooling medium, and further a tubular parison.
  • a cooling mandrel whose surface is blasted and roughened inside (the inside of the mandrel is flushed with water) allows cooling from both the inside and outside of the tube-shaped parison to rapidly cool and solidify the parison. It is done. Any method may be used in the present invention.
  • the position where the cooling mandrel is installed is important in controlling the thickness of the parison.
  • the end of the cooling mandrel is preferably located at a position 10 to 70 mm away from the annular die surface of the annular die, more preferably 20 to 60 mm. .
  • the length of the cooling mandrel is preferably 150 to 300 mm from the viewpoint of operability and cooling capacity.
  • the diameter of the cooling mandrel is preferably 1.0 to 1.7 times the annular die lip diameter of the above-mentioned annular die from the viewpoint of operability and cooling capacity. Is double.
  • the application method include a method in which the substance is sprayed and applied from the inside or outside of the tubular parison, a method in which the substance liquid is placed inside the tubular parison, and a certain amount is applied while squeezing with a roll. .
  • the method of applying from the inside is preferred because of its simple operation.
  • the cooled and solidified tubular parison is guided into the stretching machine, and air is injected between the rolls with a speed difference while heating the stretching start point between 70 and 140 ° C.
  • Stretch at. from the viewpoint of stretching stability, the draw ratio is preferably 1.5 to: LO times, more preferably 2 to 7 times in each of the flow direction (MD) and the width direction (TD). Stretch.
  • the stretching start point refers to the position where the TD direction of the parison begins to expand due to the internal pressure of the bubble.
  • the stretching start temperature is set to 70 ° C to 140 ° C, and the stretching ratio is controlled to be 1.5 to 10 times in any of the MD and TD directions.
  • a film having a tensile elastic modulus of 0 to 300 MPa and a heat shrinkage of 15 to 75% at 200 ° F. can be obtained.
  • the tubular neurons may be subjected to a crosslinking treatment with an electron beam.
  • the electron beam cross-linking treatment may be performed either before or after stretching, but is preferably performed before stretching because a relatively small crosslinking apparatus can be used.
  • the film of the present invention has a gel fraction of the whole film of 0.5 to 50% by weight from the viewpoints of sealing properties when there is a contaminant between the tray and the film, and elongation stability.
  • the electron beam irradiation is performed at 15 to 150 kGy, and more preferably 25 to 120 kGy.
  • the electron beam irradiation may be totally transmitted through the tubular parison.
  • the electron beam should be connected to the surface (1) side of the tubular parison. More irradiation is preferable. By irradiating from the surface layer (1) side, it becomes easy to control the gel component ratio in the surface layer (1), and it is possible to improve the sealing property of foreign matter at the time of sealing.
  • the stretched film prefferably to subject the stretched film to a surface treatment such as corona treatment, ozone treatment, or flame treatment because a film suitable for printing applications can be obtained.
  • the obtained raw film is slit to a predetermined size to obtain a packaging film.
  • an antioxidant, a plasticizer and the like may be added to the multilayer film of the present invention to such an extent that the original properties are not impaired.
  • the multilayer film of the present invention may be blended with a high pressure method low density polyethylene or the like in a layer necessary as a processing aid as long as it does not impair the original properties that may contain petroleum-based resin.
  • hydrogenated petroleum resin Arcon (Arakawa Chemical Co., Ltd .: product name)
  • hydrogenated terpene resin (Clearon (Yasuhara Chemical Co., Ltd .: product name)
  • the content is the entire multilayer film. When the content is 0.1 to 10% by weight, the shrinkage and transparency are good, which is preferable.
  • the elastic modulus was determined according to JIS-K7127.
  • the heat shrinkage ratio is expressed as a percentage of the value obtained by dividing the original dimensions by measuring the shrinkage of the film after heat treatment for 1 minute after placing a 100mm square film in an air oven type high-temperature bath set at 200 ° F. did.
  • this heat shrinkage rate set arbitrary three places in the TD direction about the obtained film, calculated
  • the film is extracted in boiling P-xylene for 12 hours, filtered through a mesh of 150 mesh size, the insoluble part weight is measured, and the ratio is expressed by the following formula.
  • Vicat soft temperature was determined according to IS-K7206.
  • the component amount of styrene was determined by an ultraviolet spectrophotometer method.
  • a copolymer comprising hydrogenated conjugated diene and vinyl aromatic compound it can be determined by a nuclear magnetic resonance apparatus method (NMR method).
  • GMH-6 using orthodichlorobenzene (ODCB) as a solvent, was measured under the conditions of a temperature of 135 ° C, a flow rate of 1 mL Zmin, and a concentration of lOmgZlOmL.
  • the weight average molecular weight and molecular weight distribution (Mw / Mn) were determined from the weight average molecular weight (Mw) and number average molecular weight (Mn) converted from the composition curve of standard polystyrene.
  • top-seal packaging is performed using the multilayer films of the examples and comparative examples.
  • X A state in which a circular or oval indentation of about 10 mm remains strong, and there are many loose and wrinkled areas around the area.
  • the distance from the top of the tray to the highest position of the contents was about 20 mm, and the multilayer film was raised.
  • the two types of packaging obtained above are placed in a three-layer stack on each cardboard box, transported by truck for a distance of about 200 km, and after transport, the cardboard box is dropped twice from the height of lm, The state of the seal, the film tearing, the state of the sheath generated on the film, and the state of leakage of liquid from the inside of the top seal package to the outside of the package were visually confirmed.
  • EVA2 Ethylene acetate butyl copolymer
  • SB1 is introduced into the extruder for the surface layer (1)
  • PE1 is introduced into the extruder for the surface layer (2)
  • the extruder for the intermediate layer (third layer) is used.
  • EVA1 was added to the machine, and three types of three-layered nozzles were extruded using an intra-die bonded annular die.
  • the obtained tube-shaped parison is cooled from the outside of the parison using water as a cooling medium, and at the same time, the inside of the parison is placed along a cooling mandrel that has been blasted and roughened with a water-permeable surface inside.
  • the tube-shaped parison with a width of 180 mm and a thickness of 400 m was created by cooling and solidifying by cooling from both the inside and outside of the tube-shaped parison.
  • This tube-shaped parison was guided to an electron beam irradiation device, irradiated with an electron beam from the surface layer (1) side, and subjected to crosslinking treatment so that the absorbed dose was 80 kGy.
  • the parison was guided into a drawing machine and reheated, passed between two pairs of differential nip rolls, and bubbles were formed by air injection.
  • the temperature near the stretching start point was about 98 ° C. Stretching to a magnification of 5 times in the vertical direction and 4 times in the horizontal direction, A multilayer film with a thickness of about 20 ⁇ m is obtained with a treadmill.
  • a film having a thickness of about 20 ⁇ m was obtained in the same manner as in Example 1 except that SB2 was charged into the extruder for the surface layer (1).
  • the styrene component in the surface layer (1) in this example was 76% by weight.
  • SB3 70 wt%) + ⁇ 1 (30 wt%) was put into the extruder for the surface layer (1), and sodium oleate was wetted in the parison inside the tube-shaped tube. A certain amount of iron was applied with a pinch roll. The tube-shaped parison was guided to an electron beam irradiation device, irradiated with an electron beam from the surface layer (2) side, and subjected to crosslinking treatment so that the absorbed dose was 80 kGy.
  • a film having a thickness of about 20 ⁇ m was obtained in the same manner as in Example 1 except that PP1 was charged into the extruder for the surface layer (2).
  • ⁇ 2 was added to the extruder for the surface layer (2), and ⁇ 1 (20 wt%) + EVA2 (80 wt%) was added to the extruder for the intermediate layer, and the other operations were the same as in Example 1. A film about 20 m thick was obtained.
  • the material (PE1) constituting the surface layer (2) contains 1.5% by weight of diglycerin fatty acid ester.
  • a film having a thickness of about 20 m was obtained in the same manner as in Example 1, except that
  • the material (SB1) constituting the surface layer (1) contains 0.5% by weight of talc (Talc PKP81 (Fuji talc industry)), and the material constituting the surface layer (2) (PE1) contains diglycerin fatty acid ester.
  • a film having a thickness of about 20 / zm was obtained in the same manner as in Example 1 except that the content was 1.5% by weight.
  • a film was obtained by the double bubble inflation method using SB2 as the surface layer (1) and PP1 as the surface layer (2).
  • a parison was extruded using an in-die bonded annular die.
  • the obtained tube-shaped parison is cooled from the outside of the parison using water as a cooling medium, and is also cooled from the inside of the parison by placing the inside of the parison along a rough cooling mandrel that has been blasted with water inside.
  • the tube-shaped parison with a width of 180 mm and a thickness of 350 m was made by cooling and solidifying from both inside and outside of the tube-shaped parison.
  • This tube-shaped parison was guided to an electron beam irradiation device, irradiated with an electron beam from the surface layer (1) side, and subjected to crosslinking treatment so that the absorbed dose was 35 kGy.
  • the parison was introduced into a stretching machine and reheated, passed through two pairs of differential nip rolls, and bubbles were formed by air injection.
  • the temperature near the stretching start point was about 110 ° C.
  • the film is stretched to a magnification of 5 times in the vertical direction and 4 times in the horizontal direction, and a multilayer film with a thickness of about 18 ⁇ m is obtained with a scraper.
  • Example 9 An operation similar to that in Example 9 was performed except that the electron beam crosslinking treatment was not performed in Example 9, and an attempt was made to obtain a multilayer film having a thickness of about 18 m.
  • Table 1 shows the results obtained in Examples 1 to 9 and Comparative Example 1. In the table, “ND 1 ” means that the evaluation was not possible because the sealability was poor and could not withstand transportation.
  • the multilayer film of the present invention can be suitably used as a top seal packaging film.
  • it is suitable for processed foods and raw meats, especially processed foods using trays with polystyrene-based resin on the surface, and top-seal packaging for poultry raw meat such as chicken.

Landscapes

  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

La présente invention concerne un film multicouche pour un usage dans un joint supérieur, qui peut être utilisé dans un plateau ayant une couche extérieure comprenant une résine de polystyrène. Le film multicouche possède au moins une première couche et une seconde couche. La première couche contient 50 % en poids ou plus d’au moins une substance choisie dans le groupe constitué par (a) un copolymère comprenant un diène conjugué et un composé de type vinyle aromatique, (b) un copolymère préparé par l’hydrogénation d'un copolymère comprenant un diène conjugué et un composé de type vinyle aromatique, (e) un mélange d'une résine conjuguée et d’un polyéthylène basse densité ramifié, la résine conjuguée étant préparée en conjuguant un produit d'hydrogénation d'un copolymère comprenant un diène conjugué et un composé de type vinyle aromatique à un copolymère d'α-oléfine et autres. Le film multicouche possède une fraction gel de 0,5 à 50 % en poids, une épaisseur inférieure ou égale à 70 μm, un module d’élasticité dans une direction arbitraire de 40 à 300 MPa, et un thermorétrécissement à 200 °F dans une direction arbitraire de 15 à 75 %. La présente invention concerne également un matériau d'emballage produit en utilisant le film multicouche. L’invention concerne en outre un procédé de production du film multicouche.
PCT/JP2006/318183 2005-09-13 2006-09-13 Film multicouche pour un usage dans un joint supérieur WO2007032401A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007535516A JP4880608B2 (ja) 2005-09-13 2006-09-13 トップシール用多層フィルム

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-265703 2005-09-13
JP2005265703 2005-09-13

Publications (1)

Publication Number Publication Date
WO2007032401A1 true WO2007032401A1 (fr) 2007-03-22

Family

ID=37864992

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/318183 WO2007032401A1 (fr) 2005-09-13 2006-09-13 Film multicouche pour un usage dans un joint supérieur

Country Status (2)

Country Link
JP (1) JP4880608B2 (fr)
WO (1) WO2007032401A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010234547A (ja) * 2009-03-30 2010-10-21 Asahi Kasei Chemicals Corp 多層熱収縮性フィルム
WO2013121874A1 (fr) * 2012-02-16 2013-08-22 株式会社クレハ Film multicouche thermorétractable
JP2017088194A (ja) * 2015-11-05 2017-05-25 旭化成株式会社 トップシール用多層フィルム

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000351860A (ja) * 1999-06-10 2000-12-19 Nippon Polystyrene Kk ゴム変性ポリスチレン樹脂組成物からなるフィルム
JP2004075197A (ja) * 2002-07-31 2004-03-11 Shikoku Kakoki Co Ltd 密封容器及びその製造方法
JP2004136594A (ja) * 2002-10-18 2004-05-13 Kuraray Co Ltd 複層成形体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000351860A (ja) * 1999-06-10 2000-12-19 Nippon Polystyrene Kk ゴム変性ポリスチレン樹脂組成物からなるフィルム
JP2004075197A (ja) * 2002-07-31 2004-03-11 Shikoku Kakoki Co Ltd 密封容器及びその製造方法
JP2004136594A (ja) * 2002-10-18 2004-05-13 Kuraray Co Ltd 複層成形体

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010234547A (ja) * 2009-03-30 2010-10-21 Asahi Kasei Chemicals Corp 多層熱収縮性フィルム
WO2013121874A1 (fr) * 2012-02-16 2013-08-22 株式会社クレハ Film multicouche thermorétractable
JPWO2013121874A1 (ja) * 2012-02-16 2015-05-11 株式会社クレハ 熱収縮性多層フィルム
JP2017088194A (ja) * 2015-11-05 2017-05-25 旭化成株式会社 トップシール用多層フィルム

Also Published As

Publication number Publication date
JPWO2007032401A1 (ja) 2009-03-19
JP4880608B2 (ja) 2012-02-22

Similar Documents

Publication Publication Date Title
JP6302726B2 (ja) 二軸延伸ポリプロピレン系フィルム及び包装用袋
WO2006118030A1 (fr) Film de resine de polypropylene a couches multiples thermoscellable et materiau d’emballage
US7923119B2 (en) Multilayer film for top-seal
JPWO2018181011A1 (ja) 二軸配向ポリプロピレン系樹脂フィルム
EP2683772B1 (fr) Composition antibuée scellable pour films thermoscellables et emballages à ouverture facile obtenus à partir de celle-ci
JP4812411B2 (ja) 熱収縮性多層フィルム
JP4880608B2 (ja) トップシール用多層フィルム
JP2005305998A (ja) ヒートシール性ポリプロピレン系樹脂積層フィルム及び包装体
JP5084353B2 (ja) 熱収縮性多層フィルム
JP2009096130A (ja) 熱収縮性フィルム
JP3366879B2 (ja) ポリオレフィン系樹脂フィルム
JP4721925B2 (ja) ストレッチシュリンク積層フィルム及びその製造方法
JP4846613B2 (ja) 多層フィルム
JPH1058626A (ja) 食品包装用ストレッチシュリンクフィルム及びその製造方法
JP2007237458A (ja) ストレッチシュリンク積層フィルム及びその製造方法
WO2013115909A1 (fr) Films soudables en polypropylène de stabilité améliorée
JP7251153B2 (ja) ストレッチ包装用フィルム
JP7018794B2 (ja) 良好な剥離性が得られるポリプロピレン系延伸フィルム
CN114072285A (zh) 包装用层叠膜及热收缩性层叠膜
JP3462129B2 (ja) ポリオレフィン系樹脂多層延伸フィルム
JP2017088194A (ja) トップシール用多層フィルム
JP3746405B2 (ja) 食品包装用フィルム
JP4896421B2 (ja) ストレッチシュリンク積層フィルムおよびその製造方法
JP4684093B2 (ja) 多層熱収縮フィルム
JP2894120B2 (ja) ストレッチラップ多層フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2007535516

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06797933

Country of ref document: EP

Kind code of ref document: A1