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WO2002038376A1 - Stratifie pour materiau d'emballage - Google Patents

Stratifie pour materiau d'emballage Download PDF

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Publication number
WO2002038376A1
WO2002038376A1 PCT/JP2001/009705 JP0109705W WO0238376A1 WO 2002038376 A1 WO2002038376 A1 WO 2002038376A1 JP 0109705 W JP0109705 W JP 0109705W WO 0238376 A1 WO0238376 A1 WO 0238376A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
laminate
polycyclic olefin
olefin copolymer
polyethylene
Prior art date
Application number
PCT/JP2001/009705
Other languages
English (en)
Japanese (ja)
Inventor
Peter Frisk
Hiroaki Ogita
Thorbjorn Andersson
Ib Leth
Original Assignee
Tetra Laval Holdings & Finance S.A.
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 Tetra Laval Holdings & Finance S.A. filed Critical Tetra Laval Holdings & Finance S.A.
Priority to AU2002212711A priority Critical patent/AU2002212711A1/en
Publication of WO2002038376A1 publication Critical patent/WO2002038376A1/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
    • 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
    • B32B27/10—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 paper or cardboard

Definitions

  • the present invention relates to a laminate for packaging materials, and more particularly to a laminate for packaging materials suitable for packaging liquids such as liquid foods.
  • packaging materials such as liquid foods are mainly made of paper and laminated with materials such as plastic films such as polyethylene, polypropylene, polyester, and polyvinyl chloride.
  • a barrier layer is often provided inside the packaging material in order to protect the liquid as the internal filling material.
  • a metal foil such as an aluminum foil is often used for the barrier layer.
  • the barrier layer such as an aluminum foil, may be corroded, or the adhesiveness of the adhesive layer of the packaging material may be lost. As a result, the internal filling may seep out.
  • the above-mentioned obstacles caused by the internal filling are particularly caused by bending the container filled with the internal filling at a high temperature such as bending at 7 Ot: or more, retorting at a temperature up to about 13.0 ° C, etc.
  • the above-mentioned obstacles tend to be remarkable by handling.
  • the present invention relates to a liquid food of a barrier layer of a packaging material having a paper layer and a barrier layer inside the paper layer.
  • An object of the present invention is to provide a packaging material provided with a protective layer inside the barrier layer in order to prevent damage due to a liquid filling such as a product.
  • the present inventors have conducted intensive studies to improve the above problems, and as a result, provided an inner layer having a polycyclic olefin copolymer-containing layer inside a paper layer and an outer layer having a barrier layer on the inside thereof.
  • the inner layer refers to a layer on the side in contact with the inner filler when the inner filler is packaged using the packaging material laminate
  • the outer layer refers to a layer on the opposite side.
  • the inside refers to the side closer to the inner filling
  • the outside refers to the opposite side.
  • the gist of the present invention resides in a laminate for a packaging material in which at least a paper layer and an outer layer having a barrier layer inside the paper layer and at least an inner layer having a polycyclic olefin copolymer-containing layer are laminated.
  • the laminate for a packaging material of the present invention is characterized in that the polycyclic copolymer is a copolymer of a cyclic oligomer and ethylene or olefin.
  • the laminate for packaging materials of the present invention is characterized by having a thermoplastic resin layer outside the paper layer.
  • the laminate for packaging materials of the present invention is characterized by having a polyethylene layer on the innermost side of the inner layer.
  • the laminate for packaging materials of the present invention is characterized in that the polyethylene layer is made of a linear low-density polyethylene produced by using a methyl benzene catalyst.
  • the outer layer of the laminate for packaging materials of the present invention has at least a paper layer and a barrier layer inside the paper layer. Therefore, in addition to the configuration consisting of only the paper layer and the barrier layer, a configuration in which one or more other layers are provided between the paper layer and the barrier layer, and a configuration in which one or more other layers are provided outside the paper layer A configuration in which one or more other layers are provided inside the barrier layer, and a configuration in which they are combined can be adopted.
  • the barrier layer may be a barrier material alone, or may be a multilayer structure containing a barrier material. May be something.
  • the barrier material include aluminum foil, silicon oxide-deposited polyethylene phthalate, ethylene-butyl alcohol copolymer, and nylon resin.
  • the multilayer structure including barrier materials include polyethylene film / aluminum foil, adhesive polyethylene, biaxially stretched film of silicon oxide-deposited polyethylene terephthalate (adhesive), polyethylene film adhesive, and Z-ethylene-butyl alcohol co-polymer. Coated film adhesive, nylon resin film / adhesive, and the like.
  • the thickness of the barrier layer is usually 5-20 ⁇ .
  • the outer layer forming the laminate for packaging material of the present invention has at least a paper layer and the above-mentioned paria layer inside the paper layer, and one or more thermoplastic resin film layers are provided outside the paper layer.
  • the configuration and the configuration in which one or a plurality of thermoplastic resin film layers are provided between the paper layer and the barrier layer are particularly preferable.
  • thermoplastic resin examples include polyolefin, nylon, polyester, and polyvinyl chloride.
  • polyolefin examples include polyethylene, polypropylene, ethylene-propylene copolymer, and polybutene-1.
  • nylon examples include nylon 6, nylon 6-6, nylon-11, nylon-12, and the like.
  • polyester examples include polyethylene terephthalate and polybutylene terephthalate.
  • polyethylene is particularly preferred as polyolefin.
  • the polyethylene may be any of high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene.
  • each of the thermoplastic resin film layers may be the same type of film layer or a different type of film layer.
  • the thickness of the thermoplastic resin film layer is usually 5 to 200 ⁇ .
  • the outer layer may further include, for example, a printing layer.
  • the printing layer may be formed by using a normal ink and printing by a normal method on the outside of the outer paper layer or on the inside of the thermoplastic resin film layer provided as needed on the outside of the paper layer.
  • the inner layer forming the inner side in the laminate for packaging materials of the present invention has at least a layer containing a polycyclic olefin copolymer.
  • Polycyclic olefin copolymers include copolymers of polycyclic olefin and ethylene or ⁇ -olefin, and polycyclic olefins. Copolymers of olefins with monocyclic olefins, copolymers of polycyclic olefins with non-conjugated gens and the like can be mentioned. Copolymers of polycyclic olefin and ethylene or ct-olefin, particularly copolymers of polycyclic olefin and ethylene, are preferred.
  • ⁇ -olefins copolymerized with polycyclic olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methinole 1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like.
  • Examples of the monocyclic olefin include cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene and the like.
  • Examples thereof include 1,4-hexadiene, 4-methyl-1,4-hexadiene, and 1,7-octadiene.
  • these olefins that are copolymerized with the polycyclic olefin can be used.
  • the copolymerization of the polycyclic olefin and the above olefins is usually carried out in the presence of a medium such as an organic solvent using a catalyst in which a transition metal compound such as titanium, zirconium, vanadium or hafnium is combined with an organic aluminum compound. In the absence, carried out at a temperature of-50-150 ° C.
  • the polycyclic olefin copolymer used in the present invention produced by the above-mentioned copolymerization is a random copolymer of the polycyclic olefin and the above-mentioned olefins, and the structural unit derived from the polycyclic olefin is 30%. one 9 5 mole 0/0, especially those of 4 0 8 0 mole 0/0 preferred.
  • the inner layer forming the laminate for packaging materials of the present invention has at least the above-mentioned polycyclic olefin copolymer-containing layer, and the polycyclic olefin copolymer-containing layer is composed of the polycyclic olefin copolymer alone. Or a mixture with other substances.
  • a polyolefin such as polyethylene, polypropylene, ethylene-propylene copolymer, or polybutene-1 is preferable.
  • polyethylene examples include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and linear low-density polyethylene produced by using a meta-mouth catalyst. As described above, it is desirable to use a linear low-density polyethylene produced by using a meta-mouth catalyst used for a layer preferably provided on the innermost side of the inner layer forming the laminate for packaging material of the present invention.
  • the content of the polycyclic olefin copolymer is preferably at least 50% by weight, particularly preferably at least 60% by weight.
  • the thickness of the layer containing the polycyclic olefin copolymer is usually 150 / m.
  • the inner layer forming the laminate for packaging material of the present invention has at least the above-mentioned polycyclic olefin copolymer-containing layer, and a polyethylene layer is provided on the innermost side of the polycyclic olefin copolymer-containing layer.
  • Polyethylene includes high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and linear low-density polyethylene manufactured using Either of ethylene (mLLDPE) may be used, but mLLDPE is particularly preferred.
  • mLLDP E is an ⁇ -olefin having ethylene and a comonomer having 418 carbon atoms, preferably 1-hexene, 4_methyl-1-pentene, 1_heptene, 1-octene in the presence of a meta-mouth catalyst. It is desirable to use one produced by copolymerizing a freerefin having 6 or more carbon atoms, such as
  • the meta-open catalyst is a compound having a structure in which a transition metal such as titanium, zirconium, or hafnium is sandwiched by an unsaturated cyclic compound containing a ⁇ -electron cyclopentenyl group or a substituted cyclopentenyl group. It is a combination of styrene and a cocatalyst such as an aluminum compound such as an alkyl aluminoxane, an alkyl aluminum, an aluminum octalide, and an alkyl amine halide.
  • melt flow index (MFI: 190 ° C, load: 2.16 kg) be 10 to 20 gZl 0 minutes.
  • the thickness of the polyethylene layer is usually 10-50 ⁇ .
  • the inner layer forming the laminate for packaging material of the present invention has a polycyclic olefin copolymer-containing layer as a central layer, and a layer made of, for example, polypropylene or polyethylene is provided on one of the layers as the innermost layer, and the other is provided on the other.
  • a laminate having an adhesive layer can be obtained.
  • the laminate can be simultaneously extruded and formed at a low temperature, and the adhesive layer of the laminate is combined with the outer layer of the laminate for packaging material of the present invention. Can be laminated.
  • the laminate for packaging materials of the present invention is a laminate of at least the outer layer and at least the inner layer.
  • a method of hot-melting a layer that can be melted and bonding it to a layer that is in contact with it, and a method of simultaneously extruding layers that can be simultaneously extruded Any of the methods conventionally used for manufacturing a laminated body, such as a method of laminating by stacking and a method of combining them, etc. Can be adopted.
  • Covered rectangular parallelepiped, cubic, cylindrical, parallel octagonal prism represented by a 1-liter milk container, a tetraprizuma (trademark) type with a rectangular parallelepiped at the center of the torso and a rectangular cross section at the top and bottom, and a bouch, etc.
  • a conventionally known arbitrary shape of a packaging container or the like can be formed.
  • Low density polyethylene film (1 0; m), kraft paper (basis weight: 2 2 0 g / m 2 ), is laminated with a low density polyethylene film (2 0 m) and an aluminum foil (7 Iotaiotapai adhesives The composite was 1.
  • a polycyclic olefin copolymer (60 mol% of a polycyclic olefin component, 40 mol% of an ethylene component) and a density: 0.910 MF I: mLLDPE of 14 gZl 0 min was simultaneously extruded from the extruder to obtain a composite 2 composed of a polycyclic olefin copolymer film (30 m) and a mLLDPE film (20 m).
  • the aluminum foil of the composite 1 was melt-laminated with the polycyclic olefin copolymer film of the composite 2 to produce a laminate of the present invention.
  • the aluminum foil of the composite 1 obtained in Example 1 and the polycyclic olefin copolymer film of the composite 2 were adhered with an ethylene-methyl methacrylate copolymer-based adhesive to produce a laminate of the present invention.
  • Example 2 instead of the polycyclic olefin copolymer used for obtaining the complex 2 in Example 1, 70% by weight of the polycyclic olefin copolymer, density: 0.910 gZcm 3 , MFI: 1
  • the mixture film (30 m) and the mLLDP E film (20 m) were prepared in the same manner as in Example 1 except that a mixture of 4 g / 10 minutes of mL LDP E 30% by weight was used.
  • Complex 3 was obtained. Except that Complex 3 was used instead of Complex 2, A laminate of the present invention was produced in the same manner as in Example 1.
  • the aluminum foil, low-density polyethylene film (20 ⁇ m) and low-density polyethylene film (30 ⁇ m) of the composite 1 obtained in Example 1 were thermally bonded to produce a laminate.
  • Example 13 Using the laminates produced in Example 13 and Comparative Example, 200 ml-containing tetrabrick (trademark) type liquid food containers were prepared, filled with water, and the performance of those containers was evaluated in the following manner. evaluated.
  • the container molded using the laminate according to each example has superior shape retention even at high temperatures, compared to the container molded using the conventional laminate according to the comparative example. Also, it shows stable results as a container without leakage even at high temperatures. Since the polycyclic olefin copolymer-containing layer is excellent in heat resistance, no container leakage occurs even at a high temperature. advantage
  • the rigidity, gloss, transparency, and pull resistance of plastics and the like conventionally used by the polycyclic olefin copolymer-containing layer constituting the inner layer of the paper layer are obtained.
  • the contact, heat resistance, moisture resistance, etc. are improved, and the appearance and appearance of the container are improved.
  • the polycyclic olefin copolymer-containing layer has good compatibility with the polyethylene layer constituting the inner layer of the laminate of the present invention, and improves and improves the adhesion of the polyethylene inner layer. As a result, the resulting container shows good sealing properties.
  • the container molded with the layered polycyclic olefin copolymer-containing layer has excellent shape retention. Therefore, the workmanship of the container is good.
  • the polycyclic olefin copolymer-containing layer is provided in the constituent layer of the container wall, it is not necessarily clear in theory, but it complements the mechanical strength of the paper layer and maintains the container shape well. Therefore, the appearance of the container is good.
  • the polycyclic olefin copolymer-containing layer is not only excellent in heat resistance, but also at a high temperature of about 130 ° C., even when a treatment is performed such that the containers come into contact with each other on the outer surface. It is most suitable for packaging containers that require autocreping and retorting without causing damage or heat history inside the container wall.
  • the inside of the container and the container itself are protected by the layer containing the polycyclic olefin copolymer, even if the content of the filling is strongly acidic, the barrier properties of aluminum foil and the like are maintained, and the Even at high temperatures, no container leakage occurs.
  • the innermost layer of the laminate of the present invention as a linear low-density polyethylene layer obtained by polymerization with a meta-aqueous catalyst, a linear low-density polyethylene layer and a polycyclic olefin copolymer are formed on the inner side. Are appropriately mixed and sealed, so that the sealing property of the container formed from the packaging laminate can be improved.
  • a linear low-density polyethylene layer obtained by polymerization with a meta-mouth catalyst is constituted as the innermost layer. Excellent container openability.
  • the polycyclic olefin copolymer of the layer constituting the container formed from the laminate of the present invention has a very good moisture barrier property, and the moisture barrier property of the container is improved.
  • the oxygen trapping performance of the barrier layer inside the polycyclic olefin copolymer layer can be maintained and protected.
  • a complete barrier function can be added to the container.
  • the container of the present invention is used as a container for liquid foods such as milk, juice, coffee, and liquor.

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  • Laminated Bodies (AREA)

Abstract

L'invention concerne un stratifié pour matériau d'emballage comportant une couche extérieure comprenant au moins une couche de papier et, à l'intérieur, une couche barrière et une couche intérieure comprenant au moins une couche renfermant un copolymère oléfinique polycyclique. Dans ce stratifié, la couche de papier et la couche barrière intérieure peuvent revêtir une fonction de protection contre les détériorations du matériau d'emballage, y compris lorsque ce dernier est soumis à un traitement à température élevée.
PCT/JP2001/009705 2000-11-09 2001-11-07 Stratifie pour materiau d'emballage WO2002038376A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002212711A AU2002212711A1 (en) 2000-11-09 2001-11-07 Laminate for packaging material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000342272 2000-11-09
JP2000-342272 2000-11-09

Publications (1)

Publication Number Publication Date
WO2002038376A1 true WO2002038376A1 (fr) 2002-05-16

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ID=18816863

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/009705 WO2002038376A1 (fr) 2000-11-09 2001-11-07 Stratifie pour materiau d'emballage

Country Status (2)

Country Link
AU (1) AU2002212711A1 (fr)
WO (1) WO2002038376A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014058336A (ja) * 2012-09-18 2014-04-03 Dainippon Printing Co Ltd 紙カップ

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134794A (ja) * 1994-11-14 1996-05-28 Mitsui Petrochem Ind Ltd 環状オレフィン系樹脂で被覆された表面加工紙
EP0972634A2 (fr) * 1998-07-14 2000-01-19 Sumitomo Bakelite Co., Ltd. Laminé, récipient multicouche et récipient fermé hermétiquement
JP2000062109A (ja) * 1998-08-19 2000-02-29 Dainippon Printing Co Ltd 紙容器用積層シート

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134794A (ja) * 1994-11-14 1996-05-28 Mitsui Petrochem Ind Ltd 環状オレフィン系樹脂で被覆された表面加工紙
EP0972634A2 (fr) * 1998-07-14 2000-01-19 Sumitomo Bakelite Co., Ltd. Laminé, récipient multicouche et récipient fermé hermétiquement
JP2000062109A (ja) * 1998-08-19 2000-02-29 Dainippon Printing Co Ltd 紙容器用積層シート

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014058336A (ja) * 2012-09-18 2014-04-03 Dainippon Printing Co Ltd 紙カップ

Also Published As

Publication number Publication date
AU2002212711A1 (en) 2002-05-21

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