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WO2002038377A1 - Recipient creux en polyethylene moule par extrusion - Google Patents

Recipient creux en polyethylene moule par extrusion Download PDF

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Publication number
WO2002038377A1
WO2002038377A1 PCT/JP2001/009707 JP0109707W WO0238377A1 WO 2002038377 A1 WO2002038377 A1 WO 2002038377A1 JP 0109707 W JP0109707 W JP 0109707W WO 0238377 A1 WO0238377 A1 WO 0238377A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
density polyethylene
container
polyethylene
linear low
Prior art date
Application number
PCT/JP2001/009707
Other languages
English (en)
Japanese (ja)
Inventor
Peter Frisk
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 AU2002212713A priority Critical patent/AU2002212713A1/en
Publication of WO2002038377A1 publication Critical patent/WO2002038377A1/fr

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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
    • B32B27/06—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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins

Definitions

  • the present invention relates to a polyethylene extruded hollow molded container, and more particularly, to a polyethylene extruded hollow molded container for liquid foods and the like which exhibits excellent barrier resistance and aroma-preserving properties and is environmentally friendly.
  • high-density polyethylene containers have been used as extruded hollow molded containers for liquid foods such as milk, juice, coffee, and alcoholic beverages, but the fragrance of high-grade liquid foods is maintained during storage. It is strongly required to be done. High-grade liquid foods that emphasize fragrance, such as fragrance components that are oxidized during storage, absorbed by the materials of surrounding containers, or transferred to the filling in the materials of surrounding containers, and the fragrance is Will be impaired.
  • the oxygen barrier layer of the fragrance component to protect the fragrance component from oxidation etc. is provided as close as possible to the contents that are high-grade liquid foods. No.
  • the shielding layer is also important for the strength of the container, but if the shielding layer is too thick, the container will become brittle.
  • a container with a very high-density polyethylene layer, and a container with a low-density polyethylene layer inside the high-density polyethylene layer Further, a container provided with an inner layer composed of a high-density polyethylene layer and a barrier layer such as an ethylene-butyl alcohol copolymer or nylon 6 has been tried.
  • An object of the present invention is to provide a polyethylene extruded hollow molded container that is filled with a high-grade liquid food or the like that exhibits excellent barrier resistance and fragrance retention, is environmentally friendly, and emphasizes good fragrance. .
  • the present inventors have conducted intensive studies to improve the above-mentioned problems, and as a result, a polyamide resin layer containing an aromatic polyamide resin inside a high-density polyethylene layer containing already used high-density polyethylene which has been recycled, etc.
  • the inventors have found that the object of the present invention can be achieved by providing a linear low-density polyethylene layer inside, and have reached the present invention.
  • the present invention relates to a laminate comprising a polycyclic olefin copolymer-containing layer, a high-density polyethylene-containing layer, an adhesive layer, an aromatic polyamide resin-containing layer, an adhesive layer, and a linear low-density polyethylene layer laminated in that order.
  • the linear low-density polyethylene layer forms the innermost layer of a container, and has a gist of a polyethylene extruded hollow molded container (hereinafter, referred to as a container 1), which is characterized by being formed.
  • the present invention comprises a laminate in which a high-density polyethylene-containing layer, an adhesive layer, an aromatic polyamide resin-containing layer, an adhesive layer, a polycyclic olefin copolymer-containing layer, and a linear low-density polyethylene layer are laminated in this order.
  • the straight-line low-density polyethylene layer forms the innermost layer of the container, and has a gist of a polyethylene extruded hollow molded container (hereinafter, referred to as container 2), which is characterized by being formed.
  • the present invention comprises a laminate in which a high-density polyethylene-containing layer, an adhesive layer, an aromatic polyamide resin-containing layer, an adhesive layer, and a layer containing a linear low-density polyethylene and a polycyclic olefin copolymer are laminated in that order.
  • the layer containing the linear low-density polyethylene and the polycyclic olefin copolymer forms the innermost layer of a container, and is characterized by a polyethylene extruded hollow molded container (hereinafter, referred to as container 3). You.
  • the container 13 of the present invention is characterized in that the high-density polyethylene-containing layer comprises a mixture layer of unused (purged) high-density polyethylene and used (recycled) high-density polyethylene.
  • the container 13 of the present invention is characterized in that the aromatic polyamide resin-containing layer is a polyamide resin layer containing at least 70% by mass of an aromatic polyamide resin.
  • the container 13 of the present invention is characterized in that the linear low-density polyethylene is a linear low-density polyethylene produced by using a metallocene catalyst.
  • the container 1, the container 2 and the container 3 of the present invention are characterized in that the polycyclic olefin copolymer is a copolymer of a polycyclic olefin and ethylene or ⁇ -olefin.
  • the high-density polyethylene of the high-density polyethylene layer forming the container 13 of the present invention is a melt flow index ( ⁇ FI: 190 ° C., load: 2.16 kg) used for polyethylene bottles. Can be used for about 0.1-3 g / 10 minutes.
  • the high-density polyethylene may be only virgin (unused) high-density polyethylene, but a mixture of virgin (unused) high-density polyethylene and recycled (used) high-density polyethylene forms an environmental burden. Desirable in terms of reduction. Examples of the high-density polyethylene used include those that can be separated and collected from discarded high-density polyethylene and that can be recycled, and those that are discharged as scrap from factories and the like.
  • the content of the high-density polyethylene used in the mixture is preferably 30% by mass or less.
  • the thickness of the high-density polyethylene layer is preferably 300-500 ⁇ .
  • the aromatic polyamide resin-containing layer forming the container 13 of the present invention is preferably a mixture layer of an aromatic polyamide resin and a polyamide resin other than the aromatic polyamide resin.
  • the content of the group III polyamide resin is preferably at least 70% by mass.
  • aromatic polyamide resin examples include polyamide MX D6, polyhexamethylene diamine terephthalate (polyamide 6T), polyhexamethylene diamine isophthalamide, and a polyamide containing a xylene group. D6 is particularly preferred.
  • Polyamide resins other than aromatic polyamide resins include aliphatic polyamides such as polyamide 4-6, polyamide 6, polyamide 6-6, polyamide 6_10, polyamide 6_12, polyamide 11 and polyamide 12. And polyamide 6 and polyamide 6-6 are particularly preferred.
  • the thickness of the aromatic polyamide resin-containing layer is preferably from 30 to 50 ⁇ .
  • the linear low-density polyethylene layers forming the containers 1 and 2 of the present invention and the linear low-density polyethylene and the polycyclic olefin copolymer-forming layer forming the container 3 have a linear low density.
  • high-density polyethylene include ⁇ -olefins having ethylene and a comonomer having 4 to 10 carbon atoms, for example, 1-butene, 1-hexene, 4-methyl-1- Although those manufactured by copolymerizing pentene, 1-heptene, 1_ otaten, etc. can be used, linear low-density polyethylene (mLLDPE) manufactured by using a meta-mouth catalyst is particularly preferable. .
  • mLLDPE is an ⁇ -olefin having ethylene and a comonomer having 418 carbon atoms, preferably 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-otaten in the presence of a meta-mouth catalyst. It is preferable to use a polymer produced by copolymerizing ⁇ -olefin having 6 or more carbon atoms, such as ⁇ -olefin.
  • the above-mentioned meta-mouth 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 7-electron cyclopentenyl group or a substituted cyclopentenyl group.
  • a cocatalyst such as an aluminum compound such as an alkyl aluminoxane, an alkyl aluminum, an aluminum octalide, or an alkyl amine dihalide.
  • m LLD ⁇ ⁇ has a narrow molecular weight distribution of 2 to 4 in weight average molecular weight and number average molecular weight, and has a density of 0.900 to 0.925 gZcm 3 , but a density of 0.900 to 0.90. Those having 915 g / cm 3 are preferred.
  • MF I (190T: load 2.16 kg) force S 10-20 gZl 0 min is preferable.
  • Such mLLDP E has very strong strength and good processability, and by using this, Shows very good shape retention.
  • the thickness of the linear low-density polyethylene layer is preferably from 200 to 500 m.
  • the polycyclic olefin copolymer layer forming the containers 1 and 2 of the present invention and the polycyclic olefin copolymer of the layer containing the linear low-density polyethylene and the polycyclic olefin copolymer forming the container 3 are And copolymers of polycyclic olefins and ethylene or ⁇ -olefin, copolymers of polycyclic olefins and monocyclic olefins, and copolymers of polycyclic olefins and non-conjugated gens.
  • a copolymer of polycyclic olefin and ethylene or olefin, particularly a copolymer of polycyclic olefin and ethylene is 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.
  • the non-conjugated gen 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 mol 0/0, especially 4 0 8 0 mole 0 do things Shi preferred Rere.
  • the polycyclic olefin copolymer-containing layer forming the containers 1 and 2 may be a mixture layer with another substance, but is preferably a single layer of the polycyclic olefin copolymer.
  • a substance that can be mixed with the polycyclic olefin copolymer polyethylene, polypropylene, ethylene-propylene copolymer, polyolefin such as polybutene-1, particularly polyethylene is preferable.
  • polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene.
  • the other substance is preferably 50% by mass or less, particularly preferably 40% by mass or less.
  • the content of the polycyclic olefin copolymer in the layer containing the linear low-density polyethylene and the polycyclic olefin copolymer forming the container 3 is 50% by mass or less, particularly 60-80% by mass. It is preferred that Linear low-density polyethylene, especially m LLDPE, and polycyclic olefin copolymers are easily mixed and compatible.
  • the thickness of the polycyclic olefin copolymer layer forming the containers 1 and 2 is preferably from 200 to 500; m. Further, the thickness of the layer containing the linear low-density polyethylene and the polycyclic olefin copolymer forming the container 3 is preferably 20000 ⁇ .
  • the adhesive layer for bonding each layer of each container of the present invention is an adhesive that can be used when manufacturing a laminate constituting each container by hollow extrusion molding, for example, an acrylic resin Adhesives, modified polyolefin adhesives, ethylene-vinyl acetate copolymer, polyamide adhesives, epoxy resin adhesives, and the like.
  • an acrylic resin Adhesives modified polyolefin adhesives, ethylene-vinyl acetate copolymer, polyamide adhesives, epoxy resin adhesives, and the like.
  • the acryl resin-based adhesive include polymers and copolymers of acrylic acid or methacrylic acid or alkyl esters thereof.
  • modified polyolefin adhesive examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, nadic acid, and nadic acid anhydride such as polyethylene and polypropylene, or anhydrides thereof. In the presence of an organic peroxide.
  • the thickness of the adhesive layer is preferably from 30 to 50 ⁇ .
  • Each container of the present invention can be manufactured by melting and extruding the above-mentioned components forming each layer by an in-die laminating method or an out-of-die laminating method so as to form the hollow layers so that the above-mentioned layers are in that order. it can.
  • the thickness of each container of the present invention is usually set at 600 ⁇ m—1.2 mm.
  • polycyclic olefin copolymer-containing layer containing polycyclic olefin copolymer 60 mol% of polycyclic olefin component, 40 mol% of ethylene component
  • high-density polyethylene MFI: 2 gZl 0 Min.
  • modified polyolefin adhesive trade name: Vineel 428, manufactured by Dupont
  • a polycyclic olefin copolymer containing layer (60 mol% of a polycyclic olefin component, 40 mol% of an ethylene component) so as to provide a layer containing a polycyclic olefin copolymer of 30 zm between the adhesive layer and the mLLDPE layer.
  • a bottle-shaped hollow molded body (container 2) was formed in the same manner as in Example 1 except that the above-mentioned was used.
  • Example 2 Example 5 was repeated except that a mixture of 65% by mass of the m LLDPE and 35% by mass of the polycyclic olefin copolymer was used instead of the mLLDPE and the polycyclic olefin copolymer used in Example 1. In the same manner as in 1, a pottle-shaped hollow molded body (container 3) having a thickness of 200 m of the mixture layer of the mLLDPE and the polycyclic olefin copolymer was formed.
  • Example 1 The high-density polyethylene used in Example 1 was melt-extruded to form a pot-like hollow molded body having a thickness of 1.0 mm.
  • Polyamide 6 was prepared in the same manner as in Example 1 except that the polyolefin copolymer was not used, polyamide 6 was used instead of the polyamide MXD 6 and polyamide 6 mixture, and low-density polyethylene was used instead of mLLDPE.
  • the barrier resistance of the 20 bottles obtained in Examples and Comparative Examples in which a bottle-shaped hollow molded article having a layer thickness of 50 im and a low-density polyethylene layer of 500 m was molded was evaluated for the oxygen permeation amount. (Cc ⁇ 24 hours ⁇ 101.3 kPaZ1 container) was evaluated. The results are as follows.
  • the container 1 of the present invention shows excellent barrier properties and fragrance retention properties by the aromatic polyamide resin of the aromatic polyamide resin-containing layer, and the linear low density polyethylene of the innermost layer, especially mL LDPE, Due to its extremely high strength, the container shows good shape retention and durability when the liquid filling is filled at a high temperature, even if its thickness is less than 250 m.
  • the containers 2 and 3 of the present invention exhibit the same effects as those of the container 1, and the polycyclic olefin copolymer of the layers constituting the containers has a very good moisture barrier property.
  • the moisture barrier property has been improved, and since it has very good transparency, it can be made into a transparent container comparable to glass, and it has excellent compatibility with linear low-density polyethylene, especially mL LDPE.
  • the bonding between the linear low-density polyethylene layer and the polycyclic olefin copolymer layer does not require an adhesive, and the shape retention and durability of containers when filled at high temperatures Is further improved.
  • the hollow container according to the present invention has a significantly improved dross on the surface of the container as compared with a conventional high-density polyethylene hollow molded container, and thus has a very good appearance.
  • the polycyclic olefin copolymer is highly rigid, which improves the rigidity of the container.
  • the hollow container of the present invention has improved rigidity, luster, transparency, resistance to tearing, heat resistance, moisture resistance, etc. of conventionally used plastics and the like by the polycyclic olefin copolymer-containing layer. Means better appearance and appearance of the container.
  • the polycyclic olefin copolymer-containing layer has, for example, good compatibility with the constituent polyethylene layer, and improves and improves the adhesion of the polyethylene layer. As a result, the resulting container shows good integrity without delamination.
  • the container molded with the layered polycyclic olefin copolymer-containing layer has excellent shape retention. Therefore, the workmanship of the container is good.
  • a layer containing a polycyclic olefin copolymer is provided as a constituent layer of the container wall, it is not necessarily clear in theory, but the mechanical strength of the other layers is complemented and the container shape is improved. Hold well. Therefore, the appearance of the container is good.
  • the polycyclic olefin copolymer-containing layer not only has excellent heat resistance, but also does not cause damage to the inside of the vessel wall, heat history, etc. even at a high temperature of about 130 ° C, and has an autoclave treatment and a retort. Ideal for packaging containers that need to be processed.
  • the integrity of the container is maintained even if the content of the filling is strong or corrosion-resistant, and the container leaks, especially at high temperatures. Does not occur.
  • the polycyclic olefin copolymer of the layer constituting the container of the present invention has a very good moisture barrier property, and the moisture barrier property of the container is improved.
  • the oxygen scavenging performance of the barrier layer inside the polycyclic olefin copolymer layer can be maintained and protected. With the oxygen barrier property of the barrier layer inside the container wall, a complete barrier function can be added to the container.
  • the hollow molded container of the present invention is used as a molded container for liquid foods such as milk, juice, coffee, and alcoholic beverages.

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  • Laminated Bodies (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)

Abstract

L'invention concerne un récipient creux en polyéthylène moulé par extrusion formant un produit en couches, qui comprend une couche constituée d'un copolymère d'oléfine polyacrylique, une couche constituée d'une résine polyamide aromatique, une couche adhésive, et une couche de polyéthylène faible densité, ladite couche de polyéthylène faible densité étant la couche intérieure du récipient. Ledit récipient possède d'excellentes propriétés de barrière, de conservation d'arôme, et respecte l'environnement. On l'utilise pour l'emballage, par exemple, d'aliments liquides de qualité élevée pour lesquels l'arôme est important.
PCT/JP2001/009707 2000-11-09 2001-11-07 Recipient creux en polyethylene moule par extrusion WO2002038377A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002212713A AU2002212713A1 (en) 2000-11-09 2001-11-07 Extrusion-molded hollow container made of polyethylene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000342292 2000-11-09
JP2000-342292 2000-11-09

Publications (1)

Publication Number Publication Date
WO2002038377A1 true WO2002038377A1 (fr) 2002-05-16

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PCT/JP2001/009707 WO2002038377A1 (fr) 2000-11-09 2001-11-07 Recipient creux en polyethylene moule par extrusion

Country Status (2)

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AU (1) AU2002212713A1 (fr)
WO (1) WO2002038377A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0985914A (ja) * 1995-09-27 1997-03-31 Toppan Printing Co Ltd 多層プラスチック容器
JP2000263727A (ja) * 1999-03-15 2000-09-26 Dainippon Printing Co Ltd 積層材およびそれを使用した包装用容器
EP1043235A2 (fr) * 1999-04-07 2000-10-11 Owens-Brockway Plastic Products Inc. Conteneur multicouche

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0985914A (ja) * 1995-09-27 1997-03-31 Toppan Printing Co Ltd 多層プラスチック容器
JP2000263727A (ja) * 1999-03-15 2000-09-26 Dainippon Printing Co Ltd 積層材およびそれを使用した包装用容器
EP1043235A2 (fr) * 1999-04-07 2000-10-11 Owens-Brockway Plastic Products Inc. Conteneur multicouche

Also Published As

Publication number Publication date
AU2002212713A1 (en) 2002-05-21

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