EP0423270A1 - Materiau etanche aux gaz - Google Patents

Materiau etanche aux gaz

Info

Publication number
EP0423270A1
EP0423270A1 EP19900905544 EP90905544A EP0423270A1 EP 0423270 A1 EP0423270 A1 EP 0423270A1 EP 19900905544 EP19900905544 EP 19900905544 EP 90905544 A EP90905544 A EP 90905544A EP 0423270 A1 EP0423270 A1 EP 0423270A1
Authority
EP
European Patent Office
Prior art keywords
gas
polyolefin
acid
sealed material
material according
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP19900905544
Other languages
German (de)
English (en)
Inventor
Hanneli Seppänen
Christer BERGSTRÖM
Leila Kettunen
Helge Lindström
Maria Stjernberg
Olli Tuominen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Neste Oyj
Original Assignee
Neste Oyj
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
Priority claimed from FI891756A external-priority patent/FI86874C/fi
Priority claimed from FI891757A external-priority patent/FI86875C/fi
Application filed by Neste Oyj filed Critical Neste Oyj
Publication of EP0423270A1 publication Critical patent/EP0423270A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention concerns a gas-sealed material and products containing gas-sealed material.
  • the invention concerns a gas-sealed material containing polyolefin, polyvinyl alcohol, and polyamide, and products containing the same.
  • Polyolefins are widely used, for instance, in packaging industry in manufacturing various film products. Advantages of polyolefins are in particular appropriate strength and water resistance properties. Among the drawbacks may be mentioned permeability to certain gases and liquids, concerning particularly oxygen and hydrocarbon dissolvents.
  • multiple layer film 20 structures in which materials of different layers are selected for a given purpose. Therefore, such multiple layer structures may contain layers which form a good barrier against gases, such as oxygen, and layers which provide other properties for the product, such as strength properties.
  • multiple layer structures may 25 contain- other layers which generate, for instance, adhesion between different layers. Products of this kind are, however, expensive to manufacture.
  • Polyvinyl alcohol is one of such polymers which has a low oxygen 30 permeability property. Said property has most often been utilized in olefin-vinyl alcohol random-mixed polymers and in olefin-vinyl alcohol segment-mixed polymers. It is also known in the art to manufacture products containing polyolefin and polyvinyl alcohol in the form of mixtures, which have a low oxygen permeability and which therefore 35 a re exceedingly appropriate for manufacturing e.g. packaging films. In the Finnish patent application No. 87-5772 is disclosed a mixture of polyolefin and polyvinyl alcohol, moreover containing optionally 1 plasticizers. When polyolefin and polyvinyl alcohol are mixed in molten state, a mixture is obtained which is composed of two phases, a continuous phase and a dispersed phase, when the diameter of the particles in the dispersed phase is small enough, totally transparent
  • the mixing is usually carried out in a separate compounding phase prior to the extrusion of the end product.
  • the object of the present invention is a material containing polyolefin, polyvinyl alcohol, and polyamide, in which the moisture sensitivity of the product regarding oxygen sealing is reduced, the lightness of the product has increased, and the need for plasticizers
  • the invention concerns a gas-sealed material containing polyolefin, vinyl alcohol polymer, and polyamide.
  • the gas-sealed material of the invention is characterized in that it is produced by mixing in molten state 3 to 60 per cent by weight of polyolefin, and
  • internally plasticized vinyl alcohol polymer refers to a vinyl alcohol polymer which contains polyglycol groups (polyether
  • plasticizer groups are connected into a chain by copolymerizing, grafting or by means of reactive compounding.
  • One such internally plasticized polyvinyl alcohol is Vinex polymer (trade name, Air Products and Chemicals Inc.) , in which for comonomer is 5 used an ester of methacrylic acid and of polyethylene glycol.
  • Said internally plasticized vinyl alcohol polymers may be manu- 1 factured, for instance in the manner as disclosed in the US. patent No. 4,709,999. Said patent presents that the product is provided with good oxygen sealing and that it is appropriate for cast, in ⁇ jection moulding and extrusion products, and that it is characterized
  • Q polyamide mixture of the invention is advantageously such in which in the poly(alkyleneoxy)ester derivative for use as a comonomer the alkylene of the alcohol component is an ethylene or propylene, and the acid component is an acrylic acid or methacrylic acid.
  • Said modified vinyl alcohol polymers may be manufactured, for instance, by poly- ⁇ J5 merizing vinyl acetate monomer and poly(alkyleneoxy)aerylate co ⁇ monomer, and hydrolyzing the copolymer thus obtained in order to produce an internally plasticized vinyl alcohol polymer.
  • the quantity of the internally plasticized vinyl alcohol polymer in 0 the polyethylene-polyvinyl alcohol-polyamide mixture of the invention may be in the range from 10 to 96 per cent by weight, preferably in the range of from 30 to 60 per cent by weight. In some instances, it may be preferable to substitute part of the internally plasticized vinyl alcohol polymer used in the gas-sealed material for unmodified 5 polyvinyl al ⁇ hol if the purpose of the product allows.
  • the polyolefin in a gas-sealed material of the invention may be based on homopolymers or copolymers of the olefins. Therefore, it may be low density polyethylene (LDPE) , medium density polyethylene 0 (MDPE) or high density polyethylene (HDPE) , polypropylene, or poly- butene.
  • LDPE low density polyethylene
  • MDPE medium density polyethylene 0
  • HDPE high density polyethylene
  • the polyolefin may also be a copolymer of ethylene together with other olefins, such as propylene, butene, hexene and octene.
  • the polyolefin may also be an olefin-ester copolymer, such as ethylene-vinyl acetate copolymer, ethylene-acrylate-ester copolymer, 5 or ethylene-methacrylate ester copolymer, or it may be a thermoplastic olefin-based elastomer, such as EP or EPD rubber.
  • the polyolefin in the process according to the invention may also be a homopolymer or a copolymer of the above-mentioned olefins which has been modified with the aid of carboxylic acid. To such a modified olefin polymer is copolymerized or grafted 0.1 to 10 per cent by weight of carboxylic acid.
  • the carboxylic acid may comprise any unsaturated carboxylic acid or carboxylic acid anhydride which can be grafted or copolymerized in polyolefin.
  • examples of such acids are, for instance, acrylic acid, methacrylic acid, maleic acid fumaric acid, itaconic acid, crotonic acid, sorbic acid, and anhydrides of the afore-mentioned acids. In grafting or in copolymerizing one or several above acids may be used.
  • the polyolefin grafted or copolymer ⁇ ized with carboxylic acid may also be a mixture containing a poly ⁇ olefin modified in the manner described above, and un unmodified polyolefin.
  • the quantity of the polyolefin in the gas-sealed material of the invention may be in the range 1 to 99 per cent by weight, but preferably in the range from 30 to 60 per cent by weight of the quantity of the entire mixture.
  • a third component in a gas-sealed material of the invention is amorphous polyamide.
  • the quantity of amorphous polyamide in a material of the invention may be selected from the range 1 to 50 per cent by weight.
  • the amorphous polyamide enhances the viscosity and deep-drawing properties of the mixture of polyolefin and polyvinyl alcohol co ⁇ polymer.
  • the gas-sealed polyolefin/PVA/PA mixture of the invention can be manufactured mixing the polyolefin component, vinyl alcohol/copolymer component, and polyamide component in a melt mixer simultaneously as a dry mixture, premixed in solid or in molten state, or then various components are added separately.
  • various products may be prepared by combining the mixture with polyolefins, other plastics or other materials, such as fibre-based materials.
  • Multiple layer products may be manufactured by coextrusion, (co)extrusion
  • products containing a gas-sealed material of the invention e.g. films, moulded-blown bottles and containers, plates, tubes, injection
  • P02 - LT.DPE linear low density polyethylene
  • melt index 0.5 g/10 min (190°C)
  • PVA2 - polyvinyl alcohol, viscosity 4, hydrolysis degree 88%
  • PA1 amorphous polyamide, degree of crystallization
  • PA2 - polyamide 6 ⁇ J5 PA3 - polyamide 11 PA4 - polyamide 12
  • Polyolefin/PVA/polyamide mixtures of the invention were prepared by 25 mixing polyolefin, polyvinyl alcohol and polyamide, in molten state, with the aid of a Berstorff mixer which was provided with a flat film nozzle.
  • the temperature profile was 130 to 190 to 200 to 210 to 210 to 210 to 220 to 220 to 215 to 215 to 210.
  • the production rate was 10 kilograms per hour.
  • the thicknesses of the obtained films were 150 to 200 ⁇ m.
  • the com ⁇ pounds thereof are presented in the accompanying Table 1 A.
  • the properties of the films are presented in the accompanying Table 1 B.
  • the oxygen permeability values of the films are calculated for 25 ⁇ m 35 thickness.
  • the lightness of the films was measured as a so-called yellowness index conforming to the standard ASTM D 1925-70 with the Ultra Scan apparatus of Hunter Lab. TABLE ]L A
  • the quantity of polyvinyl alcohol includes 4.5% glycerol of the PVA quantity.
  • Polyolefin/PVA/polyamide mixtures of the invention were prepared by mixing polyolefin, polyvinyl alcohol and polyamide, in molten state, with the aid of a Berstorff mixer which was provided with a flat film nozzle.
  • the temperature profile was 130 to 190 to 200 to 210 to 210 to 210 to 220 to 220 to 215 to 210.
  • the production rate was 10 kilograms per hour.
  • the thicknesses of the obtained films were 140 to 190 ⁇ m.
  • the com- pounds thereof are presented in the accompanying Table 2 A.
  • the properties of the films are presented in the accompanying Table 2 B.
  • the oxygen permeability values of the films are calculated for 25 ⁇ m thickness.
  • the lightness of the films was measured as a so-called yellowness index conforming to the standard ASTM D 1925-70 with the Ultra Scan apparatus of Hunter Lab.
  • the quantity of polyvinyl alcohol includes 4.5% glycerol of the PVA quantity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention se rapporte à un matériau étanche aux gaz, qui contient une polyoléfine, un alcool polyvinylique et un polyamide. On fabrique un tel matériau en mélangeant à l'état de fusion 3 à 60 % en poids d'une polyoléfine, 10 à 96 % en poids d'un polymère d'alcool vinylique intérieurement plastifié, et 1 à 50 % en poids d'un polyamide amorphe.
EP19900905544 1989-04-13 1990-04-11 Materiau etanche aux gaz Withdrawn EP0423270A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FI891756A FI86874C (fi) 1989-04-13 1989-04-13 Gastaett material, som innehaoller invaendigt mjukgjord polyvinylalkohol
FI891757 1989-04-13
FI891757A FI86875C (fi) 1989-04-13 1989-04-13 Gastaett material, som innehaoller invaendigt mjukgjord polyvinylalkohol
FI891756 1989-04-13

Publications (1)

Publication Number Publication Date
EP0423270A1 true EP0423270A1 (fr) 1991-04-24

Family

ID=26158539

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900905544 Withdrawn EP0423270A1 (fr) 1989-04-13 1990-04-11 Materiau etanche aux gaz

Country Status (5)

Country Link
EP (1) EP0423270A1 (fr)
JP (1) JPH04500538A (fr)
AU (1) AU5417190A (fr)
CA (1) CA2032122A1 (fr)
WO (1) WO1990012063A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990012062A1 (fr) * 1989-04-13 1990-10-18 Neste Oy Materiau etanche aux gaz
EP0483695B1 (fr) * 1990-10-29 1996-10-02 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Composition de résine et son utilisation
FI922378A (fi) * 1991-06-19 1992-12-20 Chevron Res & Tech Polymerblandningar av polyolefin, polyamid och en modifierad etylenkopolymer
FI922379A (fi) * 1991-06-19 1992-12-20 Chevron Res & Tech Syreavlaegsnande homogena blandningar av en modifierad polyolefin, en oxiderbar polymer och ett metallsalt
US5939158A (en) * 1998-03-24 1999-08-17 E.I. Du Pont De Nemours And Company Laminar articles of polyolefin and nylon/polyvinyl alcohol blend and methods related thereto
DE10351563A1 (de) * 2003-11-03 2005-06-02 Kuraray Specialities Europe Gmbh Verfahren zur Herstellung von Polyamid-Polyvinylalkohol-Formkörpern

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4575532A (en) * 1984-02-08 1986-03-11 Norchem, Inc. Polyvinyl alcohol alloys and method of making the same
US4708999A (en) * 1985-04-26 1987-11-24 Air Products And Chemicals, Inc. Copolymers of vinyl acetate and poly(alkyleneoxy) acrylates
US4824904A (en) * 1986-03-31 1989-04-25 Kuraray Co., Ltd. Resin compositions, laminates and block copolymers
JPS63182313A (ja) * 1987-01-16 1988-07-27 エアー．プロダクツ．アンド．ケミカルス．インコーポレーテッド 酢酸ビニル−アクリレート系共重合体
GB8704385D0 (en) * 1987-02-25 1987-04-01 Du Pont Canada Injection moulding of articles
NZ225901A (en) * 1987-08-24 1990-04-26 Du Pont Blends of ethylene-vinyl alcohol polymer and a minor amount of amorphous polyamide
US4952628A (en) * 1987-08-24 1990-08-28 E. I. Du Pont De Nemours And Company Barrier blends based on amorphous polyamide and ethylene/vinyl alcohol, unaffected by humidity
US4950513A (en) * 1988-03-17 1990-08-21 E. I. Du Pont De Nemours And Company Laminar articles of a polyolefin and a nylon/polyvinyl alcohol blend

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9012063A1 *

Also Published As

Publication number Publication date
WO1990012063A1 (fr) 1990-10-18
CA2032122A1 (fr) 1990-10-14
JPH04500538A (ja) 1992-01-30
AU5417190A (en) 1990-11-05

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