CA2032120A1 - Gas-sealed material - Google Patents
Gas-sealed materialInfo
- Publication number
- CA2032120A1 CA2032120A1 CA002032120A CA2032120A CA2032120A1 CA 2032120 A1 CA2032120 A1 CA 2032120A1 CA 002032120 A CA002032120 A CA 002032120A CA 2032120 A CA2032120 A CA 2032120A CA 2032120 A1 CA2032120 A1 CA 2032120A1
- Authority
- CA
- Canada
- Prior art keywords
- polyamide
- gas
- polyolefin
- acid
- sealed material
- 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.)
- Abandoned
Links
Classifications
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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)
Abstract
Abstract of Disclosure The present invention concerns a gas-sealed material, containing polyolefin, polyvinyl alcohol and amide. Said material is manufac-tured by mixing in molten state 3 to 60 per cent by weight of poly-olefin, 10 to 96 per cent by weight of internally plasticized vinyl alcohol polymer, and 1 to 50 per cent by weight of polyamide.
Description
2 ~ 3 ~
W O 90/12062 PCT/F190/00l06 1 Gas-sealed ma~erial The present invention concerns a gas-s2aled material and products containing gas-sealed material. In particular, th~ in~ention concerns a gas-sealed material con~aining polyolefin, polyvinyl alcohol, and polyamide, and products con~aining the sa~e.
1~ Polyolefins are widely used, for instance, in packaging indus~ry in ~anufacturing vario~s fil~ products. Ad~antages of polyolefins are in particular appropriate strength and water resistance properties.
Among the drawbacks may be mentioned permeabili~y to cer~ain gases and liquids, concerning particularly oxygen and hydrocarbon dissolven~s.
Therefore, ~he usability of polyolefin films is limited to packaging certain substances, such as foodstuffs, in which minor oxygen perme-2bility is required.
It is customary to use in packaging indus~ry multiple layer i`ilm ~0 struc~ures in which materials of dif~erent layers are selected for a given purpose. Therefore, such multiple layer structures may contain layers whicn form a good barrier against gases, such as oxygen, and layers whioh provide o~her properCies for the product, such as strength properties. In addition, mul~iple layer structures may contain other layers which generate, for instance, adhesion be~ween different layers. Products of this kind are, however, expensive to manufacture. -.
~ Polyvinyl alcohol is one of such polymers which has a low oxygen permeability property. Said property has most often been utilized inolefin-vinyl alcohol random-mixed polymers and in olefin-vinyl alcohol segment-mixed polymers. It is also known in the art to manufacture prodllcts containing polyolefin and polyvinyl alcohol in ~he form of mixtures, which have a low oxygen permeability and which ~herei'ore are exceedingly appropriate for manufacturing e.g. packaging films.
In the Finnish patent application No. 87-5772 is disclosed a mixture of polyolefln and polyvinyl alcohol, moreover containing optionally ` . ~ '. ' ., ': , ' ' ' '; ' ' ~
1 plaseici~ers WhPn polyolefin and polyvinyl alcuhol are mixed in molten state, a mixture is ob~ained which is composed of ~wo phases, a coneinuous phase and a dispersed phase. ~hen the diameter of the par~icles in the dispersed phase is small enough, totally transparent films are obtained. The mixing is usually carried out in a separate compounding phase prior to the extrusion of the end product.
When the PVA in the mixture of polyolefin and PVA establishes a continuous phase, a good sealing is provided in the product, for . 10 instance oxygen sealingj.and the product is bright and stable, in spite of two phases, both in molten and in solid state, and it is easy to soften by adding plasticizers.
In the EP patent publicizing print No. 280455-A discloss oxygen-sealed materials containing polyethylene, a polyolei'in containing carboxyl groups, and a third polymer which is incompatible with the polyethylene. Said third polymer may be, as stated in the publication, a polyamide (PA), ethylene-vinyl alcohol copolymer, polyvinyl alco-hol (P~A), palyester, or a mixture thereof, although no examples of mixtures, for instance mixtures of polyamide and polyvinyl alcohol, are pres2nted. A mixture of polyethylene and PVA is not useful because of its brittleness, neither is the mixture of polyethylene and polyamide useful because of its barrier properties. If, instead, polyethylene is mixed with PVA and polyamide, the product is both sealed and viscous.
Although polyolefin-PVA-PA mixtures are generally speaking provided with good oxygen sealing properties in dry circumstances, in moist circumsta~ces their oxygen sealing property reduGes significan~ly, so that they are sensitive to moisture. In addition, when mixtures oi polyolefins, PVA, and polyamide are mixed in molten state, partial dissolution of PVA and colouring of the product take place. When plasticizers are used, their stability in the mixture is no~ as good as possible because of whlch migration oi plasticizers cake pl.ace in the product. One more drawback in con~entional PE/PVA/PA mixtures is that the melt index oiJ the product is not low enough.
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W O 90/12062 2 0 3 212 ~ PCT/FIg0/00106 1 The object of the present invention is a material containin~
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 has been eliminated, and, in addition, the strength properties of the films manufactured from the product, such as viscosity, tensile strength, impact tensile strength, and resistance to rupture, have improved.
lC As taught by the invention, it h s been surprisingly found that when certain internally plasticized polyvinyl alcohol copolymers and polyamide are mixed in moltRn state with polyolefins, such products are obtained which have a lighter colour and the oxy~en sealing gained in which is considerably less sensitive to mois~ure than in using con~entional polyvinyl alcohol, and in addition, the strength properties of the films manufactured from the product are be~ter than in using ordinary polyvinyl alcohol and polyamide.
Therefore, the invention conc.erns a gas-sealed material containing polyolefin, polyvinyl alcohol, and polyamide. The gas~sealed material of the invention is characterized in that said material is produced by mixing in molten state 3 to 60 per cent by weight of polyolefin, 10 to 96 per cent by weight of internally plasticized vinyl alcohol polymer, and 1 to 50 per cent by weight of polyamide.
The term 'internally plasticized vinyl alcohol polymer' refers to a vinyl alcohol polymer which contains poly~lycol groups (polyzther groups) or other groups plasticizing polyvinyl alcohol in the side c~ains thereof. Said plasticizer groups are connected into a chain by copolymerizin~, grafting or by means of reactive compounding. One such internally plastizied polyvinyl alcohol is Vinex polymer (trade name, Air Products and Chemicals Inc.), in which for comonomer is used an ester of Me~hacrylic acid and of polyethylene glycol.
W O 90/12062 PCT/F190/00l06 1 Gas-sealed ma~erial The present invention concerns a gas-s2aled material and products containing gas-sealed material. In particular, th~ in~ention concerns a gas-sealed material con~aining polyolefin, polyvinyl alcohol, and polyamide, and products con~aining the sa~e.
1~ Polyolefins are widely used, for instance, in packaging indus~ry in ~anufacturing vario~s fil~ products. Ad~antages of polyolefins are in particular appropriate strength and water resistance properties.
Among the drawbacks may be mentioned permeabili~y to cer~ain gases and liquids, concerning particularly oxygen and hydrocarbon dissolven~s.
Therefore, ~he usability of polyolefin films is limited to packaging certain substances, such as foodstuffs, in which minor oxygen perme-2bility is required.
It is customary to use in packaging indus~ry multiple layer i`ilm ~0 struc~ures in which materials of dif~erent layers are selected for a given purpose. Therefore, such multiple layer structures may contain layers whicn form a good barrier against gases, such as oxygen, and layers whioh provide o~her properCies for the product, such as strength properties. In addition, mul~iple layer structures may contain other layers which generate, for instance, adhesion be~ween different layers. Products of this kind are, however, expensive to manufacture. -.
~ Polyvinyl alcohol is one of such polymers which has a low oxygen permeability property. Said property has most often been utilized inolefin-vinyl alcohol random-mixed polymers and in olefin-vinyl alcohol segment-mixed polymers. It is also known in the art to manufacture prodllcts containing polyolefin and polyvinyl alcohol in ~he form of mixtures, which have a low oxygen permeability and which ~herei'ore are exceedingly appropriate for manufacturing e.g. packaging films.
In the Finnish patent application No. 87-5772 is disclosed a mixture of polyolefln and polyvinyl alcohol, moreover containing optionally ` . ~ '. ' ., ': , ' ' ' '; ' ' ~
1 plaseici~ers WhPn polyolefin and polyvinyl alcuhol are mixed in molten state, a mixture is ob~ained which is composed of ~wo phases, a coneinuous phase and a dispersed phase. ~hen the diameter of the par~icles in the dispersed phase is small enough, totally transparent films are obtained. The mixing is usually carried out in a separate compounding phase prior to the extrusion of the end product.
When the PVA in the mixture of polyolefin and PVA establishes a continuous phase, a good sealing is provided in the product, for . 10 instance oxygen sealingj.and the product is bright and stable, in spite of two phases, both in molten and in solid state, and it is easy to soften by adding plasticizers.
In the EP patent publicizing print No. 280455-A discloss oxygen-sealed materials containing polyethylene, a polyolei'in containing carboxyl groups, and a third polymer which is incompatible with the polyethylene. Said third polymer may be, as stated in the publication, a polyamide (PA), ethylene-vinyl alcohol copolymer, polyvinyl alco-hol (P~A), palyester, or a mixture thereof, although no examples of mixtures, for instance mixtures of polyamide and polyvinyl alcohol, are pres2nted. A mixture of polyethylene and PVA is not useful because of its brittleness, neither is the mixture of polyethylene and polyamide useful because of its barrier properties. If, instead, polyethylene is mixed with PVA and polyamide, the product is both sealed and viscous.
Although polyolefin-PVA-PA mixtures are generally speaking provided with good oxygen sealing properties in dry circumstances, in moist circumsta~ces their oxygen sealing property reduGes significan~ly, so that they are sensitive to moisture. In addition, when mixtures oi polyolefins, PVA, and polyamide are mixed in molten state, partial dissolution of PVA and colouring of the product take place. When plasticizers are used, their stability in the mixture is no~ as good as possible because of whlch migration oi plasticizers cake pl.ace in the product. One more drawback in con~entional PE/PVA/PA mixtures is that the melt index oiJ the product is not low enough.
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W O 90/12062 2 0 3 212 ~ PCT/FIg0/00106 1 The object of the present invention is a material containin~
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 has been eliminated, and, in addition, the strength properties of the films manufactured from the product, such as viscosity, tensile strength, impact tensile strength, and resistance to rupture, have improved.
lC As taught by the invention, it h s been surprisingly found that when certain internally plasticized polyvinyl alcohol copolymers and polyamide are mixed in moltRn state with polyolefins, such products are obtained which have a lighter colour and the oxy~en sealing gained in which is considerably less sensitive to mois~ure than in using con~entional polyvinyl alcohol, and in addition, the strength properties of the films manufactured from the product are be~ter than in using ordinary polyvinyl alcohol and polyamide.
Therefore, the invention conc.erns a gas-sealed material containing polyolefin, polyvinyl alcohol, and polyamide. The gas~sealed material of the invention is characterized in that said material is produced by mixing in molten state 3 to 60 per cent by weight of polyolefin, 10 to 96 per cent by weight of internally plasticized vinyl alcohol polymer, and 1 to 50 per cent by weight of polyamide.
The term 'internally plasticized vinyl alcohol polymer' refers to a vinyl alcohol polymer which contains poly~lycol groups (polyzther groups) or other groups plasticizing polyvinyl alcohol in the side c~ains thereof. Said plasticizer groups are connected into a chain by copolymerizin~, grafting or by means of reactive compounding. One such internally plastizied polyvinyl alcohol is Vinex polymer (trade name, Air Products and Chemicals Inc.), in which for comonomer is used an ester of Me~hacrylic acid and of polyethylene glycol.
3~ Said internally plasticized vinyl alcohol polymers may be manu-factured, for instance in the manner as disclosed in the US. patent No. 4,709,999. Sald patent presents that the product is provided .
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2~32~0 1 with good oxygen sealing and that it is appropriate for cast, ln-jection moulding and extrusion produces, and that it is characteri7ed by good water solubiliey, and therefore, it is particularly ~ell appropriate for manufac~uring films which are required to possess water solubility.
The vinyl alcohol polymer used in the polyolefin/polyvinyL alcohol/
polyamide mixture of the inven~ion is advaneageously 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 polyrners may be manufaceured, for instance, by poly-merizin~, vinyl acetate monomer and poly(alkyleneoxy)acrylate co-monomer, and hydrolyzin~ the copolymer thus obtained in order to produce an internally plasticized vinyl alcohol polymer.
The quanticy of the internally plasticized vinyl alcohol polymer in the polyethylene-polyvinyl alcohol-polyamide mixture of the invention may be in the range from lO to 96 per cent by weighr, preferably in ~0 t-h~ 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 polyvinyl alcohol if the purpose of the product allows.
The polyolefin in a gas-sealed material of the invention may be based on homopolymers or copolyrners of the olefins. Therefore, it may be low density polyethylene (LDPE), medium density polyethylene (MDPE) or high density polyethylene (HDPE), polypropylene, or poly-butene. The polyolefin may also be a copolymes 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-vînyl acecate copolyrner, ethylene-acrylate-ester copol~ner, or ethylene-methacrylate ester copol~ner, or ie may be a ehermoplastic olefin-based elastomer, such as EP or EPD rubber.
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The polyolefin in che process according to the Lnveneion mav also be a homopoly~er or a copolymer oP the above-mentioned olePins which .
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W O 90/12062 2032~ 2~ PCT/F190/00106 l 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, cro~onic 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-lC ized with carboxylic acid ~ay 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 from 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 poly-~0 amide. For the polyamide, for instance the following polyamides may be used: polyamide 6, polyamide 8, polyamide 10, polyamide 11, polv-amide 12, polyamide 6.6, polyaMide 6.10, and polyamide 12-elastomers, or mixtures thereof. The quantity of polymer in the material of the invention may be selected from the range 1 to 50 per cent by weigh~
The polyamide enhances the viscosity and deep-drawing properties of the mixture of polyolefin and the poly~inyl alcohol copolymer.
The gas-sealed polyolefin/PVA/PA mixture of the invention can be 3~ manufactured mixing the polyolefin component modified with thz acid, the vinyl alcohol/copolymer component, and the polyamide component in a melt mixer simultaneously as a dry mixture, premixed in solid or Ln molten staee, or then various componenc5 are added separately.
3~ From the polyolefin/PVA/PA mixture of the invention various products may be prepared by combining the mixture with polyolefins, other plastics or othsr ma~erials, such as fibre-based materials. Multiple . . , . ~. - :
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`' : , ~' " ' ' W O 90/12062 2 ~ 3 212 ~ p~r/Fl9o/oolo6 1 layer products may be manufactured by coeY.~rUqiO~, (co)extrusion coaeing, (co)ex~rusion la~ination, adhesion lamination, or using other techniques, a~d these production procedures may also be combined.
As products containing a gas sealed material of the invention, e.g.
films, moulded-blown bottles and containers, plates, tubes, injection moulded vessels, deep-drawn fil~s and plates, liquid packaging card-board, etc. may be mentioned. Sealed multiple-layer products are ~enerally used for packaging foodstuffs, when oxygen sealing is - 10 desired also in moist circu~stances, but the sealing of carbon dioxide or some other gas may be thought of. In addition, fat, chemical and odour sealing may be desired both in various foodstuff packages and technical products.
In the following non-limitin~ examples the manufacturing, properties and application of the polyol~fin/~inyl alcohol polymer/polyamide ~ixture of the inven~ion in sealed on~-layer products are described.
The oxy~en per~eability of the films was measured with an OX-TRAN
1000 apparatus (ASTM D 3985). The polyolefins, the vinyl alcohol po-lymers and polyamides used in the tests of the e~amples are presentedin the table below.
~olvolefins ~5 POl - LDPE (lo~ density polyethylene), molten index (MI) 1.8 g/10 min (190C) PO2 - LLDPE (linear low density polyethylene), grafted with 0.25 per cent by weight of fumaric acid, melt index 0.5 g/10 min (190C) P03 - EAA (ethylene-acrylic acid copolymer), acrylic acid content 6.5~, melt index 9.5 g/10 min (190C) ' ' ' ": ' ' :' ' ' ' W O 90/12062 2 ~ 3 ~12 ~ pcr/Fl9otoo1o6 PVAl - vinyl aloohol copolymer wherein the comono~er is an ester of a methacrylic acid and a polyechy-lene glycol (Vinex 4004, trade name, Air Products and Chemicals Inc.) PVA2 - polyvinyl alcohol, viscosi~y 4, degree of hydro-lysis 88 Pol~amides PAl - polyamide 6 PA2 - polyamide 11 PA3 - polyamide 12 Plasticizer glycerol, degree of purity 99 ~0 Exam~le 1 Polyolefin/PVA/polyamide mixtures of the i~vention were prepared by mixing polyolefin, pol~inyl alcohol and polyamide, in molten state, with the aid of a Berstorff ~ixer which was provided with a fla~
film nozzle. The temperature profile was 130 to 190 ~o 200 to 210 to 210 to 210 to 220 to 215 to 210. The production rate was 10 kilogra~s -per hour.
The thickn~sses oi the obtained fil~s were 120 to 170 ~m. The com-pounds thereof are presented in the acco~panying Table 1 A. The properties of the films are: presented in the acco~panying Table 1 B. :
The oxygen per~eability 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.
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` ' : ~ " ' ' Test Polw invl alcohol Polvolefin Polvamide type % by weight type ~ by w. type ~ by w.
_ _ _ 1 PVAl 60 POl 30 PAl 10 2 PVAl 60 POl 30 PA2 10 3 PVAl 60 POl 30 PA3 10 4 PVAl 30 POl 40 PA3 30 PVA2 60 POl 40 - -_ Note. In test 5 the quantity of polyvinyl alcohol includes 4.5 glycerol of the PVA quantity.
ThBL~1 P, __ _ 15 Test Oxygen permeabil. Y~lL4Y;9~ Tensile (mlL_-x24h~bar) index, thick- s~rength O~RH 90%RH ness ~m mach./trans dir. dir.
MPa ~Pa r 1 0.10 239 0.90 12118.5 15.9 ~ 2 0.15 l.S 0.90 14217.8 12.5 3 0.18 2.0 0.95 15017.9 13.5 4 0.20 2.4 0.89 14739.7 32.5 0.20 10.0 10.9 17210.0 7.0 .~
Exam~le 2 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 wi~h a flat 30 film nozzlP. The temperature profile was 130 tO 190 to 200 to 210 ~o 210 to 210 to 220 to 220 to 215 to 210. The production rate was 10 kilograms per hour.
The thicknesses of the obtalned ~ilms were 130 to 210 ~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 permeabili~y values of the films are calculated for 25 ~m . ~ ` '~-', ' ', "
W O 90/12062 ~ ~ 3 ~ ~ ~ PCTtF190/0~106 1 thickness. The lightness of the films was measured as a so-called yellowness index conforming to the standard ASTM D 1925-70 with the ~ltra Scan appara~us of Hunter Lab.
Test Pol winvl alcohol P_lyolefin ~Qly~mide type % by weight type ~ by w. type % by w.
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l PVAl 80 P02 lO PAl lO
10 2 PVAl 70 P02 3 PAl 27 3 PVAl 70 P02 3 PA2 27 4 PVAl 70 P02 3 PA3 27 PVAl 60 P02 30 PAl lO
6 PVAl 30 P02 20 PAl 50 7 PVAl lO P02 60 PAl 30 8 PVAl 60 POl 30 PAl lO
15 9 PVAl 60 P03 30 PAl lO
lO PVAl 60 P02 30 PAl lO
ll PVA2 60 POl 40 - -12 PVA2 70 P02 30 ~ -13 PVA2 70 POl 20 PAllO
14 PVA2 70 POl 20 PAllO
PVA2 70 POl 30 - -~0 ~ - - _ _ , ... . .
Note. In tests ll, 12 and 14, the quantity of polyvinyl alcohol in-cIudes 4.5% glycerol of the PVA quantity.
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W O 90/12062 2 0 3 %12 ~ PCT/FI90/00106 1 TABLE 2_P.
Test Oxygen per~eabil. Yellowness f~l~m--x24hxbar~ index, thick- strength 0%RH90~RH ness ~m mach./trans dir. dir.
MPa MPa ,, .
1 0.20.8 0.80 140 20.4 19.0 2 l.03.4 0.70 130 33.9 27.5 3 1.13.8 0.70 131 31.2 25.5 4 1.23.5 0.70 145 30.4 23.2 1.11.5 0.53 1.70 22.8 24.8 6 5 20 0.85 172 39.1 27.2 7 3.5S0 O.gO 186 31.5 30.1 8 1.21.6 0.76 192 21.4 20.8 9 0.92.2 0.82 171 20.9 19.7 1.18.8 30.1 164 23.6 21.0 11 0.210.0 10.9 211 10.0 7.0 ~5 12 0.29.6 11.5 198 14.0 ll.0 13 0.87.6 11.2 172 17.7 12.3 14 0.88.1 11.0 145 17.8 8.4 0.29.7 11.0 163 10.3 8.7 The results indicate that by using vinyl alcohol copolymer for the polyvinyl alcohol in the mixture, in which the comonomer is an ester of methacrylic acid and polyethylene ~,lycol (Vlnex 4004), a product is obtained ~he low oxygen permeabllity of which chan~es very little in a moist vicinity. The colour of the product (yellownessj is very 2S low. Polyamide addition increases the t?nsile stren~,th of the product both in =achine and transversal direction.
:
3;
, :
:
- : , ~
: . :
.. . .
- : , . ,' ': ' ' ~ " ~ ' ' :
.
. , , ~. .. .
2~32~0 1 with good oxygen sealing and that it is appropriate for cast, ln-jection moulding and extrusion produces, and that it is characteri7ed by good water solubiliey, and therefore, it is particularly ~ell appropriate for manufac~uring films which are required to possess water solubility.
The vinyl alcohol polymer used in the polyolefin/polyvinyL alcohol/
polyamide mixture of the inven~ion is advaneageously 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 polyrners may be manufaceured, for instance, by poly-merizin~, vinyl acetate monomer and poly(alkyleneoxy)acrylate co-monomer, and hydrolyzin~ the copolymer thus obtained in order to produce an internally plasticized vinyl alcohol polymer.
The quanticy of the internally plasticized vinyl alcohol polymer in the polyethylene-polyvinyl alcohol-polyamide mixture of the invention may be in the range from lO to 96 per cent by weighr, preferably in ~0 t-h~ 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 polyvinyl alcohol if the purpose of the product allows.
The polyolefin in a gas-sealed material of the invention may be based on homopolymers or copolyrners of the olefins. Therefore, it may be low density polyethylene (LDPE), medium density polyethylene (MDPE) or high density polyethylene (HDPE), polypropylene, or poly-butene. The polyolefin may also be a copolymes 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-vînyl acecate copolyrner, ethylene-acrylate-ester copol~ner, or ethylene-methacrylate ester copol~ner, or ie may be a ehermoplastic olefin-based elastomer, such as EP or EPD rubber.
3~ ~
The polyolefin in che process according to the Lnveneion mav also be a homopoly~er or a copolymer oP the above-mentioned olePins which .
~ ., . ~, .
.
' ' ' . ' . '' :
,~ .. . .
W O 90/12062 2032~ 2~ PCT/F190/00106 l 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, cro~onic 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-lC ized with carboxylic acid ~ay 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 from 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 poly-~0 amide. For the polyamide, for instance the following polyamides may be used: polyamide 6, polyamide 8, polyamide 10, polyamide 11, polv-amide 12, polyamide 6.6, polyaMide 6.10, and polyamide 12-elastomers, or mixtures thereof. The quantity of polymer in the material of the invention may be selected from the range 1 to 50 per cent by weigh~
The polyamide enhances the viscosity and deep-drawing properties of the mixture of polyolefin and the poly~inyl alcohol copolymer.
The gas-sealed polyolefin/PVA/PA mixture of the invention can be 3~ manufactured mixing the polyolefin component modified with thz acid, the vinyl alcohol/copolymer component, and the polyamide component in a melt mixer simultaneously as a dry mixture, premixed in solid or Ln molten staee, or then various componenc5 are added separately.
3~ From the polyolefin/PVA/PA mixture of the invention various products may be prepared by combining the mixture with polyolefins, other plastics or othsr ma~erials, such as fibre-based materials. Multiple . . , . ~. - :
~:` ,' ' : ' ' , ~' '', , ' .
. . .- . ~ , : .
`' : , ~' " ' ' W O 90/12062 2 ~ 3 212 ~ p~r/Fl9o/oolo6 1 layer products may be manufactured by coeY.~rUqiO~, (co)extrusion coaeing, (co)ex~rusion la~ination, adhesion lamination, or using other techniques, a~d these production procedures may also be combined.
As products containing a gas sealed material of the invention, e.g.
films, moulded-blown bottles and containers, plates, tubes, injection moulded vessels, deep-drawn fil~s and plates, liquid packaging card-board, etc. may be mentioned. Sealed multiple-layer products are ~enerally used for packaging foodstuffs, when oxygen sealing is - 10 desired also in moist circu~stances, but the sealing of carbon dioxide or some other gas may be thought of. In addition, fat, chemical and odour sealing may be desired both in various foodstuff packages and technical products.
In the following non-limitin~ examples the manufacturing, properties and application of the polyol~fin/~inyl alcohol polymer/polyamide ~ixture of the inven~ion in sealed on~-layer products are described.
The oxy~en per~eability of the films was measured with an OX-TRAN
1000 apparatus (ASTM D 3985). The polyolefins, the vinyl alcohol po-lymers and polyamides used in the tests of the e~amples are presentedin the table below.
~olvolefins ~5 POl - LDPE (lo~ density polyethylene), molten index (MI) 1.8 g/10 min (190C) PO2 - LLDPE (linear low density polyethylene), grafted with 0.25 per cent by weight of fumaric acid, melt index 0.5 g/10 min (190C) P03 - EAA (ethylene-acrylic acid copolymer), acrylic acid content 6.5~, melt index 9.5 g/10 min (190C) ' ' ' ": ' ' :' ' ' ' W O 90/12062 2 ~ 3 ~12 ~ pcr/Fl9otoo1o6 PVAl - vinyl aloohol copolymer wherein the comono~er is an ester of a methacrylic acid and a polyechy-lene glycol (Vinex 4004, trade name, Air Products and Chemicals Inc.) PVA2 - polyvinyl alcohol, viscosi~y 4, degree of hydro-lysis 88 Pol~amides PAl - polyamide 6 PA2 - polyamide 11 PA3 - polyamide 12 Plasticizer glycerol, degree of purity 99 ~0 Exam~le 1 Polyolefin/PVA/polyamide mixtures of the i~vention were prepared by mixing polyolefin, pol~inyl alcohol and polyamide, in molten state, with the aid of a Berstorff ~ixer which was provided with a fla~
film nozzle. The temperature profile was 130 to 190 ~o 200 to 210 to 210 to 210 to 220 to 215 to 210. The production rate was 10 kilogra~s -per hour.
The thickn~sses oi the obtained fil~s were 120 to 170 ~m. The com-pounds thereof are presented in the acco~panying Table 1 A. The properties of the films are: presented in the acco~panying Table 1 B. :
The oxygen per~eability 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.
.
. :
.
' - - .' :' : ',~ : ' ' .
` ' : ~ " ' ' Test Polw invl alcohol Polvolefin Polvamide type % by weight type ~ by w. type ~ by w.
_ _ _ 1 PVAl 60 POl 30 PAl 10 2 PVAl 60 POl 30 PA2 10 3 PVAl 60 POl 30 PA3 10 4 PVAl 30 POl 40 PA3 30 PVA2 60 POl 40 - -_ Note. In test 5 the quantity of polyvinyl alcohol includes 4.5 glycerol of the PVA quantity.
ThBL~1 P, __ _ 15 Test Oxygen permeabil. Y~lL4Y;9~ Tensile (mlL_-x24h~bar) index, thick- s~rength O~RH 90%RH ness ~m mach./trans dir. dir.
MPa ~Pa r 1 0.10 239 0.90 12118.5 15.9 ~ 2 0.15 l.S 0.90 14217.8 12.5 3 0.18 2.0 0.95 15017.9 13.5 4 0.20 2.4 0.89 14739.7 32.5 0.20 10.0 10.9 17210.0 7.0 .~
Exam~le 2 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 wi~h a flat 30 film nozzlP. The temperature profile was 130 tO 190 to 200 to 210 ~o 210 to 210 to 220 to 220 to 215 to 210. The production rate was 10 kilograms per hour.
The thicknesses of the obtalned ~ilms were 130 to 210 ~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 permeabili~y values of the films are calculated for 25 ~m . ~ ` '~-', ' ', "
W O 90/12062 ~ ~ 3 ~ ~ ~ PCTtF190/0~106 1 thickness. The lightness of the films was measured as a so-called yellowness index conforming to the standard ASTM D 1925-70 with the ~ltra Scan appara~us of Hunter Lab.
Test Pol winvl alcohol P_lyolefin ~Qly~mide type % by weight type ~ by w. type % by w.
.
l PVAl 80 P02 lO PAl lO
10 2 PVAl 70 P02 3 PAl 27 3 PVAl 70 P02 3 PA2 27 4 PVAl 70 P02 3 PA3 27 PVAl 60 P02 30 PAl lO
6 PVAl 30 P02 20 PAl 50 7 PVAl lO P02 60 PAl 30 8 PVAl 60 POl 30 PAl lO
15 9 PVAl 60 P03 30 PAl lO
lO PVAl 60 P02 30 PAl lO
ll PVA2 60 POl 40 - -12 PVA2 70 P02 30 ~ -13 PVA2 70 POl 20 PAllO
14 PVA2 70 POl 20 PAllO
PVA2 70 POl 30 - -~0 ~ - - _ _ , ... . .
Note. In tests ll, 12 and 14, the quantity of polyvinyl alcohol in-cIudes 4.5% glycerol of the PVA quantity.
~' ZS
::
3~ : :
- .
: ~ :
...... , ~ .. . .
.
. - ~ ;. : .: ~ :
W O 90/12062 2 0 3 %12 ~ PCT/FI90/00106 1 TABLE 2_P.
Test Oxygen per~eabil. Yellowness f~l~m--x24hxbar~ index, thick- strength 0%RH90~RH ness ~m mach./trans dir. dir.
MPa MPa ,, .
1 0.20.8 0.80 140 20.4 19.0 2 l.03.4 0.70 130 33.9 27.5 3 1.13.8 0.70 131 31.2 25.5 4 1.23.5 0.70 145 30.4 23.2 1.11.5 0.53 1.70 22.8 24.8 6 5 20 0.85 172 39.1 27.2 7 3.5S0 O.gO 186 31.5 30.1 8 1.21.6 0.76 192 21.4 20.8 9 0.92.2 0.82 171 20.9 19.7 1.18.8 30.1 164 23.6 21.0 11 0.210.0 10.9 211 10.0 7.0 ~5 12 0.29.6 11.5 198 14.0 ll.0 13 0.87.6 11.2 172 17.7 12.3 14 0.88.1 11.0 145 17.8 8.4 0.29.7 11.0 163 10.3 8.7 The results indicate that by using vinyl alcohol copolymer for the polyvinyl alcohol in the mixture, in which the comonomer is an ester of methacrylic acid and polyethylene ~,lycol (Vlnex 4004), a product is obtained ~he low oxygen permeabllity of which chan~es very little in a moist vicinity. The colour of the product (yellownessj is very 2S low. Polyamide addition increases the t?nsile stren~,th of the product both in =achine and transversal direction.
:
3;
, :
:
- : , ~
: . :
Claims (10)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A gas-sealed material, containing polyolefin, polyvinyl alcohol, and polyamide, characterized in that said material is prepared by mixing in molten state 3 to 60 per cent by weight of polyolefin, l0 to 96 per cent by weight of internally plasticized vinyl alcohol polymer, and l to 50 per cent by weight of polyamide. - 2. Gas-sealed material according to claim l, characterized in that in the vinyl alcohol polymer chains contain polyglycol groups (poly-ether groups) as side groups.
- 3. Gas-sealed material according to claim l or 2, characterized in that the polyvinyl alcohol is a copolymer in which the comonomer is an unsaturated poly(alkyleneoxy)ester derivative.
- 4. Gas-sealed material according to claim 3, characterized in that said alkylene is an ethylene or propylene and that the acid component of said ester is an acrylic acid or methacrylic acid.
- 5. A gas-sealed mixture according to any one of the preceding claims, characterized in that the polyvinyl alcohol contains in a mixture an unmodified polyvinyl alcohol, and vinyl alcohol polymer according to claims 2 to 4.
- 6. A gas-sealed material according to any one of the preceding claims, characterized in that the polyolefin is a low density polyethylene (LDPE), medium density polyethylene (MDPE) or high density poly-ethylene (HDPE), polypropylene or polybutene, or ethylene copolymer with propylene, butene, hexene and octene, or an olefin/ester co-polymer, such as ethylene-vinyl-acetate copolymer, ethylene-acrylate ester copolymer or ethylene methacrylate ester copolymer, EP rubber, EPD rubber, or other thermoplastic olefin-based elastomer.
- 7. A gas-sealed material according to any one of the preceding claims characterized in that the polyolefin is modified by copolymerizing or grafting thereto 0.l to 10 per cent by weight of carboxyl acid selected from the group of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, sorbic acid, and anhydrides of the afore-mentioned acids.
- 8. Gas-sealed material according to any one of the preceding claims, characterized in that the polyolefin is formed from a mixture of an unmodified polyolefin and a polyolefin modified with carboxyl acid
- 9. Gas-sealed material according to any one of the preceding claims, characterized in that the polyamide has been selected from among the group of polyamide 6, polyamide 8, polyamide 10, polyamide 11, poly-amide 12, polyamide 6.6, polyamide 6.10, and polyamide 12 elastomers, or mixtures thereof.
- 10. Products containing gas-sealed material according to any one of the preceding claims.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI891754A FI86872C (en) | 1989-04-13 | 1989-04-13 | Gas-sealed material containing internally plasticized polyvinyl alcohol |
| FI891755 | 1989-04-13 | ||
| FI891754 | 1989-04-13 | ||
| FI891755A FI86873C (en) | 1989-04-13 | 1989-04-13 | GASTAETT MATERIAL, SOM INNEHAOLLER INVAENDIGT MJUKGJORD POLYVINYLALCOOL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2032120A1 true CA2032120A1 (en) | 1991-10-12 |
Family
ID=26158538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002032120A Abandoned CA2032120A1 (en) | 1989-04-13 | 1990-04-11 | Gas-sealed material |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0420954A1 (en) |
| JP (1) | JPH04500537A (en) |
| AU (1) | AU631205B2 (en) |
| CA (1) | CA2032120A1 (en) |
| WO (1) | WO1990012062A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI922378A (en) * | 1991-06-19 | 1992-12-20 | Chevron Res & Tech | POLYMER BEARING OF POLYOLEFIN, POLYAMID OCH EN MODIFIEDAD ETHLENICOPOLYMER |
| JPH08283570A (en) * | 1995-04-17 | 1996-10-29 | Sumitomo Chem Co Ltd | Resin composition |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3975463A (en) * | 1971-06-18 | 1976-08-17 | Toyo Seikan Kaisha Limited | Molded structures containing crystalling polyolefin saponified ethylene vinyl acetate copolymer and carbonyl containing copolymers |
| JPS6014695B2 (en) * | 1979-03-06 | 1985-04-15 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Layered molded product and its manufacturing method |
| 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 |
| JPH0813898B2 (en) * | 1985-08-06 | 1996-02-14 | 呉羽化学工業株式会社 | Smoke-disposable food packaging film |
| US4824904A (en) * | 1986-03-31 | 1989-04-25 | Kuraray Co., Ltd. | Resin compositions, laminates and block copolymers |
| EP0327551B1 (en) * | 1986-10-20 | 1991-04-10 | AlliedSignal Inc. | Blends of polyamide, polyolefin, and ethylene vinyl alcohol copolymer |
| JPS63182313A (en) * | 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 | Vinyl acetate-acrylate base copolymer |
| GB8704385D0 (en) * | 1987-02-25 | 1987-04-01 | Du Pont Canada | Injection moulding of articles |
| 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 |
| AU5417190A (en) * | 1989-04-13 | 1990-11-05 | Neste Oy | Gas-sealed material |
-
1990
- 1990-04-11 CA CA002032120A patent/CA2032120A1/en not_active Abandoned
- 1990-04-11 JP JP50579790A patent/JPH04500537A/en active Pending
- 1990-04-11 EP EP19900905541 patent/EP0420954A1/en not_active Withdrawn
- 1990-04-11 AU AU54161/90A patent/AU631205B2/en not_active Ceased
- 1990-04-11 WO PCT/FI1990/000106 patent/WO1990012062A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU5416190A (en) | 1990-11-05 |
| WO1990012062A1 (en) | 1990-10-18 |
| AU631205B2 (en) | 1992-11-19 |
| EP0420954A1 (en) | 1991-04-10 |
| JPH04500537A (en) | 1992-01-30 |
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