CA2032122A1 - Gas-sealed material - Google Patents
Gas-sealed materialInfo
- Publication number
- CA2032122A1 CA2032122A1 CA 2032122 CA2032122A CA2032122A1 CA 2032122 A1 CA2032122 A1 CA 2032122A1 CA 2032122 CA2032122 CA 2032122 CA 2032122 A CA2032122 A CA 2032122A CA 2032122 A1 CA2032122 A1 CA 2032122A1
- Authority
- CA
- Canada
- 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.)
- Abandoned
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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
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- 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
Abstract of Disclosure The present invention concerns a gas-sealed material, containing polyolefin, polyvinyl alcohol and polyamide. The material is manu-factured 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 amorphous polyamide.
Description
2~32~22 ~~VO 90/12063 PCT/F190/00107 1 Gas-sealed mat~rial The present invention concerns a gas-sealed material and products containing gas-sealed material. In particular, ~he invention concerns a gas-sealed material containing polyolefin, polyvinyl alcohol, and polyamide, and products containing the same.
Polyolefins are widely used, for ins~ance, in packaging industry in manufacturing various film products. Ad~antages 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.
Therefore, the usability of polyolefin films is limited to packa~ing certain substances, such as fcods~uffs, in which minor oxygen perme-ability is r~-quired.
It is customary to use in packa~ing intus~ry mul~iple layer film structures in which materials of different layers are selected for a given purpose. Therefore, s~lch 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. In addition, mu}tiple layer structures may contain other layers which generate, for instance, adhesion between differeat layers. Products of this kind are, however t expensive to manufacture.
Polyvinyl alcohol is one of such polymers which has a low oxygen 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 ma~ufacture products containing polyolefin and polyvinyl alcohol in the form of mixturesj which have a low oxygen permeabllity and which therefore are exceedingly appropriate for manufacturing e.g. packagln~ films.
In the~Finnish patent application No. 87-5772 is disclosed a mixture of polyolefin and polyvinyl alcohol, moreover containing optionally . ~
".~
: ~ ' ~:. ' .
2~32~2~
W O 90/12063 PCT/Fl90/00107 1 plasticizers. When polyoleiln and polyvinyl alcohol are mixed in molten s~ate, a mixture is obtained which is composed of two phases, a continuous phase and a dispersed phase. When the diameter of the par~icles in the dispersed phase is small enough, to~ally transparent films are obtained. The mixing is usually carried out in a separa~e compounding phase prior to the extrusion of the end product.
Uhen the PVA in the mixture of polyoleiin and PVA establishes a continuous phase, a good sealing is provided in the product, for instance oxygen sealin~, and the product is bright and stable, in spite of ~wo 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 discloses oxygen-sealed materials containing polyethylene, a polyolefin containing carboxyl groups, and a third polymer which is incompatible with the polyethylene. Said third polymer may be, as stated in ~he publication, a polyamide (PA), e~hylene-vinyl alcohol copoly~er, polyvinyl alcohol (PVA), polyester, or a mixture thereof, although no exa~ples of mixtures, for instance mixtures of polyamide and polyvinyl alcohol is presented. A mixture of polyethylene and PVA is not useful because of its brittleness, neither is the mixture of polyethylene and poly-amide useful because o its barrier properties. If, instead, poly-ethylene is mixed with PVA and polyamide, the product is both sealed ~5 and vi8cous.
Although polyolefin-PVA-PA mixtures are ~enerally speakin~ provided with good oxygen sealing properties in dry circumstances, in moist circumstances their oxygen sealing property reduces signifieantly,
Polyolefins are widely used, for ins~ance, in packaging industry in manufacturing various film products. Ad~antages 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.
Therefore, the usability of polyolefin films is limited to packa~ing certain substances, such as fcods~uffs, in which minor oxygen perme-ability is r~-quired.
It is customary to use in packa~ing intus~ry mul~iple layer film structures in which materials of different layers are selected for a given purpose. Therefore, s~lch 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. In addition, mu}tiple layer structures may contain other layers which generate, for instance, adhesion between differeat layers. Products of this kind are, however t expensive to manufacture.
Polyvinyl alcohol is one of such polymers which has a low oxygen 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 ma~ufacture products containing polyolefin and polyvinyl alcohol in the form of mixturesj which have a low oxygen permeabllity and which therefore are exceedingly appropriate for manufacturing e.g. packagln~ films.
In the~Finnish patent application No. 87-5772 is disclosed a mixture of polyolefin and polyvinyl alcohol, moreover containing optionally . ~
".~
: ~ ' ~:. ' .
2~32~2~
W O 90/12063 PCT/Fl90/00107 1 plasticizers. When polyoleiln and polyvinyl alcohol are mixed in molten s~ate, a mixture is obtained which is composed of two phases, a continuous phase and a dispersed phase. When the diameter of the par~icles in the dispersed phase is small enough, to~ally transparent films are obtained. The mixing is usually carried out in a separa~e compounding phase prior to the extrusion of the end product.
Uhen the PVA in the mixture of polyoleiin and PVA establishes a continuous phase, a good sealing is provided in the product, for instance oxygen sealin~, and the product is bright and stable, in spite of ~wo 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 discloses oxygen-sealed materials containing polyethylene, a polyolefin containing carboxyl groups, and a third polymer which is incompatible with the polyethylene. Said third polymer may be, as stated in ~he publication, a polyamide (PA), e~hylene-vinyl alcohol copoly~er, polyvinyl alcohol (PVA), polyester, or a mixture thereof, although no exa~ples of mixtures, for instance mixtures of polyamide and polyvinyl alcohol is presented. A mixture of polyethylene and PVA is not useful because of its brittleness, neither is the mixture of polyethylene and poly-amide useful because o its barrier properties. If, instead, poly-ethylene is mixed with PVA and polyamide, the product is both sealed ~5 and vi8cous.
Although polyolefin-PVA-PA mixtures are ~enerally speakin~ provided with good oxygen sealing properties in dry circumstances, in moist circumstances their oxygen sealing property reduces signifieantly,
3~ so that they are sensitive to moisture. In addition, when mixtures of polyolefins, PVA, and polyamide are mi~ed in molten state, partial dissolution of PVA and colouring of the product take place. ~hen plasticizers are used, their stabili~y in the mixture is not as good as possible because of which migration o plasticizers take plac~ in the product. One more drawback in conventional PE/PVA/PA mixtures is that the melt index of the product is not low enough.
- :
` ~ ' , .
W O 90/12063 2 0 3 2 ~ 2 2 PCT/F190/0~107 1 The object of the present invention is a material containing polyole~in, 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 stren~th properties of the films manufactured from the product, such as viscosity, tensile strength, impact tensile strength, and resistance to rupture, have improved.
As taught by the invention, it has been surprisingly ound that when cc~tain internally plasticized polyvinyl alsohol polymers and amorphous polyamide are mixed in molten state with polyolefins to which carboxyl acid has been copolymerized or grafted, such products ar~ obtained which have a lighter colour and th~ oxygen sealing ~ained in which is considerably less sensitive to mois~ure than in using conventional polyvinyl alcohol, and in addition, the strength proper-ties of the films manufac~uret from the product are better than in using unmodified polyolefin, ordinary polyvinyl alcohol, and poly-amide.
Therefore, the invention concerns a ~as-sealed material containing polyoleiin, vinyl alcohol polymer, and polyamide. The gas-~ealed 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 lO to 96 per cent by weight of internally plasticizsd vinyl alcohol polymer, and l to 50 per cent by weight of an amorphous polyamide.
The term 'internally plasticized vinyl alcohol polymer' refers to a vinyl alcohol polymer which contains polyglycol groups (polye~her 30 groups) or other groups plasticizing polyvinyl alcohol in the side chains thereo~. Said plasticizer ~ro~ps are connected into a chain by copolymerizing, grafting or by means of reactive compoundi~g. One such internally plasticized 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.
Sa~d internal1y p1asticized vinyl alcohol polymers may be manu-: ~
....
:, :, . .
:. ' . .
'' , " ' ' W O 90~12063 2 0 3 21~ ~ Pcr/FIgo/Dolo7 1 factured, for instance in th~ manner as disclosed in the US. patent No. 4,709,999. Said patent presents that the product i5 provided with ~ood oxygen sealing and that it is appropriate for cast, in-~ection moulding and extrusion products, and that it is characterized by good water solubility, and therefore, it is particularly well appropriate for manufacturing films which are required to possess water solubility.
The vinyl alcohol polymer used in the polyolefin/polyvinyl alcohol/
polyamide mixture of the invention is advantageously such in which in the poly(alkyleneoxy)ester derivative for use as a comonomer the alky].ene of the alcohol component is an ethylene or propylene, and the acid component is an acrylic acid or methacrylic acid. Said modified ~inyl alcohol polymers may be manufactured, for instance, by poly-merizing vinyl acetate monomer and poly(alkyleneoxy)acrylate co-monomsr, and hydrolyzing the copoly~er thus obtained in order to produce an internally plasticized vinyl alcohol poly~er.
The quantity 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 wei~ht, preferably in the range of from 30 to 60 psr 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 copoly~ers 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 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, or ethylene-methacrylate ester copolymer, or it may be a thermoplastic olefin-based elastomer, such as EP or EPD rubber.
.: -'- : '' :;. ' ., ' . : , .: :
.
W O 90/12063 2 ~ 3 212 2 PCT/FIgO/00107 1 The polyolefin in the process according to ~he invention may also be a homopolymer or a copolymer of ~he above-mentioned olefins which has been modified with the aid of carboxylic acid. To such a modified olefin polymer is copolymerized or grafted O.l to lO 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 copolymeri~ed in polyolefin. Examples of such acids are, for instance, acrylic acid, methacrylic acid, maleic acid fumaric acid, itaconic acid, crotonic acid, sorblc acid, and anhydrldes 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 con.aining a poly-olefin modified in the manner described above, and un unmodified polyolefin.
Tha quantity of the polyolefin in the gas-sealed material of the invention may be in the range l to 99 per eent by weight, but preferably in the range from 30 to 60 per eent by ~eight of the quantity of the entire mixtur~.
A third component in a gas-sealed material of the invention is amorphous polyamide. For the polyamide is used a polyamide in whieh the degree of crystallization varies in the range l to lO per cent, advantageously in the range l to 5 per cent.
The quantity of amorphous polyamide in a material of the i~vention may be selected from the range l to 50 per cent by weight.
The amorphous polyamide enhances the viscosi~y 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.
. ' ' ' '. . . ' _W O 90/12063 2 0 3 212 2 PCT/F19~/00107 1 From the polyolefin/PVA/PA mixture of the inYention various products may be prepared by combining the mixture ~ith polyolefins, other plastics or other materials, such as fibre-based materials. Multiple layer products may be manufac~ured by coextrusion, (co)extrusion coating, (co)ex~rusion lamination, adhesion lamination, or using o~her techniques, and these production procedures may also be combined.
As products containing a gas-sealed material of ~he in~en~ion e.g.
films, moulded-blown bottles and containers, plates, tubes, injection moulded vessels, deep-drawn films and plates, liquid packaging card-board, etc. may be mentioned. Sealed multiple-layer products are generally used for packaging foodstuffs, when oxygen sealing is desired also in moist circumstances, 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-limi~ing ~xampl~s the manufacturing, properties and application of ~he polyolefin/vinyl alcohol polymer/polyamide mixture of the inven~ion in sealed one-layer products are described.
The oxygen permeability of the films was measured with an OX-TRAN
lOOO apparatus ~ASTN D 3985). The polyolefins, the vinyl alcohol po-lymers and polyamides used in the tests of the examples are presented in the table below.
. . ~
Pol~olefins POl PE (low density polyethylene), melt index (MI) 1.8 g/lO min (190C) P02 - LLDPE (linear low density polyethylene), grafted with O.25 per cent by weight of fu~aric acid, melt index 0.5 g/lO min (l90C) 3~
' -, ` ~ ` .`;` '~ '' `~ ' , ` ,'` ` ` `: :
, .:., , " .~ .
.
. . .
. ' 2~3~ ~2 W O 90~12063 PC~/FI90/0010'7 _ 1 PolyvinYl~alcohol PVAl vinyl alcohol copolymer wherein the comonomer is an ester of an methacryl acid and an ester of poly-ethylene ~lycol (Vinex 4004, Air Products and Chemicals) PVA2 - polyvinyl alcohol, viscosity 4, hydrolysis degree 88~
Polyamides PAl ~ amorphous polyamide, degree of crystallization 1-5%
PA2 ; polyamide 6 1~ PA3 polyamide 11 PA4 polyamide 12 Plasticizer glycerol, degree of purity 99%
Example 1 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 215 to 210. The production rate was 10 kilograms per hour.
The thicknesses of the obtained films wère 150 ~o 200 ~m. The com-pounds thereof are presented in the accompanying Table 1 A. The properties of the films are pr~sented in the accompanying Table 1 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 s~andard ASTM D 1925-70 wlth the Ultra Scan apparatus of Hunter Lab.
: .
.
.. : . , : , :: : . ' , , . :
. , . . .
. " ' , W O 90/12063 2 0 3 2 ~ ~ 2 PCT/Fl~0t00107 1 TABLE l A
.
Test Polyvinyl_~alcohol Polyolefin ~olvamide type ~ by weigh~ ~ype ~ by w. type ~ by w 1 PVAl 60 POl 30 PAl 10 2 PVAl 60 POl 10 PAl 9 3 PVAl 60 POl 10 PAl 9
- :
` ~ ' , .
W O 90/12063 2 0 3 2 ~ 2 2 PCT/F190/0~107 1 The object of the present invention is a material containing polyole~in, 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 stren~th properties of the films manufactured from the product, such as viscosity, tensile strength, impact tensile strength, and resistance to rupture, have improved.
As taught by the invention, it has been surprisingly ound that when cc~tain internally plasticized polyvinyl alsohol polymers and amorphous polyamide are mixed in molten state with polyolefins to which carboxyl acid has been copolymerized or grafted, such products ar~ obtained which have a lighter colour and th~ oxygen sealing ~ained in which is considerably less sensitive to mois~ure than in using conventional polyvinyl alcohol, and in addition, the strength proper-ties of the films manufac~uret from the product are better than in using unmodified polyolefin, ordinary polyvinyl alcohol, and poly-amide.
Therefore, the invention concerns a ~as-sealed material containing polyoleiin, vinyl alcohol polymer, and polyamide. The gas-~ealed 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 lO to 96 per cent by weight of internally plasticizsd vinyl alcohol polymer, and l to 50 per cent by weight of an amorphous polyamide.
The term 'internally plasticized vinyl alcohol polymer' refers to a vinyl alcohol polymer which contains polyglycol groups (polye~her 30 groups) or other groups plasticizing polyvinyl alcohol in the side chains thereo~. Said plasticizer ~ro~ps are connected into a chain by copolymerizing, grafting or by means of reactive compoundi~g. One such internally plasticized 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.
Sa~d internal1y p1asticized vinyl alcohol polymers may be manu-: ~
....
:, :, . .
:. ' . .
'' , " ' ' W O 90~12063 2 0 3 21~ ~ Pcr/FIgo/Dolo7 1 factured, for instance in th~ manner as disclosed in the US. patent No. 4,709,999. Said patent presents that the product i5 provided with ~ood oxygen sealing and that it is appropriate for cast, in-~ection moulding and extrusion products, and that it is characterized by good water solubility, and therefore, it is particularly well appropriate for manufacturing films which are required to possess water solubility.
The vinyl alcohol polymer used in the polyolefin/polyvinyl alcohol/
polyamide mixture of the invention is advantageously such in which in the poly(alkyleneoxy)ester derivative for use as a comonomer the alky].ene of the alcohol component is an ethylene or propylene, and the acid component is an acrylic acid or methacrylic acid. Said modified ~inyl alcohol polymers may be manufactured, for instance, by poly-merizing vinyl acetate monomer and poly(alkyleneoxy)acrylate co-monomsr, and hydrolyzing the copoly~er thus obtained in order to produce an internally plasticized vinyl alcohol poly~er.
The quantity 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 wei~ht, preferably in the range of from 30 to 60 psr 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 copoly~ers 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 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, or ethylene-methacrylate ester copolymer, or it may be a thermoplastic olefin-based elastomer, such as EP or EPD rubber.
.: -'- : '' :;. ' ., ' . : , .: :
.
W O 90/12063 2 ~ 3 212 2 PCT/FIgO/00107 1 The polyolefin in the process according to ~he invention may also be a homopolymer or a copolymer of ~he above-mentioned olefins which has been modified with the aid of carboxylic acid. To such a modified olefin polymer is copolymerized or grafted O.l to lO 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 copolymeri~ed in polyolefin. Examples of such acids are, for instance, acrylic acid, methacrylic acid, maleic acid fumaric acid, itaconic acid, crotonic acid, sorblc acid, and anhydrldes 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 con.aining a poly-olefin modified in the manner described above, and un unmodified polyolefin.
Tha quantity of the polyolefin in the gas-sealed material of the invention may be in the range l to 99 per eent by weight, but preferably in the range from 30 to 60 per eent by ~eight of the quantity of the entire mixtur~.
A third component in a gas-sealed material of the invention is amorphous polyamide. For the polyamide is used a polyamide in whieh the degree of crystallization varies in the range l to lO per cent, advantageously in the range l to 5 per cent.
The quantity of amorphous polyamide in a material of the i~vention may be selected from the range l to 50 per cent by weight.
The amorphous polyamide enhances the viscosi~y 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.
. ' ' ' '. . . ' _W O 90/12063 2 0 3 212 2 PCT/F19~/00107 1 From the polyolefin/PVA/PA mixture of the inYention various products may be prepared by combining the mixture ~ith polyolefins, other plastics or other materials, such as fibre-based materials. Multiple layer products may be manufac~ured by coextrusion, (co)extrusion coating, (co)ex~rusion lamination, adhesion lamination, or using o~her techniques, and these production procedures may also be combined.
As products containing a gas-sealed material of ~he in~en~ion e.g.
films, moulded-blown bottles and containers, plates, tubes, injection moulded vessels, deep-drawn films and plates, liquid packaging card-board, etc. may be mentioned. Sealed multiple-layer products are generally used for packaging foodstuffs, when oxygen sealing is desired also in moist circumstances, 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-limi~ing ~xampl~s the manufacturing, properties and application of ~he polyolefin/vinyl alcohol polymer/polyamide mixture of the inven~ion in sealed one-layer products are described.
The oxygen permeability of the films was measured with an OX-TRAN
lOOO apparatus ~ASTN D 3985). The polyolefins, the vinyl alcohol po-lymers and polyamides used in the tests of the examples are presented in the table below.
. . ~
Pol~olefins POl PE (low density polyethylene), melt index (MI) 1.8 g/lO min (190C) P02 - LLDPE (linear low density polyethylene), grafted with O.25 per cent by weight of fu~aric acid, melt index 0.5 g/lO min (l90C) 3~
' -, ` ~ ` .`;` '~ '' `~ ' , ` ,'` ` ` `: :
, .:., , " .~ .
.
. . .
. ' 2~3~ ~2 W O 90~12063 PC~/FI90/0010'7 _ 1 PolyvinYl~alcohol PVAl vinyl alcohol copolymer wherein the comonomer is an ester of an methacryl acid and an ester of poly-ethylene ~lycol (Vinex 4004, Air Products and Chemicals) PVA2 - polyvinyl alcohol, viscosity 4, hydrolysis degree 88~
Polyamides PAl ~ amorphous polyamide, degree of crystallization 1-5%
PA2 ; polyamide 6 1~ PA3 polyamide 11 PA4 polyamide 12 Plasticizer glycerol, degree of purity 99%
Example 1 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 215 to 210. The production rate was 10 kilograms per hour.
The thicknesses of the obtained films wère 150 ~o 200 ~m. The com-pounds thereof are presented in the accompanying Table 1 A. The properties of the films are pr~sented in the accompanying Table 1 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 s~andard ASTM D 1925-70 wlth the Ultra Scan apparatus of Hunter Lab.
: .
.
.. : . , : , :: : . ' , , . :
. , . . .
. " ' , W O 90/12063 2 0 3 2 ~ ~ 2 PCT/Fl~0t00107 1 TABLE l A
.
Test Polyvinyl_~alcohol Polyolefin ~olvamide type ~ by weigh~ ~ype ~ by w. type ~ by w 1 PVAl 60 POl 30 PAl 10 2 PVAl 60 POl 10 PAl 9 3 PVAl 60 POl 10 PAl 9
4 PVAl 60 POl 10 PAl 9 PVAl 60 POl 10- PAl 30 6 PVA2 60 POl 40 - -Note. In test 6, the quantity of polyvinyl alcohol includes 4.5%
glycerol of the PVA quantity.
__ ~ _ _ Test Oxy~en permeabil. Y~ll9Y5~ Tensile ~ml~m-x24hxbar2 index, thick- strength 0~RH 90~RH ness ~mmach. /trans (210C) dir. dir.
NPa MPa ,, .... _ . , . . . _ _ . _ _ _ _ _ _ 1 0.01 2.5 0.7S 151 15.0 14.5 2 0.09 1.5 0.75 163 44.8 25.0 3 0.12 1.5 0.75 148 4~.0 24.5 4 1.11 l.S 0.75 191 42.5 22.7 2~ 5 0.01 3.0 0.85 190 47.8 29.0 6 0.20 10.0 10.9 172 10.0 7.0 .. . . . __ Polyolefin/PVA/polyamide mixtures of the invention were prepared by mixing polyolefin, polyvinyl alcohol and polyamide, in molten s~ate, 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 o~ the obtained films were 140 to 190 ~m. The com-... .. : - .
' ",, ': : : :
" . , ~ , .
.. . . .. .
, `
W O 90/12063 2 ~ 3 2 ~ 2 2 Pcr/F~go/nolo7 . , 1 pounds thereof are presented in ~he 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 lndex conforming to the standard ASTM D 1925-70 with the Ultra Scan apparatus of Hunter Lab.
0 Test Pol w inYl alcohol Polyolefin PolYamide type ~ by weight type ~ by w. type % by w.
.
l PVAl 80 P02 10 PAl 10 2 PVAl 70 P02 3 PAl 27 3 PVAl 60 PQ2 30 PAl lO
4 PVAl 30 P02 20 PAl S0 15 5 PVAl 10 P02 60 PAl 30 6 PVAl 60 P02 10 PAl 9 7 PVAl 60 P02 10 PAl 9 8 PVAl 60 P02 10 PAl 9 ~0 9 PVA2 60 P01 40 . _ Note. In tests 9 and 10, the quantity of polyvin~l alcohol includes 4.5~ glycerol of the PVA quan~ity.
2~
,- .. :
'~
'' ' , . "' W O 90/12063 2 0 3 21~ 2 PCT/FI90/00l07 Test Oxy~en permeabil. Yellowness ~ Q
(ml/m-x24hxbar? index, thick- strength 0%RH 90~RH ness ~m mach./tr~ns dir. dlr.
MPa ~Pa :
l 0.1 2.9 0.80 142 19.918.5 2 0.051.9 0.70 171 32.225.0 3 0.012.5 0.75 166 16.~~5.0 4 1.5 25 0.85 151 42.539.7 3.6 55 0.85 147 35.031.6 6 0.081.4 0.75 1~6 46.826.0 7 0.101.5 0.75 150 45.227.8 8 0.10i.5 0.75 141 44.525.5 9 0.2010.0 10.9 172 10.07.0 l~ 0.209.6 11.5 162 14.011.0 .
:
, : . .
- :~. : , '' "' ' ' .
. .
glycerol of the PVA quantity.
__ ~ _ _ Test Oxy~en permeabil. Y~ll9Y5~ Tensile ~ml~m-x24hxbar2 index, thick- strength 0~RH 90~RH ness ~mmach. /trans (210C) dir. dir.
NPa MPa ,, .... _ . , . . . _ _ . _ _ _ _ _ _ 1 0.01 2.5 0.7S 151 15.0 14.5 2 0.09 1.5 0.75 163 44.8 25.0 3 0.12 1.5 0.75 148 4~.0 24.5 4 1.11 l.S 0.75 191 42.5 22.7 2~ 5 0.01 3.0 0.85 190 47.8 29.0 6 0.20 10.0 10.9 172 10.0 7.0 .. . . . __ Polyolefin/PVA/polyamide mixtures of the invention were prepared by mixing polyolefin, polyvinyl alcohol and polyamide, in molten s~ate, 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 o~ the obtained films were 140 to 190 ~m. The com-... .. : - .
' ",, ': : : :
" . , ~ , .
.. . . .. .
, `
W O 90/12063 2 ~ 3 2 ~ 2 2 Pcr/F~go/nolo7 . , 1 pounds thereof are presented in ~he 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 lndex conforming to the standard ASTM D 1925-70 with the Ultra Scan apparatus of Hunter Lab.
0 Test Pol w inYl alcohol Polyolefin PolYamide type ~ by weight type ~ by w. type % by w.
.
l PVAl 80 P02 10 PAl 10 2 PVAl 70 P02 3 PAl 27 3 PVAl 60 PQ2 30 PAl lO
4 PVAl 30 P02 20 PAl S0 15 5 PVAl 10 P02 60 PAl 30 6 PVAl 60 P02 10 PAl 9 7 PVAl 60 P02 10 PAl 9 8 PVAl 60 P02 10 PAl 9 ~0 9 PVA2 60 P01 40 . _ Note. In tests 9 and 10, the quantity of polyvin~l alcohol includes 4.5~ glycerol of the PVA quan~ity.
2~
,- .. :
'~
'' ' , . "' W O 90/12063 2 0 3 21~ 2 PCT/FI90/00l07 Test Oxy~en permeabil. Yellowness ~ Q
(ml/m-x24hxbar? index, thick- strength 0%RH 90~RH ness ~m mach./tr~ns dir. dlr.
MPa ~Pa :
l 0.1 2.9 0.80 142 19.918.5 2 0.051.9 0.70 171 32.225.0 3 0.012.5 0.75 166 16.~~5.0 4 1.5 25 0.85 151 42.539.7 3.6 55 0.85 147 35.031.6 6 0.081.4 0.75 1~6 46.826.0 7 0.101.5 0.75 150 45.227.8 8 0.10i.5 0.75 141 44.525.5 9 0.2010.0 10.9 172 10.07.0 l~ 0.209.6 11.5 162 14.011.0 .
:
, : . .
- :~. : , '' "' ' ' .
. .
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. 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, 10 to 96 per cent by weight of internally plasticized vinyl alcohol polymer, and 1 to 50 per cent by weight of amorphous polyamide.
2. Gas-sealed material according to claim 1, 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 1 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 0.1 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 pereceding claims, characterized in that the polyolefin is formed from a mixture of an unmodified polyolefin and a polyolefin modified with carboxyl acid.
9. A gas-sealed material according to any one of the preceding claims, characterized in that the degree of crystallization of the polyamide is in the range l to 5 per cent.
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 |
|---|---|---|---|
| FI891757A FI86875C (en) | 1989-04-13 | 1989-04-13 | GASTAETT MATERIAL, SOM INNEHAOLLER INVAENDIGT MJUKGJORD POLYVINYLALCOOL |
| FI891757 | 1989-04-13 | ||
| FI891756A FI86874C (en) | 1989-04-13 | 1989-04-13 | Gas-sealed material containing internally plasticized polyvinyl alcohol |
| FI891756 | 1989-04-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2032122A1 true CA2032122A1 (en) | 1990-10-14 |
Family
ID=26158539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2032122 Abandoned CA2032122A1 (en) | 1989-04-13 | 1990-04-11 | Gas-sealed material |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0423270A1 (en) |
| JP (1) | JPH04500538A (en) |
| AU (1) | AU5417190A (en) |
| CA (1) | CA2032122A1 (en) |
| WO (1) | WO1990012063A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990012062A1 (en) * | 1989-04-13 | 1990-10-18 | Neste Oy | Gas-sealed material |
| EP0483695B1 (en) * | 1990-10-29 | 1996-10-02 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Resin composition and use thereof |
| FI922378A (en) * | 1991-06-19 | 1992-12-20 | Chevron Res & Tech | POLYMER BEARING OF POLYOLEFIN, POLYAMID OCH EN MODIFIEDAD ETHLENICOPOLYMER |
| FI922379A (en) * | 1991-06-19 | 1992-12-20 | Chevron Res & Tech | SYREAVLAEGSNANDE HOMOGENA BLANDNINGAR AV EN MODIFIEDAD 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 (en) * | 2003-11-03 | 2005-06-02 | Kuraray Specialities Europe Gmbh | Process for the preparation of polyamide-polyvinyl alcohol moldings |
Family Cites Families (8)
| 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 (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 |
| JPS6470544A (en) * | 1987-08-24 | 1989-03-16 | Du Pont | Blend of ethylene vinyl alcohol copolymer and 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 |
-
1990
- 1990-04-11 CA CA 2032122 patent/CA2032122A1/en not_active Abandoned
- 1990-04-11 JP JP50579890A patent/JPH04500538A/en active Pending
- 1990-04-11 AU AU54171/90A patent/AU5417190A/en not_active Withdrawn
- 1990-04-11 WO PCT/FI1990/000107 patent/WO1990012063A1/en not_active Application Discontinuation
- 1990-04-11 EP EP19900905544 patent/EP0423270A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0423270A1 (en) | 1991-04-24 |
| WO1990012063A1 (en) | 1990-10-18 |
| JPH04500538A (en) | 1992-01-30 |
| AU5417190A (en) | 1990-11-05 |
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