CA2032121A1 - Gas-sealed material - Google Patents
Gas-sealed materialInfo
- Publication number
- CA2032121A1 CA2032121A1 CA002032121A CA2032121A CA2032121A1 CA 2032121 A1 CA2032121 A1 CA 2032121A1 CA 002032121 A CA002032121 A CA 002032121A CA 2032121 A CA2032121 A CA 2032121A CA 2032121 A1 CA2032121 A1 CA 2032121A1
- Authority
- CA
- Canada
- Prior art keywords
- gas
- polyolefin
- acid
- ethylene
- 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
- 239000000463 material Substances 0.000 title claims abstract description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 50
- 229920000098 polyolefin Polymers 0.000 claims abstract description 39
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims description 25
- 239000004014 plasticizer Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 229920001684 low density polyethylene Polymers 0.000 claims description 6
- 239000004702 low-density polyethylene Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 229940063583 high-density polyethylene Drugs 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229920001179 medium density polyethylene Polymers 0.000 claims description 3
- 239000004701 medium-density polyethylene Substances 0.000 claims description 3
- 229920001083 polybutene Polymers 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000004334 sorbic acid Substances 0.000 claims description 2
- 229940075582 sorbic acid Drugs 0.000 claims description 2
- 235000010199 sorbic acid Nutrition 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 50
- 239000000047 product Substances 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 241000206607 Porphyra umbilicalis Species 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical class OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002365 multiple layer Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- STGNLGBPLOVYMA-KDTZGSNLSA-N (z)-but-2-enedioic acid;(e)-but-2-enedioic acid Chemical compound OC(=O)\C=C\C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-KDTZGSNLSA-N 0.000 description 1
- DRMYLINAGHHBNG-UHFFFAOYSA-N 2-oxo-3h-furan-4-carboxylic acid Chemical compound OC(=O)C1=COC(=O)C1 DRMYLINAGHHBNG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241001527806 Iti Species 0.000 description 1
- 235000011464 Pachycereus pringlei Nutrition 0.000 description 1
- 240000006939 Pachycereus weberi Species 0.000 description 1
- 235000011466 Pachycereus weberi Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Glass Compositions (AREA)
Abstract
Abstract of Disclosure The present invention concerns a gas-sealed material, containing polyolefin and polyvinyl alcohol. The material is manufactured by mixing in molten state 1 to 99 per cent by weight of polyolefin and 99 to 1 per cent by weight of internally plasticized vinyl alcohol polymer, and optionally 1 to 15 per cent by weight of a plasticizing agent.
Description
- 2~32~.2~
~W O 90/1206~ PCr/F190/~01();
1 Gas-sealed ma~erial The presen~ invention concerns a gas-sealed material and produc~s con~aining gas-sealed material. In particular, the presen~ inven~ion concerns a gas-sealed material containing polyolefine and polyvinvl alcohol, and products containing the same.
Polyoleiins are widelv used, for inscance, in packaging indus~ry for manufacturing various film products. Advantages of polvolefins are ~,' in particular appropriate strength and water resistance proper~ies.
Among the drawbacks mav be mentioned permeability to certain gases and liquids, concernin~ particularly oxygen and hydrocarborl dis-solven~s. Thereîore, the usability of polyolefin films is limi~ed to 15 packaging certain substances, such as îood stuffs, in which minor o~ygen permeability is required.
It is customary to use in packaging industry multiple layer rilm scructures in which materials of differént layers are selected to 20 serve a given purpose. Therefore, such multiple laver structures mav contain layers which form a good barrier agains~ gases, such as o~ygen, and layers which provide other properties for the proauct, such as strength properties. In addition, multiple laver structures ma~ contain other lavers which g0nerate for instance adnesion De~Ween 25 difrerent layers. Products of this kind are, however, expensive to manufacture.
Poly~inyl alcohol is one of such polvmers which has a low oxy&en permeability property.~Said property has most ofcen been utilized in 30 olefin-vinyl alcohol random-mixed polymers and in olefin-vinyl alcohol segment-mixed polymers, It is also known in the art to manufactu~e products containing polvolefin and pol~inyl alcohol in the form of mix~ures, which have a low oxygen permeabLlitv and which therefore are e~ceedinglv appropriate for manufac~uring e.g. packagin5 films.
~5 In the Finnish pa~er.t application No. 87-5772 is disciosed a mi::~ure of poiyolefin and pol~inyl alcohol, moreover containing op~ionail:
plasticize s. 'when polvolefir: and pol~in~l alcchol are mi..ed ir.
' - ' .: ' . ' , - , , .
: ' ,` ' , ' `~ 7 :' ~ `.` . ' W 0 90/12061 2 0 3 212 i PCT/F190/00105 1 molten sta~e, 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 transpar-ent 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 instance oxygen sealing, and the product is bright and stable, in spite of two phases, bo~h in molten and in solid state, and it is easy to soften by adding plasticizers.
Although polyolefin-PVA-mix~ures are provided with good oxygen sealing properties in dry circumstances, in moist circumstances their oxygen sealing property reduces significantly, so thac they are sensitive to moisture. In addition, when mixtures of polyolefins and PVA are mixed in molten state, partial dissolution of PVA and colouring of ~he product take place. When plasticizers are used, their stability in the mixture is not as good as psssible because of which migration of plasticizers takes place in the product. One more drawback in conventional PE/PVA mixtures is that the viscosity of the product is not high enough, and that the mechanical properties of the films manufactured therefrom are not adequate.
The object af the present invention is a polyvinyl alcohol containing polyolefin, in which the mois~ure sensitivity of the product to oxygen sealing is reduced, the lightness of the product has increased, and the migration of the plasticizers has lessened.
As taught by the invention, it 'nas been surprisingly found that when certain internally plasticized polyvinyl alcohol copolymers are mixed in molten sta~e with polyol~fins, such products ars obtained ~which have a lighcer colour and the oxygen sealing gained in which is considerably less sensitive to mois~ure than in using conven-tional polyvinvl alcohol. In addition, in the material of the in-vention no plasticizer mi~ration occurs, or i~ occurs onlv to a verv ~ low degree.
:
, - - ,. ~ , :
:., , - ~
;; ~ , : :
- .:
.:
W O 90t12061 2 ~ 3 2121 PCT/F190/0010;
1 Therefore, the invention concerns a gas-sealed ~cerial containing polyolefin and polyvinyl alcohol. The gas-sealed material of the invention is characterized in that it is produced by Mixing l to 99 per cent by weight of polyolefin and 99 to l per cent by weight of a internally plasticized vinyl alcohol polymer in molten state, and optionally l to 15 per cent by weight of a plasticizer.
The term 'internally plasticized vinyl alcohol polymer' refers to a vinyl alcohol polymer which con~ains polyglycol groups (polyether groups) or other groups plasticizing polyvinyl alcohol in the side chains ~hereof. Said plasticizer groups are connected into a chain by copolymerizing, branching or by means of reacsive compounding.
One of such internally plasticized polyYinyl alcohols is Vinex polymer (trade name, Air Products and Chemicals Inc.), in which for comonomer is used an ester of methacrylic acid and polyethylene glycol.
Said internally plasticized vinyl alcohol polymers may be ~anu-factured, for instance in the m~nner as disclosed in the US. patene ~o. 4,708,999. Said patent presents that the product is provided with good oxygen sealing and that it is appropriate for cast, injection moulding and extrusion products, and that it is characterized by good water solubility and therefore, it is particu-larly well appropriate for manufacturing films which are required .o possess water solubility.
~5 The vinyl alcohol polymer used in the polyolefin/polyvinyl alcohol 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 ethylene or propylene, and the acid
~W O 90/1206~ PCr/F190/~01();
1 Gas-sealed ma~erial The presen~ invention concerns a gas-sealed material and produc~s con~aining gas-sealed material. In particular, the presen~ inven~ion concerns a gas-sealed material containing polyolefine and polyvinvl alcohol, and products containing the same.
Polyoleiins are widelv used, for inscance, in packaging indus~ry for manufacturing various film products. Advantages of polvolefins are ~,' in particular appropriate strength and water resistance proper~ies.
Among the drawbacks mav be mentioned permeability to certain gases and liquids, concernin~ particularly oxygen and hydrocarborl dis-solven~s. Thereîore, the usability of polyolefin films is limi~ed to 15 packaging certain substances, such as îood stuffs, in which minor o~ygen permeability is required.
It is customary to use in packaging industry multiple layer rilm scructures in which materials of differént layers are selected to 20 serve a given purpose. Therefore, such multiple laver structures mav contain layers which form a good barrier agains~ gases, such as o~ygen, and layers which provide other properties for the proauct, such as strength properties. In addition, multiple laver structures ma~ contain other lavers which g0nerate for instance adnesion De~Ween 25 difrerent layers. Products of this kind are, however, expensive to manufacture.
Poly~inyl alcohol is one of such polvmers which has a low oxy&en permeability property.~Said property has most ofcen been utilized in 30 olefin-vinyl alcohol random-mixed polymers and in olefin-vinyl alcohol segment-mixed polymers, It is also known in the art to manufactu~e products containing polvolefin and pol~inyl alcohol in the form of mix~ures, which have a low oxygen permeabLlitv and which therefore are e~ceedinglv appropriate for manufac~uring e.g. packagin5 films.
~5 In the Finnish pa~er.t application No. 87-5772 is disciosed a mi::~ure of poiyolefin and pol~inyl alcohol, moreover containing op~ionail:
plasticize s. 'when polvolefir: and pol~in~l alcchol are mi..ed ir.
' - ' .: ' . ' , - , , .
: ' ,` ' , ' `~ 7 :' ~ `.` . ' W 0 90/12061 2 0 3 212 i PCT/F190/00105 1 molten sta~e, 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 transpar-ent 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 instance oxygen sealing, and the product is bright and stable, in spite of two phases, bo~h in molten and in solid state, and it is easy to soften by adding plasticizers.
Although polyolefin-PVA-mix~ures are provided with good oxygen sealing properties in dry circumstances, in moist circumstances their oxygen sealing property reduces significantly, so thac they are sensitive to moisture. In addition, when mixtures of polyolefins and PVA are mixed in molten state, partial dissolution of PVA and colouring of ~he product take place. When plasticizers are used, their stability in the mixture is not as good as psssible because of which migration of plasticizers takes place in the product. One more drawback in conventional PE/PVA mixtures is that the viscosity of the product is not high enough, and that the mechanical properties of the films manufactured therefrom are not adequate.
The object af the present invention is a polyvinyl alcohol containing polyolefin, in which the mois~ure sensitivity of the product to oxygen sealing is reduced, the lightness of the product has increased, and the migration of the plasticizers has lessened.
As taught by the invention, it 'nas been surprisingly found that when certain internally plasticized polyvinyl alcohol copolymers are mixed in molten sta~e with polyol~fins, such products ars obtained ~which have a lighcer colour and the oxygen sealing gained in which is considerably less sensitive to mois~ure than in using conven-tional polyvinvl alcohol. In addition, in the material of the in-vention no plasticizer mi~ration occurs, or i~ occurs onlv to a verv ~ low degree.
:
, - - ,. ~ , :
:., , - ~
;; ~ , : :
- .:
.:
W O 90t12061 2 ~ 3 2121 PCT/F190/0010;
1 Therefore, the invention concerns a gas-sealed ~cerial containing polyolefin and polyvinyl alcohol. The gas-sealed material of the invention is characterized in that it is produced by Mixing l to 99 per cent by weight of polyolefin and 99 to l per cent by weight of a internally plasticized vinyl alcohol polymer in molten state, and optionally l to 15 per cent by weight of a plasticizer.
The term 'internally plasticized vinyl alcohol polymer' refers to a vinyl alcohol polymer which con~ains polyglycol groups (polyether groups) or other groups plasticizing polyvinyl alcohol in the side chains ~hereof. Said plasticizer groups are connected into a chain by copolymerizing, branching or by means of reacsive compounding.
One of such internally plasticized polyYinyl alcohols is Vinex polymer (trade name, Air Products and Chemicals Inc.), in which for comonomer is used an ester of methacrylic acid and polyethylene glycol.
Said internally plasticized vinyl alcohol polymers may be ~anu-factured, for instance in the m~nner as disclosed in the US. patene ~o. 4,708,999. Said patent presents that the product is provided with good oxygen sealing and that it is appropriate for cast, injection moulding and extrusion products, and that it is characterized by good water solubility and therefore, it is particu-larly well appropriate for manufacturing films which are required .o possess water solubility.
~5 The vinyl alcohol polymer used in the polyolefin/polyvinyl alcohol 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 ethylene or propylene, and the acid
3~ component is acrylic acid or methacrylic acid. Said modified vinyl alcohol polymers may be manufactured, for instance, by polymerizing vinyl acetate monomer and poly(alkyleneoxy)acrylate comonomer, and hydrolyzing the copolymer thus o.btained in order to produce an in-rernally plasticized vinyl alcohol polymer.
The amoun-~ of the internally plasticized vinyl alcohol polymer in ehe polyethylene-polyvinvl alcohol mixture of the invention mav be , .:, .
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.
W O 90/lZ061 2 U 3 2 ~ ~ ~ Pcr/~l~o/~)olo~
1 in the range of from l tO 99 per cent by weight, preferably in ~he range of from lO to 90 per cent by weight. In smaller quan~ities, the effect on oxygen permeability is, however, smaller, while the colour of the product may, nevertheless, be~maintained good. In some instance, 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 present in the gas-sealed material of the invention may be based on homopolymers or copolymers of the olefins. There-fore, it may be low density polyethylene (LDPE~, medium density polyethylene or high density polyethylene (HDPE), polypropylene or polybutene. The polyolefin may also be a copolvmer or ethylene to-gecher with other olefins, such as propylene, butene, hexene and oc~ene. The polyolefin may also be an olefin-ester copolymer, such as ethyle~e-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.
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 O.l to lO per cent by weight of carboxylic acid. Ihe carboxvlic acid may comprise anv unsaturated carboxylic acid or carboxylic acid anhydride which can be 8rafted 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 graf~ing 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 quan~ity of the polvolefin in the gas-sealed macerial oi ~he invention may be in the range from ]. to 99 per cent bv weigh~, bu;
preferably in the range from lO LO 90 per cent bv weight of the .
: - , :
, - W O 90/12061 2~32~ ~ Pcr/~ /n~1~s 1 quantity of the entire mixture.
The gas-sealed material of the invention may further con~ain l to lo per cent by weigh~ of plasticizers. A plasticizer mav be selec~ed from anv material used for polyvinyl alcohol plasticizer or a mixture thereof. As e~amples of such may be mentioned ethylene glycol, tri-methylene glycol, propylene ~lycol, triethylene glvcol, neopenthvl glycol and 2,2,4-trimethyl-1,3^pentane diol and sorbitol. A preferable plasticizer is glycerol.
The gas-sealed polyolefin/PVA mixture of the invention mav be manu-fac~ured mixing the polyolefin component, the vinyl alcohol/polymer component and a potential plasticizer component in a melt mixer simultaneously as a dry mixture, premixed in solid or molten state, or then various components are added separately. The addition of plastici~ers may also be carried out after the compounding. Also such procedure may be adopted in which a plasticizer is added in the PVA component, whereby the a~vantage is gained that the en~ire mixture need not be plasticized.
From the polyolefin/PVA mixture of the invention various produc~s mav be prepared by combining the mixture ~ith polvolefins, other plastics or other materials, such as fibre-based materials. ~ultiple laver products may be manufactured by coex~rusion. (co)extrusion coating, (co?extrusion lamination, adhesion lamina~ion, or using other ~echniques, and these production procedures mav also be com-bined.
As produc~s containing a gas-sealed material o the invention e.g.
films, moulded-blown bottles and containers, plates, tubes, injection moulded vessels, deep-drawn films and plates, liquid packaging card-boards, etc. may be mentioned. Sealed multiple-layer products are generally used for packaging food stufs, when oxvgen sealing is desired also in moist circumstances, but the sealing of carDon dioxide or some other gas mav be thought of. In addi~ion. fat, chemical and odour sealing mav be desired both in food stu~f pacKageS and technicaI
products.
' , ., ~
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. -,. -.: . ,- . :
. . . , , . . " . .
, W O 90/12061 ?J O 3 2 ~ 2 ~ Pcr/FI9~/oo1o5 1 In the followin~ non-limi~ing examples the manufacturing, properties and application of the polyolefin/vinyl alcohol polymer mix~ure of the invention in sealed one-laver products are described. The oxygen permeability oE the films was measured with an OX-TRAN l000 appara~us (ASTM D 3985~. The polyolefins and ~he vinyl alcohol polymers used in the tests of the examples are presented in the table below.
PolYolefins ~PO~
10 POl- LDPE (low density polyethylene), density 922 kg/m', molten indeY~ (MI) l.8 g/min (190C) P02~ PP (propylene block copolymer), MI 3.3 g/l0 min (230C) P03~ PB (polybutene), MI 1.4 g/l0 min (190C) P04 ~ EVA (ethylene-vinyl acetate copolymer), vinyl acetate content 5~
PO5 ~ EBA (ethylene-butyl acrylate copolymer), MI l.0 g/l0 min (190C), butyl acrylate content 7~
PO6 ~ LLDPE (linear low density polyethylene), grafted with 0.25% maleic acid anhydride (~HA), MI 0.5 g/l0 min (190C) P07 - PP (propylene block copolymer), MI 3.3 g/l0 min (230C) PO8 PP (PO3)~ grafted with 0.20% MHA
PO9 ~ PB (polvbutene), MI 1.4 g/l0 min (190C) POl0 - PB (PO5), grafted with 0.25~ i~aconic acid POll ~ EVA ~ethylene-vinvl acetate copolvmer) vinyl acetate content 5~
P012 - EVA (PO7), grafted with 0.l~ fumaric acid PO13 - EBA (ethylene-butyl acrylate copolymer), MI l.0 g/l0 min (190C), butyl acrylate content 7 P014 ~ EBA (PO9), graf~ed with 0.4 ~ acrylic acid POlS ~ EEA (ethylene-acrylic acid copolymer)~ acrylic acid content 6 3~
.
.. . . , , ~ :
' ' '' ' ' .
, ' .' W O 90/12061 2 0 3 2 ~ 21 PCr/FI90/~0!,0~
PVAl - vin~l alcohol copolymer wherein the comonomer is an ester of methacryl acid and polyethylene glycol (Vinex 4004, Air Products and Chemicals) PVA2 - polyvinyl alcohol, viscosity 4, hydrolysis degree 88%
Plasticizer glycerol, degree of purity 99 Exa~ple 1 Polyolefin-PVA mi~ures of the inven~ion were prepared by mixing polyolefin and polyvinyl alcohol in molten state by the aid of a Bers~orff mixer which was provided with a flat iilm nozzle. The temperature profile was 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 230 to 220 to 220, and the temperature of the melt was 220C. The production rate was 10 kilograms per hour.
The thicknesses of ~he obtained films were 100 to 170 ~m. The com-pounds thereof are presented in the accompanying Table 1 A. The properties of the films are presented in the accompanyi~lg Table 1 ~.
The oxygen permeability values of the films are calc~tlated for 25 ~m thickness.:Thb ligh~nesses of the films was measured as a so-called yellowness index conforning to the standard ASTM D 1925-;'0 with the Ultra Scan apparatus of Hunter Lab.
~ ~ ~
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~
.:
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, . . .
W O 90J12061 2 0 3 2 ~ 21 PCT/F190/0010;
1 Table 1 A
Test Polvvinyl alcohol Polyolefine Plasticizer type ~ by weight type, ~ by w.
... . . _ , .
l PVAl 60 P01 40 2 PVAl 60 POl 36 4 3 PVAl lO P01 36 4
The amoun-~ of the internally plasticized vinyl alcohol polymer in ehe polyethylene-polyvinvl alcohol mixture of the invention mav be , .:, .
' :' . . - : ,, .:
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.
W O 90/lZ061 2 U 3 2 ~ ~ ~ Pcr/~l~o/~)olo~
1 in the range of from l tO 99 per cent by weight, preferably in ~he range of from lO to 90 per cent by weight. In smaller quan~ities, the effect on oxygen permeability is, however, smaller, while the colour of the product may, nevertheless, be~maintained good. In some instance, 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 present in the gas-sealed material of the invention may be based on homopolymers or copolymers of the olefins. There-fore, it may be low density polyethylene (LDPE~, medium density polyethylene or high density polyethylene (HDPE), polypropylene or polybutene. The polyolefin may also be a copolvmer or ethylene to-gecher with other olefins, such as propylene, butene, hexene and oc~ene. The polyolefin may also be an olefin-ester copolymer, such as ethyle~e-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.
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 O.l to lO per cent by weight of carboxylic acid. Ihe carboxvlic acid may comprise anv unsaturated carboxylic acid or carboxylic acid anhydride which can be 8rafted 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 graf~ing 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 quan~ity of the polvolefin in the gas-sealed macerial oi ~he invention may be in the range from ]. to 99 per cent bv weigh~, bu;
preferably in the range from lO LO 90 per cent bv weight of the .
: - , :
, - W O 90/12061 2~32~ ~ Pcr/~ /n~1~s 1 quantity of the entire mixture.
The gas-sealed material of the invention may further con~ain l to lo per cent by weigh~ of plasticizers. A plasticizer mav be selec~ed from anv material used for polyvinyl alcohol plasticizer or a mixture thereof. As e~amples of such may be mentioned ethylene glycol, tri-methylene glycol, propylene ~lycol, triethylene glvcol, neopenthvl glycol and 2,2,4-trimethyl-1,3^pentane diol and sorbitol. A preferable plasticizer is glycerol.
The gas-sealed polyolefin/PVA mixture of the invention mav be manu-fac~ured mixing the polyolefin component, the vinyl alcohol/polymer component and a potential plasticizer component in a melt mixer simultaneously as a dry mixture, premixed in solid or molten state, or then various components are added separately. The addition of plastici~ers may also be carried out after the compounding. Also such procedure may be adopted in which a plasticizer is added in the PVA component, whereby the a~vantage is gained that the en~ire mixture need not be plasticized.
From the polyolefin/PVA mixture of the invention various produc~s mav be prepared by combining the mixture ~ith polvolefins, other plastics or other materials, such as fibre-based materials. ~ultiple laver products may be manufactured by coex~rusion. (co)extrusion coating, (co?extrusion lamination, adhesion lamina~ion, or using other ~echniques, and these production procedures mav also be com-bined.
As produc~s containing a gas-sealed material o the invention e.g.
films, moulded-blown bottles and containers, plates, tubes, injection moulded vessels, deep-drawn films and plates, liquid packaging card-boards, etc. may be mentioned. Sealed multiple-layer products are generally used for packaging food stufs, when oxvgen sealing is desired also in moist circumstances, but the sealing of carDon dioxide or some other gas mav be thought of. In addi~ion. fat, chemical and odour sealing mav be desired both in food stu~f pacKageS and technicaI
products.
' , ., ~
:'.'' ,- ''.,, ' -' .,', . , ',, ' ' ' ' :
. -,. -.: . ,- . :
. . . , , . . " . .
, W O 90/12061 ?J O 3 2 ~ 2 ~ Pcr/FI9~/oo1o5 1 In the followin~ non-limi~ing examples the manufacturing, properties and application of the polyolefin/vinyl alcohol polymer mix~ure of the invention in sealed one-laver products are described. The oxygen permeability oE the films was measured with an OX-TRAN l000 appara~us (ASTM D 3985~. The polyolefins and ~he vinyl alcohol polymers used in the tests of the examples are presented in the table below.
PolYolefins ~PO~
10 POl- LDPE (low density polyethylene), density 922 kg/m', molten indeY~ (MI) l.8 g/min (190C) P02~ PP (propylene block copolymer), MI 3.3 g/l0 min (230C) P03~ PB (polybutene), MI 1.4 g/l0 min (190C) P04 ~ EVA (ethylene-vinyl acetate copolymer), vinyl acetate content 5~
PO5 ~ EBA (ethylene-butyl acrylate copolymer), MI l.0 g/l0 min (190C), butyl acrylate content 7~
PO6 ~ LLDPE (linear low density polyethylene), grafted with 0.25% maleic acid anhydride (~HA), MI 0.5 g/l0 min (190C) P07 - PP (propylene block copolymer), MI 3.3 g/l0 min (230C) PO8 PP (PO3)~ grafted with 0.20% MHA
PO9 ~ PB (polvbutene), MI 1.4 g/l0 min (190C) POl0 - PB (PO5), grafted with 0.25~ i~aconic acid POll ~ EVA ~ethylene-vinvl acetate copolvmer) vinyl acetate content 5~
P012 - EVA (PO7), grafted with 0.l~ fumaric acid PO13 - EBA (ethylene-butyl acrylate copolymer), MI l.0 g/l0 min (190C), butyl acrylate content 7 P014 ~ EBA (PO9), graf~ed with 0.4 ~ acrylic acid POlS ~ EEA (ethylene-acrylic acid copolymer)~ acrylic acid content 6 3~
.
.. . . , , ~ :
' ' '' ' ' .
, ' .' W O 90/12061 2 0 3 2 ~ 21 PCr/FI90/~0!,0~
PVAl - vin~l alcohol copolymer wherein the comonomer is an ester of methacryl acid and polyethylene glycol (Vinex 4004, Air Products and Chemicals) PVA2 - polyvinyl alcohol, viscosity 4, hydrolysis degree 88%
Plasticizer glycerol, degree of purity 99 Exa~ple 1 Polyolefin-PVA mi~ures of the inven~ion were prepared by mixing polyolefin and polyvinyl alcohol in molten state by the aid of a Bers~orff mixer which was provided with a flat iilm nozzle. The temperature profile was 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 230 to 220 to 220, and the temperature of the melt was 220C. The production rate was 10 kilograms per hour.
The thicknesses of ~he obtained films were 100 to 170 ~m. The com-pounds thereof are presented in the accompanying Table 1 A. The properties of the films are presented in the accompanyi~lg Table 1 ~.
The oxygen permeability values of the films are calc~tlated for 25 ~m thickness.:Thb ligh~nesses of the films was measured as a so-called yellowness index conforning to the standard ASTM D 1925-;'0 with the Ultra Scan apparatus of Hunter Lab.
~ ~ ~
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:
~
.:
:
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, . . .
W O 90J12061 2 0 3 2 ~ 21 PCT/F190/0010;
1 Table 1 A
Test Polvvinyl alcohol Polyolefine Plasticizer type ~ by weight type, ~ by w.
... . . _ , .
l PVAl 60 P01 40 2 PVAl 60 POl 36 4 3 PVAl lO P01 36 4
4 PVAl 90 P01 10
5 PVAl 30 P01 70
6 PVAl 10 P01 90
7 PVA2 60 P01 36 4
8 PVA2 90 P01 6 4
9 PVA2 30 P01 66 4 ~ .
. . . _ _ Test Melt Oxy~en permeabil. Yello~ness Tensile__ ia~ (ml/m~x24hxbar) index,thick- strsn~th g/10 ~in O~RH 65~RH 90%RH ness ~m mach./trans (210C) dir. dir.
IqPa ~Pa .. _ _ . .. .
113 1.0 8.7 12.0 0 151 20.8 6.5 254 2.5 35 49 0 105 7.0 3.~
3 1.50.25 27 -2.3 155 14.45.0 4 540.25 30 67 0 98 1;.17.1 5 9 82 88 92 0 118 12.83.1 6 31326 1350 1390 0 135 9.68.1 726 2.1 37 543.3 141 14.13.1 839 0.2 26 98~.7 137 6.33.5 9 8 80 89 832.1 120 6.16.1 4 1296 1299 1421 . 1.0 167 8.1 7.0 Example 2 .
Polyolefin-PVA mixtures were prepared in which various polvolerins and polyvinyl alcohol (Vinex) were used in molten sta~e, bv tne aid of a Berstorif mixer which was provided wi~h a rlat ~ilm nozzle. The te~perature profile was from 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 230 to 220 to 220 and the tempera~ur~ o~ Lhe melt :
. - :
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' ,., ' ' ' ' ' . .: ~ .
WO 90tl2061 2 0 3 2121 IIC~/Fl90/00l0;
1 was 220C. The production rate was 10 kilograms per hour.
The thicknesses of the obtained films were 120 to 160 um. The com-pounds thereof are presen~ed in the accompanying Table 2 ~.. Ihe properties of the films are presented in the accompanying Table 2 B.
Table 2 A
Test Pol w n~l alcohol Polvolefin Plasticler type, ~ by weight type, ~ by w . .
11 PVAl 60 PO3 40 12 PVAl 60 PO4 40 13 PVAl 60 PO5 40 14 PVAl 60 PO6 40 _ -~2~
20 Tes~ Oxygen perm. Yellowness Tensile stren~h (ml~-x24hxbar) index, thick- machine /transversal O~RH 65%RH 90%RH ness ~m direc~ion MPa MPa 11 2.1 13.0 56.1 3.1 15410.9 7.1 12 1.8 14.9 49.2 4.~ 16311.0 6.3 13 4.3 12.7 53.1 3.8 153 9.2 8.~
14 3.0 13.2 59.2 2.7 12110.1 5.0 Exam~le 3 Polyolefin-PVA mixtures of the invention were prepared by mixing polyolefin and polyvinyl alcohol, in ~olten state, wi~h the aid of a Berstorff mlxer which was provided with a flat film nozzle. The temperature profile was 2; to 130 to 200 to 200 to 200 to 210 to 230 .;
to 230 to 220 to 220, and the cemperature of the melt was 220C. The production rate was 10 kilograms per hour.
:
~; ~ The thicknesses of the obtained films were 100 to 260 ~m. The com-;
; : : ; . :: . . .
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~- . - ~. :
W O 90/1206t 2 0 3 ~ ~ 21 PCT/F1~0/0010~
1 pounds thereof are presented in the accumpanying Table 3 A. Ihe properties of the films are presented in the accompanying Table 3 B, The oxygen per~eability values of the films are calculated ~or 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 Polyvinyl alcohol Polyolefin Plasticizer type % bv weight type % by w. % by w.
_ 1 PVAl 90 PO6 10 2 PVAl 60 POl 20 3 PVAl 60 PO6 40 4 PVAl 50 PO6 50 PVAl 40 PO6 60 6a PVAl 30 PO6 70 6b PVAl 30 PO6 40 7 PVAl 10 PO6 90 8 PVAl 50 PO15 50 .
- ; the polyvinyl does not contain a plasticizer .
Test Melt Oxygen permeabil. Yellowness Tensile index (ml/m2x24hxbar) index, thick- strength g/10 min 0%RH 65~R~ 90%RH ness ~ ~ach./trans (210C) dir. dir.
MPa ~Pa 1 8.5 0.9 1.2 1.7 0 130 16.2 13.1 2 1.5 1.1 3.2 4.8 0 100 16.7 8.9 3 0.9 1.1 1.5 3.4 0 1~2 19.8 20.2 4 0.7 1.3 1.5 4.5 0 168 20.0 15.6 0.1 1.7 2.6 5.0 0 183 15.7 13.4 : 6a 0.05 38 46 55 0.16 257 11.5 8.5 356b 1.5 1.2 2.1 17.2 2.0 179 18.9 18.5 7 : 0.051890 2560 2390 0 169 18.517.9 8 2.00.4 17 32 0.16 111 15.114.3 .
. ;, .' , .
.
W ~ 90/12061 ~ ~ 3 2 ~ 2 1 PC~ o/ooloS
1 Example 4 For reference were prepared polyolefin-PVA miY.tures in ~hich poly-olefin unmodified with an acid or modified with an acid, and ordinary unmodified polyvinyl alcohol were used (except test 12), in molten state, with the aid of a Berstorff mixer which was proYided with a flat film nozzle. The temperature profile was from 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 230 to 220 to 220, and the temperature of the.~elt was 220C. The production rate was 10 kilo-grams per hour.
The thicknesses of the obtained films were 130 to 230 ~m. The com-pounds thereof are presented in the accompanying Table 4 A. The properties of the films are presen~ed in the accompanying Table 4 B.
_ Test Polyvinyl alcohol Polyolefin Plasticizer - type, % by weight type, % by w, 9 PVA2 90 P06 10 +
PVA2 90 P01 10 +
P06 20 + , 12 PVAl 60 P01 40 14 PVA2 50 P06 50 +
2~ 15 PVA2 50 P01 50 +
lo PVA2 40 P06 60 +
17 PVA2 40 P01 60 +
18 PVA2 30 P06 70 +
19 PVA2 30 P01 70 +
PVA2 10 P06 90 +
21 PVA2 10 P01 90 +
_ _ - - the polyvinyl alcohol does not contain plasticizer + - the quantity oi polyvinyl alcohol contains 6% by weight of a plasticizer, caicula.ed by PVA quantity .. ,. , ~ :
.
. : -' :~ :
: ' ' W O 90/12061 2 0 3 212 ~ Pcr/Fl90/oo1o~
Test Melt Oxygen permeabil. Yellowness Tensile index (ml/m2x24hxbar) index, thick- streng~h g/10 min 0%RH 65~RH 90~RH ness ~m mach./trans (210C) . dir dir.
MPa MPa -9 8.9 0.15 37 43 5.37 227 16.0 16.0 27 0.17 46 52 5 191 13.0 7.5 11 1.1 0.25 25 39 3.45 194 17.5 7.9 12 14 1.0 8.7 15 0 134 20.8 6.S
13 25 0.25 27 43 3.5 136 14.0 6.0 14 0.5 0.9 25 18 1.56191 17.2 11.1 1.0 29 57 30 189 12.7 4.8 16 0.3 1.5 22 33 3.21206 15.9 14.2 17 23 1.5 25 3~ 2.5 201 11.8 4.2 18 0.5 7.2 Sl 63 5.22203 16.5 15.9 19 15 7.5 64 70 2 194 10.9 4.2 0.5 1970 2390 2560 O.SO 173 18.1 17.1 21 12 1990 2460 2380 1.5 200 18.0 13.1 .
Examrle 5 Polvolefin/PVA mixtures were prepared in which various polyolefins modified with an acid and internally plasticized polyvinyl alcohol polymer of the invention, or ordinary polyvinyl alcohol were used, in molten state, with the aid of a Berstorff mixer, wnich was provided with a fla~ fiIm nozzle. The tempera~ure profile was from 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 230 to 220 to 220, and the temperature of the melt was 220C. The production rate was 10 kilograms per hour.
The thicknesses of the obtained films were 120 to 260 ~m. The com-pounds thoreof~are presented in the accompanyir.g Table S A. The properties of the films are presen~ed in the accompanying Table 5 B.
:: . ' , . ~ , . .
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W O 90/12061 2 0 ~ 21 2 ~ Pcr/FIgo/oolo5 1 T.~BL~ j A
.
Tes, Pol w inyl alcohol Polyolefin Plasticizer type, ~ by weigh~ ;ype, ~ by w.
22PVAl 60 P08 40 23PVA2 60 P07 40 +
24PVAl 40 P010 60 26PVAl 60 P012 40 27PVA2 60 P011 40 t 28PVAl 60 P014 40 ~ 29PVA2 60 P013 40 +
30PVAl 50 P015 50 _ - - the polyvinyl alcohol does not contain a plas~icizer + - the quanti~v of polw inyl alcohol contains a plas-ticizer of 6~ by weight, calculated from the PVA
quantity TABLE 5_B
_ 0 Test Melt Oxygen perm. Yellowness Tensile s~rength index ml/m2x24hxbar index/thick- mach./trans-,m g/10 min O~RH 65~H 90~RH ness ~m dir. dir.
MPa MPa _ _ 22 8.0 2.0 3.5 ;.1 0 122 18.1 14.0 25 23 33.9 2.0 36 50 3.5 139 13.7 9.3 24 6.7 10.1 12.3 22 0.05 154 18.1 16.1 25 29 9.0 43 67 2.07 179 12.1 7.2 26 10 1.8 6.1 11 0.09 188 17.9 15.1 2732 3.2 47 61 2.7 26014.1 7.2 286.2 1.3 3.1 4.7 0 189 15.9 8.2 2930 1.3 23 37 3.5 17614.2 5.2 30 304.0 1.0 1.2 3.9 0 123 18.3 17.9 314.0 0.4 17 32 2.5 1S518.1 17.1 .:. : . .
. . . _ _ Test Melt Oxy~en permeabil. Yello~ness Tensile__ ia~ (ml/m~x24hxbar) index,thick- strsn~th g/10 ~in O~RH 65~RH 90%RH ness ~m mach./trans (210C) dir. dir.
IqPa ~Pa .. _ _ . .. .
113 1.0 8.7 12.0 0 151 20.8 6.5 254 2.5 35 49 0 105 7.0 3.~
3 1.50.25 27 -2.3 155 14.45.0 4 540.25 30 67 0 98 1;.17.1 5 9 82 88 92 0 118 12.83.1 6 31326 1350 1390 0 135 9.68.1 726 2.1 37 543.3 141 14.13.1 839 0.2 26 98~.7 137 6.33.5 9 8 80 89 832.1 120 6.16.1 4 1296 1299 1421 . 1.0 167 8.1 7.0 Example 2 .
Polyolefin-PVA mixtures were prepared in which various polvolerins and polyvinyl alcohol (Vinex) were used in molten sta~e, bv tne aid of a Berstorif mixer which was provided wi~h a rlat ~ilm nozzle. The te~perature profile was from 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 230 to 220 to 220 and the tempera~ur~ o~ Lhe melt :
. - :
`' ~' ~ -:, ..
' ,., ' ' ' ' ' . .: ~ .
WO 90tl2061 2 0 3 2121 IIC~/Fl90/00l0;
1 was 220C. The production rate was 10 kilograms per hour.
The thicknesses of the obtained films were 120 to 160 um. The com-pounds thereof are presen~ed in the accompanying Table 2 ~.. Ihe properties of the films are presented in the accompanying Table 2 B.
Table 2 A
Test Pol w n~l alcohol Polvolefin Plasticler type, ~ by weight type, ~ by w . .
11 PVAl 60 PO3 40 12 PVAl 60 PO4 40 13 PVAl 60 PO5 40 14 PVAl 60 PO6 40 _ -~2~
20 Tes~ Oxygen perm. Yellowness Tensile stren~h (ml~-x24hxbar) index, thick- machine /transversal O~RH 65%RH 90%RH ness ~m direc~ion MPa MPa 11 2.1 13.0 56.1 3.1 15410.9 7.1 12 1.8 14.9 49.2 4.~ 16311.0 6.3 13 4.3 12.7 53.1 3.8 153 9.2 8.~
14 3.0 13.2 59.2 2.7 12110.1 5.0 Exam~le 3 Polyolefin-PVA mixtures of the invention were prepared by mixing polyolefin and polyvinyl alcohol, in ~olten state, wi~h the aid of a Berstorff mlxer which was provided with a flat film nozzle. The temperature profile was 2; to 130 to 200 to 200 to 200 to 210 to 230 .;
to 230 to 220 to 220, and the cemperature of the melt was 220C. The production rate was 10 kilograms per hour.
:
~; ~ The thicknesses of the obtained films were 100 to 260 ~m. The com-;
; : : ; . :: . . .
: .::~.
~- . - ~. :
W O 90/1206t 2 0 3 ~ ~ 21 PCT/F1~0/0010~
1 pounds thereof are presented in the accumpanying Table 3 A. Ihe properties of the films are presented in the accompanying Table 3 B, The oxygen per~eability values of the films are calculated ~or 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 Polyvinyl alcohol Polyolefin Plasticizer type % bv weight type % by w. % by w.
_ 1 PVAl 90 PO6 10 2 PVAl 60 POl 20 3 PVAl 60 PO6 40 4 PVAl 50 PO6 50 PVAl 40 PO6 60 6a PVAl 30 PO6 70 6b PVAl 30 PO6 40 7 PVAl 10 PO6 90 8 PVAl 50 PO15 50 .
- ; the polyvinyl does not contain a plasticizer .
Test Melt Oxygen permeabil. Yellowness Tensile index (ml/m2x24hxbar) index, thick- strength g/10 min 0%RH 65~R~ 90%RH ness ~ ~ach./trans (210C) dir. dir.
MPa ~Pa 1 8.5 0.9 1.2 1.7 0 130 16.2 13.1 2 1.5 1.1 3.2 4.8 0 100 16.7 8.9 3 0.9 1.1 1.5 3.4 0 1~2 19.8 20.2 4 0.7 1.3 1.5 4.5 0 168 20.0 15.6 0.1 1.7 2.6 5.0 0 183 15.7 13.4 : 6a 0.05 38 46 55 0.16 257 11.5 8.5 356b 1.5 1.2 2.1 17.2 2.0 179 18.9 18.5 7 : 0.051890 2560 2390 0 169 18.517.9 8 2.00.4 17 32 0.16 111 15.114.3 .
. ;, .' , .
.
W ~ 90/12061 ~ ~ 3 2 ~ 2 1 PC~ o/ooloS
1 Example 4 For reference were prepared polyolefin-PVA miY.tures in ~hich poly-olefin unmodified with an acid or modified with an acid, and ordinary unmodified polyvinyl alcohol were used (except test 12), in molten state, with the aid of a Berstorff mixer which was proYided with a flat film nozzle. The temperature profile was from 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 230 to 220 to 220, and the temperature of the.~elt was 220C. The production rate was 10 kilo-grams per hour.
The thicknesses of the obtained films were 130 to 230 ~m. The com-pounds thereof are presented in the accompanying Table 4 A. The properties of the films are presen~ed in the accompanying Table 4 B.
_ Test Polyvinyl alcohol Polyolefin Plasticizer - type, % by weight type, % by w, 9 PVA2 90 P06 10 +
PVA2 90 P01 10 +
P06 20 + , 12 PVAl 60 P01 40 14 PVA2 50 P06 50 +
2~ 15 PVA2 50 P01 50 +
lo PVA2 40 P06 60 +
17 PVA2 40 P01 60 +
18 PVA2 30 P06 70 +
19 PVA2 30 P01 70 +
PVA2 10 P06 90 +
21 PVA2 10 P01 90 +
_ _ - - the polyvinyl alcohol does not contain plasticizer + - the quantity oi polyvinyl alcohol contains 6% by weight of a plasticizer, caicula.ed by PVA quantity .. ,. , ~ :
.
. : -' :~ :
: ' ' W O 90/12061 2 0 3 212 ~ Pcr/Fl90/oo1o~
Test Melt Oxygen permeabil. Yellowness Tensile index (ml/m2x24hxbar) index, thick- streng~h g/10 min 0%RH 65~RH 90~RH ness ~m mach./trans (210C) . dir dir.
MPa MPa -9 8.9 0.15 37 43 5.37 227 16.0 16.0 27 0.17 46 52 5 191 13.0 7.5 11 1.1 0.25 25 39 3.45 194 17.5 7.9 12 14 1.0 8.7 15 0 134 20.8 6.S
13 25 0.25 27 43 3.5 136 14.0 6.0 14 0.5 0.9 25 18 1.56191 17.2 11.1 1.0 29 57 30 189 12.7 4.8 16 0.3 1.5 22 33 3.21206 15.9 14.2 17 23 1.5 25 3~ 2.5 201 11.8 4.2 18 0.5 7.2 Sl 63 5.22203 16.5 15.9 19 15 7.5 64 70 2 194 10.9 4.2 0.5 1970 2390 2560 O.SO 173 18.1 17.1 21 12 1990 2460 2380 1.5 200 18.0 13.1 .
Examrle 5 Polvolefin/PVA mixtures were prepared in which various polyolefins modified with an acid and internally plasticized polyvinyl alcohol polymer of the invention, or ordinary polyvinyl alcohol were used, in molten state, with the aid of a Berstorff mixer, wnich was provided with a fla~ fiIm nozzle. The tempera~ure profile was from 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 230 to 220 to 220, and the temperature of the melt was 220C. The production rate was 10 kilograms per hour.
The thicknesses of the obtained films were 120 to 260 ~m. The com-pounds thoreof~are presented in the accompanyir.g Table S A. The properties of the films are presen~ed in the accompanying Table 5 B.
:: . ' , . ~ , . .
~. - . . , ".:, , , ; ~ ' ' ':
W O 90/12061 2 0 ~ 21 2 ~ Pcr/FIgo/oolo5 1 T.~BL~ j A
.
Tes, Pol w inyl alcohol Polyolefin Plasticizer type, ~ by weigh~ ;ype, ~ by w.
22PVAl 60 P08 40 23PVA2 60 P07 40 +
24PVAl 40 P010 60 26PVAl 60 P012 40 27PVA2 60 P011 40 t 28PVAl 60 P014 40 ~ 29PVA2 60 P013 40 +
30PVAl 50 P015 50 _ - - the polyvinyl alcohol does not contain a plas~icizer + - the quanti~v of polw inyl alcohol contains a plas-ticizer of 6~ by weight, calculated from the PVA
quantity TABLE 5_B
_ 0 Test Melt Oxygen perm. Yellowness Tensile s~rength index ml/m2x24hxbar index/thick- mach./trans-,m g/10 min O~RH 65~H 90~RH ness ~m dir. dir.
MPa MPa _ _ 22 8.0 2.0 3.5 ;.1 0 122 18.1 14.0 25 23 33.9 2.0 36 50 3.5 139 13.7 9.3 24 6.7 10.1 12.3 22 0.05 154 18.1 16.1 25 29 9.0 43 67 2.07 179 12.1 7.2 26 10 1.8 6.1 11 0.09 188 17.9 15.1 2732 3.2 47 61 2.7 26014.1 7.2 286.2 1.3 3.1 4.7 0 189 15.9 8.2 2930 1.3 23 37 3.5 17614.2 5.2 30 304.0 1.0 1.2 3.9 0 123 18.3 17.9 314.0 0.4 17 32 2.5 1S518.1 17.1 .:. : . .
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 and polYvinyi aicohol.
characterized in that the material is prepared by mixing 1 to 99 per cent by weight of polyolefin and 99 to 1 per cent by weight of in-ternally plasticized vinyl alcohol polymer in molten state, and optionally 1 to 15 per cent by weight of a plasticizsr. - 2. Gas-sealed material according co claim 1, characterized in that in the vinyl alcohol polymer chains are present polyglycol groups (polyether groups) as side groups.
- 3. Gas-sealed material according to claim 1 or 2, characterized in that the poiyvinyl 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 acrylic acid or methacrylic acid.
- 5. A gas-sealed mixture according to any one of the preceding claims, characterized in that the polvvinyl alcohol contains an unmodified polyvinyl alcohol in the form of mixture and vinvl 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 ethvlene copolymer with propylene, butene, hexene and octene, or an olefin/ester co-polymer, such as ethylene-vinvl-acetate copolymer, ethylene-acrylate ester copolymer or ethylene-methacrylate ester copolymer, EP rubber.
EPD rubber or some other thermoplastic olefin-based elastomer. or a mixture of one or several above-mentioned polyolefins. - 7. A gas-sealed materlai according to claim 6 characterized in that the polyolefin is modiEied by grafting or copoivmerizing tereto 0.1 WO90/12061 PCT/F190/0010;
to 10 per cent by weight of carboxylic 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 it consists further 1 to 15 per cent by weight of one or several plasticizers selected from among the group of ethylene glycol, trimethylene glycol, propylene glycol, triethylene glycol, neopenthyl glycol and 2,2,4-trimethyl-1,3-pentanediol and sorbitol. - 10. Products containing a gas-sealed material according to any one of the preceding claims.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI891752 | 1989-04-13 | ||
| FI891752A FI86870C (en) | 1989-04-13 | 1989-04-13 | GASTAETT MATERIAL, SOM INNEHAOLLER INVAENDIGT MJUKGJORD POLYVINYLALCOOL |
| FI891753 | 1989-04-13 | ||
| FI891753A FI86871C (en) | 1989-04-13 | 1989-04-13 | Gas-sealed material containing internally plasticized polyvinyl alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2032121A1 true CA2032121A1 (en) | 1991-10-12 |
Family
ID=26158537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002032121A Abandoned CA2032121A1 (en) | 1989-04-13 | 1990-04-11 | Gas-sealed material |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0423271A1 (en) |
| JP (1) | JPH04500536A (en) |
| AU (1) | AU627870B2 (en) |
| CA (1) | CA2032121A1 (en) |
| WO (1) | WO1990012061A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5972447A (en) * | 1996-09-30 | 1999-10-26 | Kuraray Co., Ltd. | Thermoformable multilayer film and thermoformed container |
| WO1999054400A1 (en) * | 1998-04-20 | 1999-10-28 | Kwang Myung Pharm. Ind. Co., Ltd. | Compositions of polyolefin and polyvinyl alcohol, and films, sheets and articles processed therefrom and multilayer products using the same |
| DE10046619A1 (en) * | 2000-09-20 | 2002-03-28 | Clariant Gmbh | Plastics composition for molded barrier medium or motor fuel tanks comprises polyolefin/maleic anhydride and polyvinyl alcohol |
| US8338508B2 (en) * | 2008-05-14 | 2012-12-25 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing an olefinic elastomer |
| CN107141672A (en) * | 2017-07-06 | 2017-09-08 | 华东理工大学 | A kind of high barrier composition and preparation method thereof |
Family Cites Families (9)
| 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 |
| US3945463A (en) * | 1974-07-27 | 1976-03-23 | Yamaha Hatsudoki Kabushiki Kaisha | Lubrication system for motorcycles |
| CA1146323A (en) * | 1979-03-06 | 1983-05-17 | Pallatheri M. Subramanian | Laminar articles of polyolefin and a second polymer and process for making them |
| US4575532A (en) * | 1984-02-08 | 1986-03-11 | Norchem, Inc. | Polyvinyl alcohol alloys and method of making the same |
| JPS6181448A (en) * | 1984-09-06 | 1986-04-25 | Kuraray Co Ltd | Resin composition with impact resistance |
| 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 |
-
1990
- 1990-04-11 CA CA002032121A patent/CA2032121A1/en not_active Abandoned
- 1990-04-11 AU AU54037/90A patent/AU627870B2/en not_active Ceased
- 1990-04-11 WO PCT/FI1990/000105 patent/WO1990012061A1/en not_active Application Discontinuation
- 1990-04-11 JP JP2505632A patent/JPH04500536A/en active Pending
- 1990-04-11 EP EP19900905546 patent/EP0423271A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| AU5403790A (en) | 1990-11-05 |
| JPH04500536A (en) | 1992-01-30 |
| EP0423271A1 (en) | 1991-04-24 |
| WO1990012061A1 (en) | 1990-10-18 |
| AU627870B2 (en) | 1992-09-03 |
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