AU2910399A - Polymeric material and its use in multilayer products - Google Patents
Polymeric material and its use in multilayer products Download PDFInfo
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- AU2910399A AU2910399A AU29103/99A AU2910399A AU2910399A AU 2910399 A AU2910399 A AU 2910399A AU 29103/99 A AU29103/99 A AU 29103/99A AU 2910399 A AU2910399 A AU 2910399A AU 2910399 A AU2910399 A AU 2910399A
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- AU
- Australia
- Prior art keywords
- ethylene
- gas
- layer
- tight
- polymer
- 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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- 239000000463 material Substances 0.000 title description 12
- 229920000573 polyethylene Polymers 0.000 claims description 22
- 239000004698 Polyethylene Substances 0.000 claims description 20
- -1 acrylic ester Chemical class 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 19
- 239000005977 Ethylene Substances 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 14
- 229920003023 plastic Polymers 0.000 claims description 12
- 239000004033 plastic Substances 0.000 claims description 12
- 239000011087 paperboard Substances 0.000 claims description 10
- 229920006112 polar polymer Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 150000002735 metacrylic acids Chemical class 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 229920001897 terpolymer Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 230000035699 permeability Effects 0.000 description 8
- 229920002959 polymer blend Polymers 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000005022 packaging material Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 241001312297 Selar Species 0.000 description 2
- 229920003365 Selar® Polymers 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 241001462977 Elina Species 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
P/00/0oII Regulation 3.2
AUSTRALIA
PATENTS ACT 1990 a a.
COMPLETE
SPECIFICATION
FOR A STANDARD
PATENT
a..
S:ORIGINAL IP Austraia~
W
iDocumnents recsi\/eci' 0'l TO BE COMPLETED BY APPLICANTtnN: liame of Applicant: BOREALIS A/S and ENSO-GUTZEIT
GY
Actual Inventor(s): LAIHO Erkki; SAINJO Markku; KUUSELA Seppo; KOSKI Elina; PENTTINEN Tapani; KOSKINIEMI Riitta; SALSTE Matti.
Address for Service: CALLINAN LAWRIE, 711 High Street, Kew, 3101, Victoria, Australia Invention Title: POLYMERIC MATERIAL AND ITS USE IN MULTILAYER
PRODUCTS
The following statement is a full description of this invention, including the best method of performing it known to me: I 8/O5/99,a18978.coi,
I
Polymeric material and its use in multilayer products The invention relates to a packaging material which has good barrier properties vis-a-vis gases and moisture. The invention further relates to a polymeric material which is used as a gastight layer in such packages, and further to multilayer products in which said polymer is used.
Liquid foodstuffs, such as juices, which are sensitive to oxidation, are in general packaged in sales packages made from laminated paperboard. Through selection of the packaging material, efforts are made to provide good chemical and mechanical protection for the product, and the material has to be sufficiently firm in shape to be easy to handle.
SThere is in general use a packaging material the structural part of which consists of paperboard or paper which is sufficiently firm but, nevertheless, flexible so that a package of a desired shape can be formed therefrom. To protect the structural material from liquid and other moisture, it is coated with plastic, usually polyethylene. However, the oxygen permeability of polyethylene and paperboard is high, and therefore the product would 2 spoil very rapidly if a gas-tight layer were not also added to the package. The gas-tight layer conventionally used has been aluminum foil bonded to the paperboard. Another alternative has been a gas barrier polymer such as ethylene/vinyl alcohol copolymer (EVOH). The purpose of the gas-tight layer is to prevent the access of oxygen into the product and thus, for example, to maintain high the level of vitamin C in the product.
For some time, attempts have been made to eliminate the aluminum foil, for example for reasons of environmental protection, but also because of its poor handlability. Furthermore, the aluminum layer is easily broken.
Finnish Patent FI89567 discloses a barrier structure in which ethylene/vinyl alcohol copolymer is used. Such structures, in the same way as when aluminum is used, usually contain, in addition to the carrier web (polyethylene paperboard), at least five layers: polyethylene/paperboardpolyethylene/adhesion plastic/gas-tight EVOH polymer/adhesion plastic/polyethylene. The multilayer structure, of course, also increases the price of the package and renders its manufacture complicated. Furthermore, the gas-tight polymer in 3 oxygen barrier layer when it is inside a coextruded structure, in the same way as does EVOH alone. When the layer made of the polymer blend is on the inside surface of the package structure, a good aroma-proofing is also achieved. As compared with a mere ethylene/vinyl alcohol polymer, a lower blistering tendency and a higher resistance to heat and moisture are achieved. Since one component in the polymer blend is polar, as a consequence better sealability properties, good hot-tack properties, and better adhesion properties are achieved than by using a pure polymer. As a result, the use of a separate adhesion plastic layer can be abandoned. Furthermore, the processibility of the polymer blend is better, and smaller layer thicknesses can be used.
Polyolefin, preferably polyethylene, which may be any polyethylene (LD, HD, LLD, VLD, etc.), is used as the moisture-proof layer. Preferably a polar polymer selected from S' the same group as the polymers in the gas-tight polymer blend is added to the polyethylene, in an amount of 2-50 preferably 20-30 By this addition, good adhesion of the layers to each other is ensured, as is good seal strength at lower sealing temperatures SFurthermore, the blistering tendency is lower. Environmental stress crack resistance (ESCR), water vapor transmission rate (WVTR) and frictions are easier to control. Resistance to wear is also better, especially if high-density (HD) or linear (LLD) polyethylene is used, and consequently, plastic dust will not be formed on rapid package-manufacturing 20 lines and the blanks will travel smoothly on the lines.
The polar polymer can be mixed with the ethylene/vinyl alcohol polymer and, respectively, with the polyolefin by any conventional mixing technique. Either melt mixing or dry mixing can be used.
The carrier web may be any web which can be coated, but a combination of paperboard and polyethylene is highly suitable for packages for liquids. The other layers are typically bonded to the carrier web by coextrusion coating.
The number of layers placed on one side of the carrier web, and their mutual order, can be varied according to the application, and in particular according to the requirements set by the product to be packaged. With smaller numbers of layers, the price of the multilayer structure, i.e. the packaging material, will be considerably lower. According to the present invention, 2-layer coextrusion instead of the previous 5-layer coextrusion will well suffice for many applications. Owing to the small number of layers, pulpability will be considerably improved, and blistering tendency in the heat-sealing step is nil. The unproved pulpability is due above all to the fact that an EVOH/PE layer bonded directly to paperboard detaches from the paperboard more easily than does an adhesion plastic layer. In consequence to easier pulping, recycling of the material will be simpler.
Depending on the application, the gas-tight layer and the moisture-proof layer may be in different orders on the carrier web: a-b, b-a, a-a- a-b-a. The order depends on the 10 product to be packaged, i.e. on whether protection is needed specifically against the permeability of moisture, oxygen, aromatic substances, etc.
The invention is described in greater detail with the help of the following examples.
15 Example 1.
SA gas-tight plastic was prepared by blending an amount of 80 of ethylene/vinyl alcohol copolymer, EVOH (44 ethylene), manufacturer Du Pont and trade name Selar OH 4416, with an amount of 20 of ethylene/ethyl acrylate copolymer, EEA, manufacturer 20 Borealis and trade name NCPE 5860. The mixing was performed in a Berstoff twin screw extruder (0 40 mm).
A carrier web (15 g/m 2 PE-LD and 300 g/m 2 paperboard) was coextrusion coated on a Beloit pilot line with a double-layer coating in which the gas-tight layer consisted of 10 g/m 2 (EVOH EEA) and the moisture-proof layer consisted of 30 g/m 2 low-density polyethylene, PE-LD, manufacturer Borealis Polymers Oy and trade name NCPE7518.
There were thus only two layers in addition to the carrier web. The oxygen permeability of the material was 6 cm 3 /m 2 per 24 h at a temperature of 23 *C and a relative humidity of 50 The oxygen permeability of a corresponding conventional 5-layer structure was 4 cm 3 /m 2 per 24 h. The layers of the conventional structure were: carrier web 15 g/m 2 PE-LD and 300 g/m 2 cardboard, and on top of it a 5-layer coextrusion coating consisting of 20 g/m 2 PE-LD, 6 g/m 2 adhesion polymer, 10 g/m 2 EVOH, adhesion plastic 6 g/m 2 and PE-LD g/m 2 (Figure The adhesion polymer used was polyethylene modified with maleic anhydride, trade name NCPE 0470, manufacturer Borealis Polymers Oy.
The saving of material in the structure according to the invention is considerable as compared with traditional structures, and the gas-tightness is of substantially the same level.
The structure according to the invention is shown in Figure 2.
Example 2.
S. A gas-tight plastic was prepared by mixing an amount of 80 of ethylene/vinyl alcohol copolymer, EVOH (38 ethylene), manufacturer Kuraray and trade name EVAL 101H, 15 with an amount of 20 of polyethylene modified with maleic acid, manufacturer Borealis Polymers Oy and trade name NCPE 0470. The mixing was carried out in the same manner as in Example 1.
A carrier web was coextrusion coated in the same manner as in Example 1, but the thickness of the gas-tight layer was only 6 g/m 2 The permeability to oxygen was 3 cm'/m 2 per 24 h, 23 50 relative humidity.
In multilayer packaging materials there has often been a problem of blistering during sealing. The blistering tendency of this product according to Example 2 was 50 less than that of the control product according to Figure 1.
Example 3.
To maximize internal adhesion and sealability, modified polyethylene was used also as the polyethylene layer (PE-LD). An amount of 25 of anhydride-modified polyethylene, NCPE 0470, and an amount of 75 of PE-LD, NCPE 7518, were mixed. The thicknesses of the layers were the same as in Example 2. As a consequence, the adhesion to the gas-tight layer and the heat-sealing properties were further improved. Blistering tendency 6 also decreased further.
Example 4.
In order to achieve maximal aroma-proofing, impermeability and flavor-tightness of ethereal oils, a structure according to Example 4 was prepared, but a surface layer similar to the gas-tight layer was added to it (Figure Such a structure has very good properties but, nevertheless, in addition to the carrier web it has only three layers instead of the traditional five.
Example In order to improve further the sealing properties and watertightness of the layer coming S•against the product, the mixing proportions of the gas-tight layer were optimized.
A
15 gas-tight plastic was prepared by mixing an amount of 60 of ethylene/vinyl alcohol copolymer, manufacturer Du Pont and trade name SELAR OH 4416, and an amount of of polyethylene modified with maleic acid, manufacturer Borealis Polymers Oy and trade name NCPE 0470. The mixing was carried out as in Example 1.
20 A film 40 pm thick was prepared of the blend. The permeability of the film to oxygen was 1.3 cm/m 2 per 24 h, 23 50 relative humidity. The oxygen permeability of a film of the same thickness made of pure ethylene/vinyl alcohol copolymer was 0.3 cm 3 /m 2 per 24 h, 23 50 relative humidity. If a gas-tight blend such as this, in which the ratio of the polymers is 60/40, is used in a layered structure a-b-a, i.e. there are two gastight layers, good gas-tightness and aroma-proofing properties are achieved, and the processibility of the gas-tight blend is considerably better than that of pure ethylene/vinyl alcohol copolymer.
The blistering tendency was very low.
Example 6.
By the use of polymer blends according to the invention, the melt strength of the gas-tight layer can be improved substantially and the so-called blistering tendency of the structure is reduced. Blistering tendency was measured by using a device specially developed for the purpose, in which hot-air blowing is used.
The sample to be tested is attached to a holder, which makes a constant-velocity reciprocal movement under hot-air blowing. The distance from the blower to the sample is 7 mm, and the temperature of the hot air is 350 0 C. The blowing causes melting of the plastic. The sample will resist without melting under hot air for a number of reciprocal Smovements which is the greater the better the resistance of the sample to blistering.
*The test device clearly correlates with results in practice in packaging machines in which hot air is also used for sealing.
Table 1 shows the results of the blistering test for the control material according to Figure •15 1 and for materials according to Examples 3 and 5. The number indicates the number of reciprocal swings. The blistering tendency of the structures according to the invention is considerably lower than that of the control structure.
This application is a divisional application of 24109/95, the subject matter of "which is incorporated herein by way of reference.
8 in a hot-air blowing device Table 1. Blistering tests number of 1 1,5 2 2,5 3 3,5 4 4,5 swings Product Control, 5-layered U F F F M M Ex. 3, 2-layered U U U U U V F F M Ex. 5, 3-layered U U U U U U U F F a a.
S.
S
S
U unbroken V very few holes F few holes M many holes 15 As can be seen from the above examples, by the use of gas-tight and moisture-proof polymer blends according to the invention, considerable savings of material can be achieved and simpler manufacturing techniques can be used and, nevertheless, the permeability and other properties obtained for the package will be at least as good as those achieved with conventional alternatives. The processibility of the EVOH/PE blend is better than that of pure EVOH, which is due to the better melt strength of the blend.
Consequently, a thinner gas-tight layer than conventional will suffice.
Claims (12)
1. A multilayer product for the production of liquid packaging, the product having special tightness properties and comprising a carrier web made from paper board and a. possible plastic layer, on one face of which there is disposed a tight multilayer coating characterized in that the coating includes,in any order, disposed one on top of the other, a moisture-proof layer and a gas-tight layer made up of a blend of an ethylene/vinyl alcohol copolymer and a polar ethylene polymer. 10
2. A multilayer product according to Claim 1, characterized in that the polar polymer *t. in the gas-tight layer is a copolymer of ethylene and acrylic ester, a copolymer of ethylene and vinyl acetate, or a copolymer of ethylene and (met)acrylic acid.
3. A polar polymer according to Claim 2, characterized in that the acrylic ester is 15 selected from the group ethyl acrylate, butyl acrylate or methyl acrylate.
4. A multilayer product according to Claim 1, characterized in that the polar polymer in the gas-tight layer is a polyolefin modified with carboxylic acid or carboxylic anhydri- de.
5. A polar polymer according to Claim 4, characterized in that it is a polyethylene modified with maleic anhydride.
6. A multilayer product according to Claim 1, characterized in that the polar polymer in the gas-tight layer is a copolymer of ethylene, acrylic ester and carboxylic acid or anhydride, such as ethylene/butyl acrylate/metacrylic acid terpolymer.
7. A gas-tight layer according to Claim 1, characterized in that the ethylene content in the ethylene/vinyl alcohol copolymer is 20-50
8. A gas-tight layer according to Claims 1-7, characterized in that the blend contains polar polymer in an amount of 5-60
9. A multilayer product according to Claim 1, characterized in that the moisture-proof layer is a blend of polyethylene and a polar ethylene polymer.
A moisture-proof layer according to Claim 9, characterized in that the polar polymer is in accordance with Claims 2-6.
11. A moisture-proof layer according to Claims 9-10, characterized in that the amount of polar polymer is 2-50 preferably 20-30 10
12. A multilayer product according to any of the above claims, characterized in that the multilayer coating is done by coextrusion coating. g o .DATED this 18 day of May 1999 BOREALIS A/S and ENSO-GUTZEIT OY By their Patent Attorneys CALLINAN LAWRIE
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU29103/99A AU2910399A (en) | 1994-05-25 | 1999-05-18 | Polymeric material and its use in multilayer products |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI942416 | 1994-05-25 | ||
| AU29103/99A AU2910399A (en) | 1994-05-25 | 1999-05-18 | Polymeric material and its use in multilayer products |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU24109/95A Division AU725221B2 (en) | 1994-05-25 | 1995-05-16 | Polymeric material and its use in multilayer products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2910399A true AU2910399A (en) | 2000-11-23 |
Family
ID=3717200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU29103/99A Abandoned AU2910399A (en) | 1994-05-25 | 1999-05-18 | Polymeric material and its use in multilayer products |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU2910399A (en) |
-
1999
- 1999-05-18 AU AU29103/99A patent/AU2910399A/en not_active Abandoned
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK1 | Application lapsed section 142(2)(a) - no request for examination in relevant period | ||
| MK4 | Application lapsed section 142(2)(d) - no continuation fee paid for the application |