Although the packaging of PET bottles in soft drinks and mineral water has been very successful and widely used, PET packaging containers for oxygen-sensitive and light-sensitive products (such as beer, juice, and ice tea, etc.) have been studied. Progress is slower. The main reason is that the barrier properties of bottles made from PET alone cannot achieve the requirements for soft drink packaging. At present, there are many solutions for the barrier properties of PET bottles. The most common method is to use PET bottles as multilayers to allow PET and barrier properties such as EVOH, nylon or a mixture of these substances. Multi-layer co-extrusion was performed to overcome the disadvantage of poor PET barrier properties.
The maximum amount of oxygen that each product can absorb during the maintenance period
(Source: Atalink Ltd. and Pira International.)
Although the multi-layer process is still the most used method to improve PET barrier properties, it is not perfect. Multi-layer co-extruded bottles have a more expensive price than single-layer containers. The various polymers in multilayer bottles make multi-layer co-extruded bottles difficult to regenerate. Especially for the innermost layer with high barrier properties in contact with food, there are often many considerations regarding the hygiene standards. Moreover, especially in the hot filling process, the peeling phenomenon easily occurs between the layers.
The limitations of multi-layer coextruded PET bottles have led people to pay more and more attention to the research of single-layer PET bottles. To achieve a single-layer PET bottle while also requiring high barrier properties, these methods can often be solved by adding a dispersible oxygen absorber to PET, and combining PET with nylon MXD6 with barrier properties. Mixing PET with other high-barrier polyester resins can also be used to form polymer alloys. No matter which method is used, the purpose is to provide a product with high cost performance. The unique polymer can produce single-layer PET bottles that meet the requirements of the standard, and does not require any improvement to the existing PET production equipment, and the produced PET bottles do not require post-processing.
Generally, post-processing of multi-layer co-extruded PET bottles involves applying a layer of silica or other resin to the outer surface of the inner surface of the PET layer to further enhance the barrier properties of the multilayer coextruded PET bottle. However, this increases the steps of the PET production process, thereby increasing the production cost of the product. The production of PET bottles using a single-layer process does not require any coating except under very harsh conditions.
Auxiliaries that have only been activated by filling
For many PET single-layer bottles, most of the oxygen scavenger in the PET carrier resin has great activity once the bottle is made. However, this activity is not always beneficial, especially in days or weeks before the bottle is filled with the product of the packaged product. Because in this case, the scavengers did not fill the entire bottle and the bottle was not sealed, this allowed the oxygen scavenger to react with the oxygen in the air, thereby reducing the amount of oxygen scavenger. Therefore, the solution to this problem is to use a PET resin-supported oxygen scavenger added to the PET resin to produce the oxygen scavenger that is present in the carrier only when filling the bottle with the product to be packaged. Only when it receives the influence of the humidity of the packaged product does it have oxygen absorbing activity, so as to achieve a good barrier effect. By using such a resin containing an oxygen scavenger, the PET bottle can extend the storage time of the packaged product to a greater extent. Because, oxygen absorbers can only have a corresponding chemical activity when the bottle is filled with the product, so that the oxygen in the bottle can be absorbed for a longer period of time.
Oxygen Absorption Comparison
(Source: M&G.)
The current manufacturer of oxygen-reducing PET resins that only have oxygen-absorbing activity during the filling process is the M&G (Gruppo Mossi & Ghisolfi) group, a producer of polymers and semi-finished products in Italy. For beer packaging applications, M&G's single-layer PET resin is called ActiTUF. This material is said to have both chemical barrier (by the use of oxygen scavenger) properties and also physical barrier properties (by blending with other barrier materials such as nylon MXD6). At present, ActiTUF technology has been favored by many brewers and has also been widely used in many regions: Belgium, the Netherlands, Russia, Hungary, the Czech Republic, Bulgaria and Romania. It is said that some parts of Korea also use this resin for the production of beer bottles.
Oxygen absorber
Adding oxygen scavenger to PET resin can improve the barrier properties of PET because these auxiliaries are chemically active and can react with the oxygen in the bottle and can also react with the oxygen that tries to penetrate the bottle wall to achieve a chemical reaction. The purpose of absorbing oxygen. Commonly used oxygen scavengers include: iron dioxide, unsaturated fatty acid salts, and metal/polyamide alloys.
Currently available on the market is a single-layer PET bottle resin containing a deoxidizer called MonOxbar, which is produced by Constar International of Philadelphia, Pennsylvania. Its products mainly package oxygen-sensitive products such as pasta sauces, ketchup, beer, vitamins, and other foods. MonOxbar resin has met regulatory requirements for food contact packaging in the United States and Europe.
Single layer - PET bottle
(Source: Constar International Inc.)
At the same time, Constar International also introduced single-layer bottles with high transparency, which are mainly produced using resins containing oxygen scavenger. Its material resin is DiamondClear, which is even more transparent than glass.
Another PET/deoxidizer alloy used to produce single-layer bottles is Amosorb DFC, developed by BP. This product is currently used by Graham Packaging. In general, the alloy and the PET resin need to be mixed before processing.
Blends with nylon
The material obtained by uniformly blending PET with nylon MXD6 can be used in the production of hollow bottles and also has good physical and chemical barrier properties. Nylon components provide very good physical barrier properties to the blend (mainly preventing gas from entering the bottle through the bottle wall). In addition, MXD6 can be oxidized if properly initiated using a metal catalyst such as a cobalt catalyst. This allows the material to absorb any oxygen present in the bottle or any oxygen that enters the bottle through the bottle wall.
One company in the United States, Invista, offers a PolyShield technology that can be used to produce PET and nylon MXD6 blended gold in injection molding machines (PET contains compatibilizers and catalysts). The company said: This alloy can provide good transparency and can be used in oxygen sensitive foods and beverages such as beer, juice, seasonings and milk and other packaging. According to Invista, PolyShield technology allows single-layer pre-formed products to be produced in standard equipment, and this equipment requires only minor changes, so there is no need to add any major cost or complicate the process.
Amber or green single layer bottle
(Source: Koch Industries.)
Blending with other polyesters
Another way to increase PET barrier properties is to blend PET with other high barrier polyesters. For example, Futura Polyester Group of India stated that the material made from PET blended with a polyester such as PTN is very tender and greatly improves the performance of PET bottles. According to the company, the barrier properties of PET/PTN alloys to carbon dioxide are 18 times that of pure PET, and oxygen barrier performance is 9 times that of pure PET. This will greatly extend the product's storage date. In addition, beer bottles with the PET/PTN alloy brand name are Beer PET.
in conclusion
Because pure PET material does not provide good barrier properties for oxygen sensitive foods and beverages, it has limited the use of this material in soft drinks and mineral packaging. Multi-layer co-extrusion has allowed PET to be extended in this market, but this approach has significant drawbacks. Single-layer PET bottles are a simpler and more economical solution that can compensate for the lack of pure PET. The current leading technology in single-layer PET is the addition of oxygen scavenger in PET or blending with polyester with barrier properties. Although multi-layer PET bottles will still dominate the market for PET beer, juices, condiments, and other oxygen-sensitive product packaging, single-layer PET bottles will pose enormous challenges for multi-layer systems.
References:
Network information:
Amcor PET Packaging, ColorMatrix, Constar International, Futura Polyesters, Graham Packaging, Interbrew, Invista, M&G Group
publication:
Joseph A. Grande, "Barrier Bottle Technologies Square Off," Plastics Technology, August, 2005.
Robert Leaversuch, "Barrier PET Bottles: No Breakthrough in Beer, but Juice and Soda Surge Ahead," Plastics Technology, March, 2003.
"Blended Beer Bottles Being Tested in India," Plastics News, June 23, 2005.
"Firms Want Russian Beer in PET Bottles," Plastics News, Jan. 333, 2005.
other:
US Patent 6,863,988 (2005), "Oxygen Scavenging Monolayer Bottles."
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