Nanopolyester bottle molding process PET beer bottle latest results (in)

. A high-frequency current acts on the electrode. At this time, the coating chamber is an external electrode, and the acetylene tube is an internal electrode; acetylene is decomposed into ionized carbon and ionic hydrogen due to current discharge, and ionized carbon and ionized hydrogen are combined on the inner surface of the bottle. , Forming a fine coating.

This carbon-based coating by vapor deposition has a thickness of 20 nm to 40 nm, which is 20 times more gas-barrier than an ordinary PET bottle, 7 times higher in CO2 permeation resistance, and 8 times higher in anti-H2O permeability. The ability is also enhanced.

2. PET bottle with barrier coating

Using a variety of high barrier coatings and coating techniques, a very thin barrier layer is formed on the inner or outer surface of PET bottles, which can also effectively extend the shelf life of PET bottled beer. Among them, plasma coating technology has become a hot spot for competitive development and application since 1999.

(1) Plasma coated "amorphous carbon" coating

Japan's Kirin Brewery Co., Ltd., in cooperation with Mitsubishi Corporation, blow molding machine manufacturer Nissei ASB Machinery Co., and Youtec Inc., a manufacturer of plasma chemical vapor deposition (CVD) devices, earlier developed a patented plasma CVD coating technology for PET bottles. The technology uses a vacuum inside and outside the PET bottle. The bottle is filled with methane, acetylene and other hydrocarbon gases. The outside of the bottle is subjected to high frequency or microwave discharge to decompose and plasma the hydrocarbon gas in the bottle. The carbon ions and hydrogen ions are produced together. Steamed on the inner wall of the bottle to form a diamond-like carbon (DLC) coating with a thickness of only 0.02 to 0.04 μm. It is said that the gas barrier property of this coated bottle is more than 10 times that of ordinary PET bottles, and it is comparable to glass bottles, and the coating is soft and does not easily crack. Now we are developing practical production equipment to make it commercial. According to reports, these Japanese companies saw that traditional beer bottle packaging containers are in short supply in China. Therefore, they intend to promote their use of this technology in China first.

(2) PET beer bottle barrier process

Japan's Mitsubishi Corporation Plastics Corporation, Nissei ISB Machinery Co., Ltd. and Utech Inc. announced that the three companies have jointly developed a PET bottle in-film technology that can evenly paste a layer of carbon dioxide with a thickness of 20 to 30 nm in the bottle to achieve glass. The bottle has the same anti-seepage effect. The 500mL beer bottle weighs 30g, which is 1/10 of the Glass Bottle.

The new three-in-one barrier technology for PET bottle stretch blow molding, developed by Tetra Corporation of Geneva, Switzerland and Toyo Seikan of Tokyo, may have a significant impact on the beer packaging market. ToyoSeilan has developed a new pull-blow molding system called S-Cosmos, which can be used to produce heat-resistant and pressure-resistant 500ml PET. It can withstand pasteurization conditions up to 75°C and 400min, and can be 30,000/ Hours of speed production.

DuPont also developed an outer coating technology called "transparent aluminum". The barrier properties of such coated bottles are 30 to 40 times that of ordinary PET bottles and are now being tested and are close to commercialization.

3. Nanotechnology to increase barrier/heat resistance

KruppCorpoplast, Germany, ToyoSeikan, Japan, and PlasticSolutionsMolding of the United States have developed their own heat-setting technologies, namely “MonoTherm”, “S-Cosmos” and “Cr-yopak”, which can significantly increase the crystallinity and heat resistance of PET bottles. For example, from 20% and 85 °C respectively to 39% ~ 42% and 120 °C, making it suitable for packaging pasteurized beer after filling, without the need to design using stiffeners and stiffeners. These heat-setting techniques still need to be combined with barrier coating techniques to achieve the required shelf life.

The Institute of Chemistry and the Institute of Physics of the Chinese Academy of Sciences has taken a different path to explore and research the application of PET/montmorillonite nanocomposites and their applications. It has been used to make translucent beer bottle samples, which are 3 to 4 times more barrier than PET bottles. The heat has also improved.

Polyethylene terephthalate (PET) is mainly used for fibers, bottles, and films. The amount of engineering plastics only accounts for a very small part of its total production. As an engineering plastic, the performance of PET resin is very attractive, but its poor melt strength, slow crystallization speed, and poor dimensional stability make it difficult to meet the needs of rapid prototyping in industry. The world's major companies have invested a lot of manpower and material resources, developed a variety of rapid crystallization nucleating agents, thereby increasing the crystallization rate of PET, but due to the high price of these nucleating agents, restricting the large-scale application of PET engineering plastics. The PET polymerization intercalation composite technology invented by the Institute of Chemistry of the Chinese Academy of Sciences, the organic montmorillonite was added together with the PET monomer into the polymerization tank, and PET nano plastic (NPET) was successfully prepared. The melt viscosity and crystallization speed of NPET are significantly improved, which overcomes the drawbacks of “flowing defects” that are common in the processing of common PET resin, and improves the processing performance and product performance of the material. Compared with ordinary PET, NPET's flame retardant performance has also been greatly improved, and self-extinguishing. In combination with NPET's flame-retardant NPET engineering plastics developed by NPET, the performance indicators have met or exceeded domestic and international PET engineering plastic products (see Table 3), and can be used to produce various electrical components instead of expensive ones. Polybutylene terephthalate (PBT) resin. The barrier property of NPET has been greatly improved compared with pure PET, and it meets the requirements for food packaging and can be directly used to blow bottles for beer, beverages, pesticides and cosmetics.

4. Nylon-based nanocomposite transfer PET containers According to the British “European Chemical News” report, Eastman Chemical Co., Ltd. and Nanocor were jointly developed for the manufacture of multi-layer PET containers and nylon nanocomposites. High-quality, processability similar to that of PET, and adhesion with PET, and trial marketing has begun. The range of applications for PET barriers with high barrier properties includes beer packaging, carbonated soft drinks, fruit and food packaging made from processed tomatoes. Products made with nanocomposites can be processed on existing equipment, such as preform injection molding machines and stretch blowers.

The oxygen barrier properties of nylon nanocomposites under development have been greatly improved. The nylon nanocomposites containing 10% to 30% by weight of clay have much better barrier properties compared to those of nylons with barrier properties. Moreover, the thickness of the barrier layer is greatly reduced. The turbidity of this material is 15% to 30%, making amber containers perfectly. However, there is a need to reduce turbidity in order to make this material usable and make transparent packaging containers. The cost-performance ratio of nanocomposites is very competitive, and clay does not affect the recycling process. Therefore, nanocomposites have a wide range of applications.

The nylon nanocomposites AegisOX, PAMXD6/nanoclay composite M9 and polyvinyl alcohol (PVA) film materials, which are raw materials for plastic beer bottles, are the three promising high-performance barrier materials.

Currently, Honeywell, USA is working to develop a nylon nanocomposite AegisOX with high barrier property and low cost, which is an activation/passivation barrier material, in which nanoclay is a passivation barrier layer. Synergy with suitable oxygen sorbents as activators. It is said that the material can reduce the oxygen transmission rate (OTR) of PA6 by 100 times, and the oxygen incorporation is almost zero. Some big PET bottle manufacturers are using AegisOX as the core of a three-tier beer bottle, and their life expectancy can reach 180 days.

Eastman Chemical also collaborated with Nanocor, a US nanoclay producer, to develop a nylon nanocomposite barrier material, PAXD6/nano-clay barrier M9 called Imperm, which was commercially available in June 2000. . Imperm's oxygen barrier is said to be 50 to 100 times larger than PET. The nano-sized clay particles also increase melt strength and bottle rigidity. Compared to the standard PAMXD6, the barrier ratios of carbon dioxide and oxygen are improved by 50% to 70%, and the transparency and peeling resistance are the same as those of the standard PAMXD6. The company tested 25 types of 29g PET/Imperm/PET 3-layer bottles, whose barrier layers respectively constituted 4% and 10% of the bottle wall. The oxygen barrier of the former is 3 to 5 times higher than that of PET bottles, 8% of atomized products, and the latter is 6 to 11 times higher in oxygen barrier properties and 15% less in atomized products. The use of these high barrier PTE bottles includes beer, carbonated soft drinks, fruit juices, and the like. The three-layer structure (PET/M9/PET) beer bottle can reach the beer shelf life of the United States (110 days) and Europe (180 days).