Top Ten Packaging Inventions of the 20th Century (3)

7. Conducting Polymers
In 1977, K Shiakawa and Mac Diarmid first discovered that using Asf5 to dope polyacetylene to obtain excellent conductive polymer materials opened up a new era of conductive polymers.
As we all know, the high insulation of plastic is one of its advantages, but it is the enemy of high-tech electrostatic sensitive products and electromagnetic sensitive products. There are two types of conductive polymers developed for this purpose, namely composite and structural types. The former, of course, is not as convenient and superior (as transparent) as the latter.
Scientists have conducted extensive scientific research on conductive Electro-active Polymers, and in the 20 years have developed a variety of conductive polymer-based (for packaging) materials.
Since the first development of polyacetylene (PAc) in 1977, various conductive polymers have been introduced. In 1980, AFDiaz and others successfully developed polyaniline (PAn) films. It has good electrical conductivity and stability, its electrical conductivity can be as high as 10s/cm, and its heat resistance is good. PAn can be heat-resistant at 360°C. It also has electrochromism, photoelectric conversion properties, nonlinear optical properties, and electromagnetic properties. Absorbing properties as well as catalysis make it versatile. In terms of packaging, it can be used in anti-static packaging, electromagnetic shielding packaging, smart observation window, stealth packaging, selective air permeability film and so on.
Research on polythiophene (PTP) began in the early 1980s. The earliest developed poly (methyl) thiophene had poor electrical conductivity and poor practicality. Since 1989, scientists systematically conducted research and developed a variety of products, mainly including: Poly(ethyl)thiophene (PEOT), poly(α-triple)thiophene (α-PTP), poly(butyl)thiophene (PBTh), poly(3-alkyl)thiophene (P3AT), and the like. The higher conductivity of polythiophene is generally 10-8s/cm. After doping, the conductance charge can increase 3-8 times, up to 10-5 ~ 10s/cm. Its application is the same as PAn.
Polypyrrole (PPy) was studied in the 1980s. In 1985, Japan's Takea Ojio and Seizo Miyata first developed PPy composite membranes, thereby widening the application of polypyrrole, and now there are also many kinds of polypyrroles, such as poly(3-alkyl)pyrazole (PAP) and poly(3). - Alkyl thiophene) pyrrole (PATP) and the like.
In addition, structural (conjugated) conductive polymers have also invented polyparaphenylene (PPP), polyphenylenevinylene (PPV), polydiacetylene (PDA), polyacene (PAS), polythiopheneacetylene (PTV), Polybutyne (PPB) and so on.
The above structured conductive polymers PPy, PTP, PAN, PPP, PPB, etc. have attracted attention from various industries due to their various uses. However, due to different uses, in addition to improving the performance of conductive polymers, the main application of composite methods, such as PPy-PPA, PTP-PAN, PAn-PET, PPy-PET composite film, its performance is greatly improved, the conductivity can be The level of silver and copper also broadened the application of packaging (PAN for polyacrylonitrile).

8. Nanomaterials for packaging
Nanotechnology is the youngest and most advanced science and technology in the 20th century, and it is also the most promising science and technology in the 21st century.
One nanometer is one billionth of a meter, which is close to the size of the atom. This is the latest scientific and technological achievement that people have been pursuing from large to small. Nanotechnology was brewing in the 1970s and 1980s. In 1984, Rustun Roy first proposed the concept of nanomaterials. In 1988, H.Gleier and R. Seagel and others proposed the structure theory of nanomaterials. In 1989, IBM Corporation of the United States realized the technology. The composition of nano-patterns; in 1990 Japan first developed (can be used for packaging) nano-composite materials (PA6/Mt).
The advent of nano-high-tech has attracted the attention of governments of all countries. In 1990, the United States included it in the "Government Key Technologies" and "Strategic Technologies in 2005" that began in 1991. In 1992, Japan began a 10-year "Nanotechnology Development Plan." In 1993, Germany proposed " In the 10-year key plan, nanotechnology has accounted for almost 1/6; in 1995, the European Union put forward a report that will develop nanotechnology into the "second largest manufacturing industry"; in 1996, the world launched a "nanotechnology boom."
In 1993, the International Nanotechnical Commission (INTC) divided nanoscience and technology into 6 university departments: nanophysics, nanobiology, nanochemistry, nanoelectronics, nanotechnology, and nanometrics, in order to advance nanoscience and technology globally. System development and promotion.
Nanoscience is the crystallization of special phenomena in the range of 0.1 to 100 nm (1 nm = 0.001 μm = 10 -9 m). The reason why it is "red fire" is its material has super performance, its product is "super mini" type, such as micro-satellites only 100 grams and performance is comparable with 1000 kg. For packaging, nanotechnology will transform packaging into a new era.
In 1990, Japan's Genki Kosan Co., Ltd. and Toyota Central Research Institute first successfully developed PA6/Mt (montmorillonite about 5%) nanocomposites and carried out industrial-scale production. The catastrophe is a cation exchange reaction between sodium ions in the montmorillonite (Mt) layer and alkyl amines, and the monomer or polymer is injected between the layers, such as the ring-opening polymerization at high temperature after incorporation of ε-caprolactam. During the polymerization, the neatly aligned Mt interlayer spacing (about 1.31 nm thick) was disrupted and dispersed into the PA6 resin to form a nanocomposite. This method has caused great concern. In 1995 and 1996, two companies in Japan developed nano-SiO2, mica and other nano-composites.
In 1995, PET (90%)/LCP (10%) was successfully developed by Superex Polymer Co., Ltd. under the trade name Vectra A950. When a special compatibilizer is used for polymerization, the liquid crystal polymer LCP is very finely dispersed in the PET resin to form a microscopic state of "fibril", which not only makes the composite material high in strength but also has heat resistance and barrier properties. Better than PET, suitable for bottle containers, its biaxially stretched film is a good packaging material, in line with green packaging requirements, because LCP is microscopic "microfiber" state, so with 10% LCP Can replace PET reinforced resin, because in the recovery of recycled PET / GF, reprocessing is a very troublesome problem.
Nowadays, nano-composite polymers such as SiO2, T1O2, Al2O3, MgO, B2O3, AIN, and Y2O3 have been used (main materials are PET, PEN, PBT, PTT, POM, PS, PP, PMMA, etc.) Packaging or other cutting-edge areas such as aviation, aerospace, information industry, defense industry and other sectors.

9. Green packages-Degradable
In 1972, the United Nations issued the "Declaration of the Human Environment" which opened the curtain for the "green revolution" in the world. For the packaging industry, "green packaging" is the largest and most shocking "packaging revolution" in the 20th century.
In 1975, Germany took the lead in launching the “Green Packaging” with the “Green Grund” (green packaging design) logo. In the following decades, "green packaging" quickly developed in countries around the world, and regional and national standards (such as the European Community standard EMAS) have come out one after another.
The publication of the "Environmental Declaration" and "Twenty-first Century Agenda" by the United Nations in June 1992 drew the attention of politicians from various countries. In view of the surging tide of “green wave”, in June 1993, the International Organization for Standardization (ISO) formally established the “Environmental Protection Committee” (TC207) and set out to formulate green environmental protection standards. After three years of hard work, the first environmental protection standard was ISO14001. January 1996 officially implemented in the world.
Over the past few years, many countries such as the United States, China, Japan, Russia, and Western Europe have successively adopted the ISO14001 series of environmental protection standards (a total of 100 are expected).
In January 1999, the International Organization for Standardization (ISO) implemented the Enviromental Labelling worldwide, and it has been adopted in more than 60 countries so far. This is a globally recognized product packaging certification mark.
For "green packaging", apart from adopting the green sign (EL), the most substantive is the development of green environmental protection, degradable packaging materials, the most promising is biodegradable plastics.
About 6000 to 80 million tons of plastics are discarded each year after use in the world. To solve this serious problem, British ICI Corporation developed a practical biodegradable ε-hydroxybutyrate-valeric acid copolymer (P3HB/3HV) under the trade name Biopol (biodegradable polymer) in the 1970s, and then Mohnsanto in the United States. The company's Japan branch also produces Biopol.
Biodegradable plastics have developed rapidly. The main applications are: poly(lactic acid) and its copolymers, polycaprolactone, P3HB/3HV/polybutylene succinate (PBS), and polybutylene succinate. Alcohol esters (PBSA), poly(propylene succinate) (PBA), poly(propylene adipate) (PPA), cellulose esters, cellulose/chitosan, starch/synthetic polymers, and polyester copolymers (eg, Butane succinate/propylene glycol ester) and so on.
“Research on the degradability (reliability) of degradable plastics has also progressed rapidly. In 1985, the American Materials Testing Association (ASTM) first began to study, and in 1989, the “Degradable Plastics Research Society” established in Japan also involved in this field, and subsequently formulated National standards, while Germany is also very concerned and has also established DIN standards.
Since 1996, the International Organization for Standardization (ISO) has also established the same relevant standards:
1ISO14851 (Oxygen consumption method in water is consistent with JIS K6 950);
2ISO14852 (CO2 method in water);
3ISO14853 (anaerobic method);
4ISO14854;
5ISO14855 (compost CO2 method), etc., used to standardize the assessment of degradability, ensure the development, production, promotion and application of green plastics and ensure the true benefit of humanity.
Although the price of biodegradable plastics is now relatively expensive (approximately 400-800 yen/kg), the price will gradually decrease with the development of science and technology and production processes. It is expected that in the early 21st century, biodegradable plastics will Will be more developed.

10. Eco-machine
Among the large and small and numerous packaging equipment, the most eye-catching is the eco-friendly green packaging equipment that came out in the 1980s and 1990s.
Green packaging equipment should meet the following conditions:
1 Save resources and energy, and invest less;
2 The production process is clean, using no pollution or low pollution technology;
3 High cost-effectiveness, relying on equipment to increase efficiency in the same material situation;
4 Eco-environmental protection, such as the FPP production line launched by Italy's AMUT company in 1997, can reduce eco-environmental expenses by 20%;
5 more than one machine, high production efficiency;
6 equipment automation, intelligent, digital, and so on.
In 1996, DMT and Bruckner launched a large-scale production line for biaxial stretching of BOPP and BOPET with a width of 8.5m, a speed of 350m/min or more, and an annual production capacity of over 35,000 tons.
In 1997, Paul Kiefel introduced a multi-layer co-extrusion blow molding machine that uses a new die, new cooling technology, and intelligent computer control to ensure product accuracy and a high cost-effectiveness ratio.
In 1997, in order to promote the use of PEN (polyethylene naphthalate), Aoki and Shell Chemical Company jointly developed PEN special injection stretch blow molding equipment to produce a series of PEN bottles, which is characterized by better performance than PET bottles, and A multi-purpose machine, use more widely.
After several years of practical investigation, the properties and applications of metallocene copolymers have been recognized. In 1999, Dow Plastics of the United States decided to put the world's largest equipment for the production of ethylene-styrene copolymer into production, with an annual output of more than 32,000 tons. Its advanced and clean production technology, production activity up to 8 million times, a considerable benefit.
Due to the implementation of the International Environmental Protection Standard (ISO14000) and the mandatory application of the International Green Mark (EL), many of the world's largest companies are forging ahead together to develop new green and environmentally friendly products to occupy the global market.
In short, packaging is a marginal discipline and a comprehensive industry. In the 100 years of the 20th century, it had tens of thousands of inventions and applications of various sizes.