- PI membrane
Polyimide film is the best film insulation material in the world. It is made of pyromellitic dianhydride (PMDA) and diaminodiphenyl ether (DDE) in strong polar solvent by polycondensation, tape casting and amination.
Polyimide film in Chinese and polyimide film in foreign
catalogue
Polyimide film
▪ characteristic
▪ classification
▪ Film classification
▪ Advantages of Polyimide
▪ Application industry
▪ application area
▪ present situation
▪ Prospect of Polyimide
▪ Future development of PI membrane
2 thin film manufacturing process
3 market analysis
Editing voice of polyimide film
characteristic
The polyimide film has excellent high and low temperature resistance, electrical insulation, adhesion, radiation resistance and dielectric resistance. It can be used for a long time in the temperature range of - 269 ℃ to 280 ℃ and can reach a high temperature of 400 ℃ in a short time. The glass transition temperatures were 280 ℃ (upilex R), 385 ℃ (Kapton) and above 500 ℃ (upilex s), respectively. The tensile strength is 200 MPa at 20 ℃ and more than 100 MPa at 200 ℃. It is especially suitable to be used as flexible printed circuit board substrate and various high temperature resistant electrical insulation materials for motors.
classification
Polyimides are generally divided into two categories:
Thermoplastic polyimides, such as Polyimides for film, coating, fiber and modern microelectronics.
Thermosetting polyimides mainly include bismaleimide (BMI) and monomer polymerization (PMR) polyimides and their modified products. BMI is easy to process but brittle.
Film classification
There are two kinds of polyimide films: homobenzene polyimide film and biphenyl polyimide film. The former is a product of DuPont company, trade name Kapton, which is made from pyromellitic dianhydride and diphenyl ether diamine. The latter is produced by Japan's Yubu Xingchan company, trade name upilex, and is made from biphenyltetracarboxylic dianhydride and diphenyl ether diamine (R-type) or m-phenylenediamine (S-type).
Advantages of Polyimide
(1) Excellent heat resistance. The decomposition temperature of polyimide is generally over 500 ℃, sometimes even higher. Polyimide is one of the most stable organic polymers, which is mainly due to the large number of aromatic rings in the molecular chain.
(2) Excellent mechanical properties. The tensile strength of unreinforced matrix materials is above 100 MPa. The tensile strength of Kapton film prepared by the method is 170 MPa, while that of upilex s is 400 MPa. The elastic modulus of polyimide fiber can reach 500MPa, second only to carbon fiber.
(3) Good chemical stability and hygrothermal resistance. Polyimide materials are generally insoluble in organic solvents and resistant to corrosion and hydrolysis. The variety with different structure can be obtained by changing the molecular design. Some varieties can stand boiling at 120 ℃ for 500h under 2 atmospheres.
(4) Good radiation resistance. Polyimide film in 5 × After 109 rad, the radiation intensity remained 86%; Some polyimide fibers were treated with 1 × After 1010 rad fast electron radiation, the intensity retention rate is 90%.
(5) Good dielectric properties. The dielectric constant is less than 3.5. If fluorine atoms are introduced into the molecular chain, the dielectric constant can be reduced to about 2.5, the dielectric loss is 10, the dielectric strength is 100-300kv / mm, and the volume resistance is 1015-17 Ω· cm. Therefore, the synthesis of fluorinated polyimides is a hot research field.
The above performances are stable over a wide temperature range and frequency range. In addition, polyimide has the characteristics of low temperature resistance, low coefficient of expansion, flame retardancy and good biocompatibility. Polyimides can be widely used in many fields due to their excellent comprehensive properties and diversity in synthetic chemistry.
Application industry
Polyimide film, known as "gold film", has excellent properties. It is widely used in space technology, F, H-class motor, electrical insulation, FPC (flexible printed circuit board), PTC electric heating film, tab (pressure sensitive adhesive tape substrate), aerospace, aviation, computer, electromagnetic wire, transformer, audio, mobile phone, computer, smelting, mining, electronic components industry, automobile Transportation, atomic energy industry and other electronic and electrical industries.
application area
(1) Film: one of the earliest products of polyimide, used for slot insulation of motor and cable wrapping material. The main products are Kapton from DuPont, upilex series from Yubu and apical from Zhongyuan. The transparent polyimide film can be used as a soft solar cell substrate;
(2) Coating: used as insulating paint for electromagnetic wire, or as high temperature resistant coating;
(3) Matrix resin of advanced composite materials: it is one of the most heat-resistant structural materials used in aerospace, aircraft structural or functional components, rocket, missile and other parts;
(4) Fiber: the elastic modulus of polyimide fiber is second only to carbon fiber, which can be used as filter material and bulletproof fireproof fabric for high temperature medium and radioactive substances;
(5) foam plastics can be used as heat-resistant and thermal insulation materials.
(6) Engineering Plastics: thermosetting and thermoplastic, can be molded, injection molding or transfer molding (RTM), mainly used for self-lubricating, sealing, insulation and structural materials. In addition, polyimide can also be used as adhesive, separation film, photoresist, dielectric buffer layer, liquid crystal orientation agent, electro-optical material, etc
present situation
As a special engineering material, polyimide has been widely used in aviation, aerospace, electrical / electronic, microelectronics, nano, liquid crystal, separation membrane, laser, locomotive, automobile, precision machinery and automatic office machinery. Recently, the research, development and utilization of polyimide have been listed as one of the most promising engineering plastics in the 21st century. Polyimide, because of its outstanding characteristics in performance and synthesis, whether as structural materials or as functional materials, its huge application prospect has been fully recognized. It is called "protection solver" and "without polyimide, there would not be today's microelectronic technology". Among all kinds of polymer materials, only six are listed separately in American Chemical Abstracts (CA), and polyimide is one of them. It can be seen that polyimide is of great significance in technology and commerce. With the rise and vigorous development of IT industry, flat panel display industry and photovoltaic industry, it is bound to drive the development of related supporting materials and the growth of market demand. As an important material of sound quality circuit board, integrated circuit, flat panel display, solar cell, electronic label and so on, polyimide film for Electronic Engineering (electronic grade) plays an increasingly important role in the application fields of the above electronic products.
Prospect of Polyimide
Polyimide as a promising polymer material has been fully recognized, and its application in insulation materials and structural materials is expanding. It is emerging in the field of functional materials, and its potential is still being explored. However, after 40 years of development, it has not yet become a larger variety. The main reason is that compared with other polymers, the cost is still too high. Therefore, one of the main directions of polyimide research in the future is to find ways to reduce the cost in monomer synthesis and polymerization.
Future development of PI membrane
According to the application, PI films can be divided into two categories: Electrical Grade for general insulation and heat resistance, and electronic grade with flexibility requirements. Due to the low requirements, electrical grade PI film can be produced in large scale in China and its performance is not significantly different from that of foreign products; Electronic grade PI film is produced with the development of FCCL, and it is the largest application field of PI film. In addition to maintaining the excellent physical and mechanical properties of electrical PI film, it puts forward more stringent requirements on the coefficient of thermal expansion and in-plane isotropy (thickness uniformity). In the future, a large number of electronic grade PI films still need to be imported. The reason is that there is a certain gap between domestic PI films and imported PI films in performance, which can not meet the requirements of high-end products of FCCL. For a long time, the pricing power of electronic grade PI film has been controlled by DuPont and Zhongyuan. However, with the reorganization of SKC and Kolon in South Korea in recent years, and the impact of economic crisis on the export of electronic products, the product price has also decreased. However, electronic grade PI film still has a high profit margin.
Editing voice of film manufacturing process
The production of polyimide film is basically a two-step process, the first step is the synthesis of polyamic acid, the second step is the film-forming imidization. The main methods of film formation are impregnation, tape casting and salivation drawing. The equipment and process of impregnation method are simple, but aluminum powder is often adhered on the surface of the film, the length of the film is limited, and the production efficiency is low; The salivation method has the advantages of high precision, good uniformity of film, clean and smooth surface, unlimited length of film, continuous production, good performance in all aspects, and can be used for the production of films with general requirements; The properties of the films produced by drawing method have been significantly improved, but the process is complex, the production conditions are harsh, the investment is large, and the product price is high. Main equipment of salivation method: stainless steel resin solution storage tank, salivation nozzle, salivation machine, imination furnace, coiler and hot air system, etc. Preparation steps: after defoaming, the polyamic acid solution is pressed into the salivating mouth storage tank on the front head through the pipeline from the stainless steel solution storage tank. The steel belt runs at a constant speed in the direction shown in the figure to take away the solution in the storage tank through the front scraper of the salivating nozzle to form a liquid film with uniform thickness, and then enters the drying channel for drying. The clean and dry air is sent to the heater by the blower and preheated to a certain temperature before entering the upper and lower drying trunk roads. The hot air flow direction is opposite to the running direction of the steel strip, so that the temperature of the liquid film will gradually increase and the solvent will gradually volatilize during drying, which will increase the drying effect. When the polyamic acid film runs on the steel strip for a week, the solvent evaporates into a solid film, and the film stripped from the steel strip is led to the imidization furnace through the guide roller. The imidization furnace is usually in the form of multi rollers. The guide roller with synchronous speed with the salivating machine guides the polyamic acid film into the imidization furnace. After high temperature imidization, the film is wound by the winder.
market analysis
Polyimide is the most heat-resistant polymer material that has been industrialized. It has been widely used in high and new technology fields as film, coating, plastic, composite material, adhesive, foam plastic, fiber, separation membrane, liquid crystal alignment agent, photoresist and so on. Polyimide film can be produced in small batch at the end of 1960s in China, which has been widely used in aviation, navigation, spaceship, rocket and missile, atomic energy, electronic and electrical industry and other fields.
Analysis of market situation and development prospect of PI membrane industry in China in 2020
Polyimide is considered to be one of the most promising engineering plastics in the 21st century and has broad application prospects. However, the development of polyimide industry in China lags behind Japan and the United States. Polyimide large categories and high-end products are monopolized by foreign enterprises, which seriously restricts the development of China's related industries. In recent years, the domestic investment scale for polyimide projects has reached 100 billion level. It is believed that in the near future, China's Polyimide industry will achieve leapfrog development.
High concentration of PI membrane in the world
At present, PL film manufacturers have developed a variety of commercialized high-performance PI films. Due to the high level and difficulty of R & D, DuPont, Uber, Kaneka, Mitsubishi Gas MGC, skck-olonpi and Damai in Taiwan are the main PI film manufacturers, accounting for more than 85% of the global market share. In August 2018, DuPont announced that by the end of the first quarter of 2019, the production capacity of DuPont Kapton polyimide film will increase by up to 20%. By 2019, DuPont's PI membrane production capacity is 3168 tons. SKC Kolon Pi's seventh production line will be officially put into operation in March 2019. This new production line will bring the company an annual capacity of 600-700 tons. By then, skckolonpi's total capacity will reach more than 3300-3400 tons / year. SKC Kolon PI also plans to add a new production line in 2020. If the eighth production line can also be put into operation in 2020, skpi will become the PI manufacturer with the largest production capacity in the world.
According to the data of global well-known research institute grand view, the global PI film market size is estimated to be $1.492 billion in 2016, and it is preliminarily estimated to grow to $2 billion by 2020 and $3.1 billion by 2025. The development of aerospace technology and the growth of the electronic industry promote the demand of the industry. The consumption of consumer electronic products such as mobile phones and flexible displays increases, which also has a positive impact on the PI film industry.
Flexible printed circuit is the main printing scene
On the basis of application, polyimide film market has been subdivided into flexible printed circuit (FPC), special products, pressure sensitive adhesive tape, motor / generator, wire and cable, etc. Flexible printed circuit (FPC) has become the largest and fastest growing application field in the global polyimide film market. They are used to make inkjet cartridges, printers and scanners, mobile phones, pagers, camcorders, and flexible printed circuit boards in military and avionics systems.
In China, electrical grade PI film is the main one
PI film is mainly used as insulating base film and covering film for FCCL in China. In 2019, the demand of PI film for FCCL in China will exceed 5000 tons, which is the main application field of PI film. The market of thermal conductive graphite film benefits from 5g, and the demand is expected to continue to grow, resulting in more demand for PI film. At present, the domestic market is mainly supplied by foreign capital, and there is a large space for domestic substitution.
The domestic polyimide film production process is still in the catch-up stage, mainly producing electrical grade polyimide film, and a few enterprises can produce high-performance electronic grade polyimide film; Domestic enterprises have not yet made a commercial breakthrough in the ultra-thin transparent PI film, which is more high-end. According to the thickness (d), PI thin films can be divided into ultra thin films (D ≤ 8um), conventional thin films (8um < D ≤ 50um, common film thickness is 12.5, 25, 50um), thick films (50um < D ≤ 125um, common thickness is 75, 125um) and ultra thick films (d > 125um). For the main application scenario of PI film, more than 75% of the PI film required by the microelectronics industry of flexible copper clad laminate FCCL is 12.5um or less.
The supply of PI membrane in China is mainly electrical grade. In terms of overall capacity, the capacity of PI membrane in China will be about 9000 tons in 2019, but the capacity of electronic grade will be less than 1000 tons.
In 2019, the domestic polyimide film production capacity is close to 9000 tons, with an average annual growth rate of 17.8% in the past decade; During this period, there were two peak periods of capacity expansion. First, from 2012 to 2014, the capacity increased from 2300 tons to 4140 tons, with a year-on-year growth of 80%; It is mainly the entry of many new production enterprises to promote the overall scale expansion of the industry. Secondly, from 2016 to 2017, the production capacity increased from 4790 tons to 7700 tons, an increase of 61% in two years, mainly due to the capacity expansion of domestic old leading enterprises. For example, Guilin Electric Appliance Research Institute and Shandong Wanda microelectronics material company have expanded and upgraded their production capacity. From 2019 to 2020, major material manufacturers and electronic manufacturers will successively announce the expansion of PI membrane production lines. It is preliminarily estimated that the PI membrane production capacity in China will be close to 10000 tons in 2020.
Prices will fall in the short term
Because the PI film production capacity in China is mainly concentrated in the electrical level, the technical threshold is low, in the past 10 years, the price of polyimide film products has been fluctuating downward trend with the increase of manufacturers. In 2011, the sales price of domestic polyimide film products was at a stage high, with an average price of 873000 yuan / ton. In the following six years, the price continued to decline, with an average price of 634000 yuan / ton in 2017, a decrease of 27%. It is found that the domestic polyimide film production capacity has continued to expand since 2011, and the capacity expansion rate is far higher than the growth rate of market demand. In the future, the market competition will become more intense, and the product price will continue to maintain a downward trend of shock. With the continuous increase of electrical grade and electronic grade production capacity in 2019, it is preliminarily estimated that the industry price of PI membrane will be about 650000 yuan / ton in 2019. In the future, under the premise of stable production capacity of electrical grade PI membrane and rising production capacity of electronic grade PI membrane, the price of PI membrane industry in China will rise for a period of time.
Patent applications are concentrated in Jiangsu Province and Guangdong Province
According to the query of inputting "polyimide film" in the sopat patent network, as of November 11, 2020, the patent applicants for PI film in China are mainly distributed in Jiangsu Province, Guangdong Province and Beijing, accounting for 24.3%, 15.6% and 7.8% respectively.
Note: the statistical time is up to November 10, 2020.
The production capacity is expected to exceed 15000 tons
In 2019, listed companies downstream of PI membrane successively carried out industry forward integration and integration. With the help of capital, more and more downstream enterprises are laying out electronic PI membrane industry.
After 2019, the production capacity construction of PI film in China will usher in a peak. Enterprises in the industry, such as Guofeng plastics and Xinlun technology, are investing in production lines. Downstream enterprises in the industry, such as aolaide flexible in the field of flexible display and Hubei Dinglong in the field of new materials, are also carrying out PI film production capacity integration of industrial chain. PI membrane supply and demand structure imbalance, industry competition is not complete, profit space is large, looking forward to the future, more enterprises will enter the industry through investment, M & A, acquisition and other ways, and then the overall production capacity of PI membrane industry will maintain high growth. Considering the lag of project construction cycle, it is preliminarily estimated that the average compound growth rate of PI membrane industry in China will reach 8% in the next five years, and the PI membrane production capacity in China will exceed 15000 tons / year by then.
The above data comes from the analysis report on market prospect prediction and investment strategic planning of China PI Membrane Industry issued by foresight Industry Research Institute. Meanwhile, foresight Industry Research Institute provides solutions for industry big data, industry planning, industry declaration, industrial park planning, industry investment promotion, etc.
Analysis of PI (polyimide) membrane industry at home and abroad
2018-12-17 18:00
IHS, an authoritative research organization, recently pointed out that AMOLED displays have been in mass production for many years, but the folding screen that the industry is looking forward to has never appeared. One of the important bottlenecks is the cover plate material.
Transparent polyimide (PI) materials are expected to be used in foldable OLED screens, and the industry generally agrees that the scheme of transparent PI + hard coating has the most potential.
Samsung and LG display are actively developing such solutions and laying out corresponding supply chains.
PI film is made of pyromellitic dianhydride (PMDA) and diaminodiphenyl ether (ODA) in solvent by polycondensation and tape casting, and then by imination. As the world's best microelectronic packaging material, PI film has high strength, high toughness, wear resistance, high temperature resistance, corrosion resistance and other special properties, and has become one of the upstream important raw materials in the two fields of electronic and motor.
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Mainland PI Film Enterprises
China is one of the earliest countries to develop PI film in the world. In terms of quantity, the domestic PI film industry has formed a certain scale.
At present, there are more than 50 PI membrane enterprises in mainland China. The following are some of them:
However, PI films can be divided into electrical grade with general insulation and heat resistance and electronic grade with flexibility requirements.
Due to the lower requirements, electrical grade PI films can be produced in large scale in China, but electronic grade PI films are quite different from foreign ones and still need to be imported in large quantities.
As a leading enterprise in the domestic microelectronic flexible interconnection and packaging industry, danbang technology invested 600 million yuan in the "microelectronic grade high performance polyimide (PI) R & D and industrialization" project at the beginning of 2013. After the project is completed, it is estimated that the annual output of PI film is 300 tons, of which 9 um and 12.5 um products account for half respectively.
On April 5, 2017, danbang technology announced the start of mass production of "microelectronic grade high-performance polyimide R & D and industrialization project", and mass production of 6 micron thick special polyimide film.
At present, DuPont, Uber, Kaneka, Mitsubishi Gas MGC, skck-olonpi and Damai are the main producers of PI film industry.
|Taiwan PI film company
Damai technology was founded in 2000 in Xinpu Town, Xinzhu county. It was listed in January 2011 and approved by the Ministry of science and technology as the leading PI material R & D center in November 2015.
Wu Shengchang, chairman and general manager of damay, said that the direction of damay's exhibition in the next five to ten years is very clear. He will join hands with Japanese manufacturers to actively develop new formulas and new applications. He aims to pay equal attention to quality in the global market competition, win with innovative functions, and actively become the first brother of global polyimide (PI) film material brands.
Dasheng technology takes differentiation as its advantage, its technical strength can be manufactured from thin to thick, and it can enter the high profit market with special high-function products.
By 2016, Dasheng technology has developed LED heat dissipation PI film, solar PI film module and low CTE high rigidity PI film.
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Overseas PI Film Enterprises
When it comes to PI film, we can't get around DuPont's Kapton film. For more than 45 years, DuPont Kapton polyimide film has become the industry standard because of its excellent electrical performance, heat resistance, chemical resistance and high mechanical strength, which makes it have high performance, reliability and durability, and can withstand extreme temperature, vibration and other demanding environment.
In 2012, Toray DuPont mass produced Kapton 20en film with a thickness of only 5m, which is the smallest commercial PI film in the world. In April this year, it was reported that Toray DuPont would start to restructure the PI membrane business unit.
As early as the 1980s, Uber developed a high-performance PI film u-pilex S. compared with Kapton, it has high heat resistance, good dimensional stability and low moisture absorption. U-pilex has better chemical resistance and is widely used in tab, because tab needs better dimensional stability and heat resistance, and its size is smaller, so it does not need high bending performance.
In 1980, Japan's Chung Yuan began to study PI films in the laboratory. In 1984, he established a PI film production line with the apical trademark in Shiga, Japan. The products are mainly used in FPCs. In 1988, the apical NPI model with superior dimensional stability was developed. In 1995, the apical ah model produced 175 m, 200 m and 225 m thick products.
Skckolonpi (SKC) started the research and development of PI film in 2001, and completed the development of in and if models (12.5-25.0) in 2005 μ m) In 2006, the LS model was developed and applied to Samsung / LG mobile phones in June 2007. In October 2009, it began to be supplied to world **** FPCB company.
Although the PI film can meet the conditions of thin enough, bending and high temperature resistance, the common Pi is pale yellow, which is definitely not good as a cover plate. Therefore, colorless and transparent PI has become the key to the development. However, there are not many transparent PI, so developing colorless, transparent and stable PI has become a very challenging work.
In 2016, Kolon industries took the lead in developing transparent polyimide, which is expected to accelerate the evolution of mobile phones with flexible screens. Founded in 1954, Korean Kolon is the first nylon manufacturer in Korea. At present, Samsung, LG and other display manufacturers are its customers.
It is expected that the transparent PI developed this time will be able to replace the core material glass used in display. And achieved more than 1 trillion won import substitution effect for South Korea.
*Content from Baijia Bali
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