Overview of masterbatch raw materials
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(1) Pigments: Plastic pigments in China have made significant progress over the years. Domestic manufacturers such as Jiehong, Baihe, Yabang, as well as some companies that produce titanium dioxide and carbon black, offer pigments of high quality that meet the requirements for color masterbatches. Foreign pigment manufacturers building factories in China will surely boost the development of China’s pigment industry. DuPont is building a 200,000-ton chlorination process rutile titanium dioxide plant in Dongying, Shandong. Cabot has established a carbon black production facility in Tianjin with an output of 108,000 tons. There is also a production line for special carbon black, with an annual output of 23,000 tons and an annual output value of 200 million yuan; completion and operation of this facility are scheduled for the second half of 2006. Clariant also has a pigment production facility in Tianjin; in 2006, it formed a joint venture with the former Hangzhou Baihe Chemical Company to establish a new production site dedicated to the manufacture of high-performance pigments. After acquiring the U.S.-based Sun Chemical Company, which produces organic pigments, Dainippon Ink Company began investing in the production of organic pigments in the Nantong Development Zone in China, and production there has now started. CIBA also has a pigment manufacturing plant in Qingdao, which mainly produces red and yellow pigments. Although BASF has transferred its pigment manufacturing plants in China, it still holds a significant share in the country’s high-end pigment market, with its main marketing strategy focused on manufacturers of high-quality products such as engineering plastics and fiber masterbatches. In recent years, domestic pigments have made significant progress by striving to improve their quality through joint ventures and technological innovation, aiming to match world-renowned brands. Foreign manufacturers have further introduced the concept of pre-dispersed pigments into the masterbatch industry, developing high-quality organic pigments tailored for this sector. Domestic pigment manufacturers have also begun to focus on pre-dispersed pigments; at present, **a few domestic companies already possess the technology and capability to produce such pigments. The Chinese pigment market is seeing Chinese companies overtaking foreign ones, while foreign companies continue to innovate and develop new products; this will undoubtedly **promote the development of China’s pigment industry, with the Chinese masterbatch industry being the biggest beneficiary. (2) Dispersant: The dispersant is an important component in color masterbatches; it enables the pigments to be wetted, allowing them to disperse into fine, stable particles that can be evenly distributed within the resin without re-agglomerating, thereby achieving good dispersion. This article discusses only polyethylene wax as an example. In China’s masterbatch market, there are mainly three types of polyethylene waxes: polymeric type: low-molecular-weight polyethylene produced using polymerization techniques. It is characterized by an appropriate molecular weight and a narrow molecular weight distribution. Some foreign companies, represented by Honeywell, are the main suppliers. Pyrolysis type: Uses finished polyethylene to be pyrolyzed into low-molecular-weight polyethylene. The Fine Chemical Plant at Beijing University of Chemical Technology is a typical representative of this technology. By-product type: Low-molecular-weight polyethylene produced through refinement using polymer by-products from Daqing, Yangzi, and Yanshan as raw materials. These three types of low-molecular-weight polyethylene each occupy a certain market share. Polymerized waxes occupy the high-end market for color masterbatches thanks to a series of excellent properties such as a narrow molecular weight distribution and stable quality. Multinational companies in China’s masterbatch industry, as well as domestic key masterbatch manufacturers, make extensive use of polymeric waxes or imported waxes. For example, Clariant not only produces high-quality masterbatches but also high-quality wax products. Low-end color masterbatch products generally use lower-quality by-product waxes, which have a significant price advantage; there are many small polyethylene wax manufacturers in the Jiangyin area of China. Additionally, in recent years China has also imported similar wax products from South Korea and Thailand, with import volumes reaching over 3,000 tons per year. Pyrolyzed wax has good quality and holds an important position in dispersants for color masterbatches. However, since its price is only slightly lower than that of polymeric waxes and **higher than that of by-product waxes, it suffers from certain impacts on its market share. The composite waxes that are popular in the domestic masterbatch market also have a certain market share, such as those in which liquid paraffin is added to polyethylene wax or other inexpensive additives are incorporated. Due to its favorable performance-to-price ratio, this type of wax also holds a certain share of the market. (3) Carrier resin: For polyolefin color masterbatches, no specialized grades of carrier resin have been produced in China in the past. The first-generation carrier resin used in polyolefin color masterbatches was random polypropylene, while the second-generation carrier resin was low-density polyethylene, such as 1F7B. A few years ago, Tianjin Petrochemical Company developed two grades of LLDPE with melt flow indices of 30 and 50, which were used in the masterbatch industry; however, they were not offered on a large scale to the market later on. Therefore, in the domestic market, when producing high-grade polyolefin masterbatches, carriers specifically designed for masterbatches such as the linear low-density polyethylene MG500026, MG200024, and MG50035 produced by SABIC are often chosen. Its sales volume in China is at least several thousand tons. In response to this situation, Sinopec Yanhua Company established a dedicated team in early 2006 to independently develop the LD400 type LDPE for its 200,000-ton-per-year tubular high-pressure polyethylene plant. As a carrier resin for color masterbatches, LD400 has the following structural features and advantages: ① Its molecular structure is relatively reasonable. An appropriate molecular weight and a wide molecular weight distribution can provide the resin with good flow properties, while a certain amount of macromolecules endow the resin with good mechanical properties. ②The methyl branching degree is 2.70; a higher branching degree provides the resin with better flow properties and flexibility. ③The crystallinity is low (61.46), and the microcrystal size is small. It can provide the product with better optical properties and luster. To date, 800 tons of LD400 have been produced on a trial basis, and it is still in the stage of promotion within the masterbatch industry. If it can be widely applied and recognized in the masterbatch industry, it is expected to become the third generation of carrier resins in this sector. For masterbatches of other varieties, a resin of the same type with properties similar to those of the resin to be colored is usually chosen as the carrier resin for the masterbatch. (4) Others: At present, the production equipment for color masterbatches in China is generally capable of meeting the requirements for their production. Double-screw extruders, reciprocating single-screw extruders, internal mixers, and triple-screw extruders provide increasingly effective methods for the dispersion of color masterbatches. Processing equipment designed and manufactured specifically for masterbatch manufacturers, such as those from Covestro W&P and Swiss Buss, are also available for selection. The colorimeter market and color matching software are primarily dominated by foreign brands such as Datacolor, X-Rite, and Minolta. The Shenyang Research Institute of Chemical Industry in China has also developed color-matching software, which performs well. The current problem is that the databases of color matching software mainly consist of foreign pigments; color matching software based on domestic pigments still needs to be developed.
(1) Standards for color masterbatches and related issues: At present, the color masterbatch industry has only one official industry standard, namely \"Polyethylene Coloring Masterbatches\", which is far from sufficient to meet the needs of the industry’s development. The standards for \"PP fiber color masterbatches\" and \"ABS color masterbatches\", which were approved through expert evaluation at the 2004 Sanya conference, went through numerous revisions and other extensive efforts before finally taking the form of a draft for approval; it was submitted in April 2006 awaiting approval. \"Low-molecular-weight polyethylene wax for color masterbatches\" has been included in the **NDRC’s 2005 supplementary plan for industry standard projects.\" The Masterbatch Professional Committee, Tianyuan Chemical Co., Ltd. of Beijing University of Chemical Technology (now known as the Fine Chemical Factory of Beijing University of Chemical Technology), and Honeywell served as the standard drafting units. Meanwhile, the special committee on masterbatches collected products from representative manufacturers in China and conducted extensive testing to prepare for the formulation of standards. At the 2006 annual meeting, industry experts expressed the following views on the standards for color masterbatches, which are worth noting: One view is that the color masterbatch industry urgently needs to establish standards. The establishment of standards brings greater standardization to the industry, providing enterprises with laws and regulations to follow in order to exercise self-discipline. The establishment of standards also protects most enterprises, preventing a severe decline in product quality resulting from the relentless pursuit of cost reduction driven by fierce competition. Another view is that the masterbatch industry does not urgently need to establish standards. Through the regulation of market principles, color masterbatch manufacturers at different levels should be able to find their proper place in the market; otherwise, they will be eliminated by it. At present, since there is still demand in the market for low-grade plastic products, low-grade masterbatches will inevitably have a market, and the establishment of standards may not necessarily impose restrictions on them. With economic development and the continuous improvement of people’s living standards, the market share of low-quality products will inevitably shrink, while mid-to-high-end masterbatches will see growth. Another view is that color masterbatches are merely intermediate products; therefore, the standards of the industries upstream and downstream serve as a good reference for the color masterbatch industry. When preparing color masterbatches, select pigments, dispersants, and processing aids that meet the standards ； After coloring specific products with the prepared color masterbatches, they should meet the standards for plastic products. After lively discussions, industry experts finally reached a consensus that more masterbatch standards should be established in an appropriate and timely manner. The gradual establishment of standards helps promote the healthy development of the industry and enables it to better adapt to the economically integrated global environment. (2) Industry organizations and bodies in the masterbatch sector: The Masterbatch Committee of the China Dye Industry Association was established in 1994; it is a private industry organization approved by the Ministry of Civil Affairs. It currently has nearly 300 members. The vice chairpersons of this committee are senior experts from leading enterprises in the industry, and its members are also among the best in the field. The Special Committee on Color Masterbatches is affiliated with Beijing University of Chemical Technology, with its secretariat located in the School of Materials Science and Engineering. The Special Committee on Masterbatches provides daily services to its members and the industry through China Masterbatch Network and the journal \"China Masterbatches.\" It also creates platforms for information exchange and technical trade collaboration among members and the industry by organizing annual conferences, holding training courses, writing professional books, and engaging in research and development activities.
Plastic products have been colored using color master batches for 50 years; they were widely used in Europe and the United States in the 1960s, and by the 1970s, their annual growth rate had reached 25–30%. Currently, most plastic products abroad are colored using color masterbatches, and among various plastic coloring methods, the color masterbatch method accounts for nearly 50% of cases. Our country began developing masterbatches in the mid-1970s. Beijing University of Chemical Technology was the first in China to carry out research and development on color masterbatches. In the mid-1980s, by introducing advanced foreign technologies, significant progress was made in China’s color masterbatch industry. After years of development, China’s masterbatch industry has attained considerable strength. It features various enterprise forms such as state-owned, private, foreign-funded, and joint ventures, all of different scales, which together shape the structure of China’s masterbatch market. The outstanding companies among them can customize the required color masterbatch varieties according to customers’ demands. Each company has its own strengths and specialties, allowing for complementary advantages in order to provide customers at home and abroad with color masterbatch products of different quality levels. Many masterbatch manufacturers are also producers of functional masterbatches and compound materials. In 2005, the Special Committee on Masterbatches conducted a survey of 251 masterbatch manufacturing enterprises in China. The survey covered over 90% of China’s production capacity for color masterbatches. (1) Demand for color masterbatches in the plastics market. The development of the petrochemical industry has led to rapid progress in the plastics processing sector; plastic product production has increased significantly, their quality and grade have improved, and new varieties continue to emerge, all of which create opportunities for the growth of the color masterbatch market. The average market growth rate was as high as around 24% from 1994 to 2002, and from 2003 to 2005, the market maintained an average annual growth rate of 20%. In 2006, the domestic demand for color masterbatches was 300,000 tons. (2) Production capacity and geographical distribution of color masterbatches: There are 251 color masterbatch manufacturers in China, mainly concentrated in Guangdong, Jiangsu and Zhejiang, as well as Shanghai. In particular, large-scale enterprises with a production capacity of over 1,000 tons are found mainly in the south, while there are some manufacturers in Shandong in the north, and fewer manufacturers in the central and western regions. This distribution also follows the same trend as China’s economic development. Table 1 shows the distribution of domestic masterbatch manufacturers. Table 1 Distribution of domestic masterbatch manufacturers by region: Large manufacturers, Small manufacturers, Total. Guangdong: 22, 18, 40; Jiangsu: 8, 42, 50; Shanghai: 8, 16, 24; Shandong: 4, 32, 36; Zhejiang: 4, 30, 34; Hebei: 1, 10, 11; Fujian: 1, 7, 8; Others: 5, 43, 48. Total: 53, 198, 251. The annual total production capacity of masterbatch among the manufacturers surveyed exceeds 240,000 tons; if manufacturers that have not been counted are included as well, China’s total masterbatch production capacity will exceed 250,000 tons. Among them, the production capacity of 53 large manufacturers accounts for over 60% of the total production capacity. In terms of geographical distribution, the production of color masterbatches in China shows a trend of being stronger in the south and weaker in the north, and stronger in the east and weaker in the west. Manufacturers with an annual production capacity of over 1,000 tons are the pillars driving the development of China’s color masterbatch industry. The regional distribution of domestic masterbatch production capacity shows that Guangdong has the highest capacity, accounting for 41.82% of the total production capacity, while Jiangsu, Zhejiang, and Shanghai together account for 33%, and Shandong accounts for 10.62%. These regions account for over 85% of China’s masterbatch production capacity. It is evident that the cities along the southeast coast are the main regions for the development of China’s masterbatch industry. (3) Distribution of masterbatch types: In the survey, the masterbatch types were analyzed by color; white masterbatches accounted for 44%, black masterbatches for 35%, colored masterbatches for 14%, and other types for 7%. As can be seen from the above analysis, black and white masterbatches account for almost 80% of the total production capacity of color masterbatches. A large portion of colored masterbatches still relies on imports. In the production of masterbatches, fiber masterbatches require higher standards in terms of technology and raw materials, and the development of masterbatch production technology was also driven by the need to color polypropylene fibers. Research shows that the total domestic production of fiber color masterbatches amounts to over 26,000 tons, which is slightly more than 10% of the total production capacity for color masterbatches. It can be seen that masterbatch, a technology invented to solve the coloring problem of polypropylene, has found wider application in the field of plastic coloring. In fiber masterbatches, PET dominates with a share of 68.2%, PP fiber masterbatches account for 30.2%, while PA fibers make up only 1.6%. In PP fibers, the spinning grade accounts for 60.2%, non-wovens account for 36.6%, and carpets account for 3.2%. (4) Development of high-grade color masterbatches for engineering plastics: With the development of China’s plastic industry, engineering plastics have become an increasingly important area of application. Compared to general-purpose plastics, engineering plastics such as PA, PC, and fluoroplastics, as well as specialty engineering plastics, have higher requirements for color masterbatches. The School of Materials Science and Engineering at Beijing University of Chemical Technology has recently developed polyperfluoroethylenepropylene color masterbatches, filling a gap in China. During the development process, challenges such as raw material selection, formula formulation, and adjustment of production processes were successfully addressed, enabling the production of polyperfluoroethylene propylene masterbatches in all colors – white, yellow, green, blue, red, orange, brown, and black. When used in wires and cables, these masterbatches meet all the required specifications regarding electrical and mechanical properties. The successful development of this project has laid a solid theoretical and practical foundation for the development of high-quality color masterbatches for engineering plastics in our country. Guangdong Foshan Tiancai Masterbatch Co., Ltd. has developed and produced high-quality PET/PTT masterbatches. The coloring of various engineering plastics requires high-quality color masterbatches, especially since the requirements in terms of heat resistance are beyond the reach of ordinary color masterbatches. Color masterbatches for engineering plastics must be able to cope with technical challenges such as high processing temperatures and complex processing rheological properties, and their addition must not have an adverse effect on the high performance of these plastics.