1 Introduction
The rise and fall of the world dye industry is closely related to the textile printing and dyeing industry. In recent years, the world's textile fiber production has grown at an average annual rate of 2.5%. In 2003, the output reached 52 million tons, of which the average annual growth rate of synthetic fiber was about 5.0%. In 2003, the output was 27.2 million tons, accounting for the total textile fiber. The amount is 52.3%. Among synthetic fibers, the annual output of polyester fiber has exceeded 21 million tons, ranking first in textile fiber, and its proportion has reached 40.4%; polyamide fiber is about 3.9 million tons, accounting for 7.5% of textile fiber; polyacrylonitrile fiber is about 2.3 million tons, accounting for 4.4% of textile fibers. The annual output of natural fiber is about 24 million tons, of which cellulose fiber has the largest output in textile fiber, about 22 million tons, accounting for 42.3% of textile fiber. Faced with the vigorous development of textile fiber, the world dye industry has also developed rapidly. In 2003, the output value of the world dye industry reached 8 billion US dollars, and the annual output was close to 1 million tons, of which textile dyes accounted for the largest share, about 80%. The four major European companies in the world dye market, DyStar, Ciba, Clariant and Yorkshire, account for 23%, 15%, 8% and 4% to 5% of the market respectively, accounting for 50% of the world's dye market. 51%, the remaining share is mainly occupied by Southeast Asian countries, about 42% to 43%, and Japanese dye companies account for 7%. In 2003, the consumption of dyes in the world was about 75-800,000 tons, of which the dye consumption for cellulose fibers was the largest, exceeding 48% of the total dye consumption, about 380,000 tons; the dye consumption for synthetic fibers accounted for 45%. About %, about 360,000 tons. According to the consumption value of dyes, the consumption value of dyes in the world is about 5.85 billion US dollars, of which disperse dyes are the largest, about 1.53 billion US dollars, accounting for 26.6%; reactive dyes are second, about 1.43 billion US dollars, accounting for 24.4%; acid dyes are about 1.06 billion. US dollars accounted for 18.1%; direct dyes were about 450 million US dollars, accounting for 7.7%, cationic dyes and basic dyes were about 400 million US dollars, accounting for 6.8%; vat dyes and sulphur dyes were about 980 million US dollars, accounting for 16.8%.
Due to the fact that the world's dye production exceeds consumption in recent years, the competition in the dye market is extremely fierce, and the price war is also intensifying. The low price of dyes in China has become one of the factors that dominate the world dye market. Table 1 shows the average price of the world's major dye markets in 2002.
2 The latest developments in the development of foreign dye industry
2.1 Corporate restructuring has stabilized and China has become the world's dye production and supply center [1]
There have been two organizational reforms in the history of dyes in the world. One was in the 1960s, when the Western European dye company ousted the American dye company from the dye stage, thus occupying the US dye market. The other was the largest and most extensive reform in the history of dyes in the mid-1990s. After reform, the dye industry in Western Europe has changed from six systems to three systems, making dye production more centralized and more specialized. On May 28, 2004, DyStar, the world's largest dye company in Western Europe, signed a sale and purchase agreement with Platinum (a company specializing in corporate mergers and acquisitions, providing decision-making services and solutions), which will be owned by Platinum. All shares of DyStar. However, this acquisition transaction requires the consent of the antitrust organization. It is understood that the upcoming DyStar equity change will not affect the company's business activities, textile dyes are still DyStar's business focus. DyStar's move certainly has a significant impact on other European dye companies, and some companies are investigating new strategies to meet the future needs of the global dye industry.
The dye production organization in Japan has also changed. They have adopted a variety of methods to strengthen the production supply system, dye marketing system and new product development system. At the same time, dye companies in Western Europe and Japan have further developed the dye industry to a global level. They have established dye joint ventures and wholly-owned enterprises in various parts of the world, especially in Southeast Asia. According to incomplete statistics, there have been more than 200 dye joint ventures and sole proprietorships to date. It is precisely because of this development and the transfer of dye manufacturing technology that it has greatly promoted and promoted the rapid development of the dye industry in Asian countries, especially in China and India, where dye production has grown the fastest, thus further establishing Asian countries, especially China. Become the world's dye production and supply center.
2.2 Strengthening the efforts of “technical barriers†and “trade barriersâ€
With the cancellation of textile export quotas after China's accession to the WTO, the efforts to set up "technical barriers" in the international market, especially the "green barriers", have been further strengthened. At the end of the 20th century, there were about 300 chemical substances in the textile and textile chemicals field that were banned and restricted. After entering the 21st century, the world market accelerated the setting of “technical barriers†and continued to issue new bans and restrictions on the use of textile chemicals. Regulations, especially the European Union, enact a new regulation that belongs to “green barriers†every two months.
The most severe "technical barriers" to date have two [2]. One is the European Union's new standard for the determination of textile ecolabels published by the European Union on May 15, 2002 in its Official Gazette, which stipulates that the number of banned and restricted textile dyes will increase to about 400 in seven categories. They include azo dyes that cleave 22 carcinogenic aromatic amines under specific conditions, carcinogenic, mutagenic or reproductively harmful dyes, allergic dyes, chrome dyes, and some metal complexes containing copper, chromium and nickel. Dyes, dyes with heavy metals exceeding the specified value, dyes containing excessive formaldehyde, etc. The new standard bans and restricts the use of textile chemicals in a larger range than in the past, and is also more demanding than OekoTexStandard100, which is known by the textile industry as the most stringent textile ecological standard to date.
The second is the revised White Paper on Future Chemicals (also known as REACH) published by the European Union on March 17, 2003. It was issued on January 21, 2004 through the World Trade Organization Secretariat. At present, the comment period has passed and it is expected to be approved before the end of 2005 and will be implemented in 2006. The regulation is a chemical registration, evaluation and licensing system that will replace more than 40 existing chemicals directives and regulations in the EU. One of its key points is that dyes, pigments, auxiliaries and their downstream products, textiles and clothing, will greatly increase the export cost of textile chemicals and their textiles, and greatly increase the cost of new textile chemicals and new textiles. . The chain reaction caused by this regulation or the “Domino effect†will lead to the deterioration of the international trade environment and restrict the export and development of China's textile chemicals and textiles. It can be said that this regulation has almost all the management of chemicals. The range of products covered, the number of products involved, and the high cost of testing products are among the most "technical barriers" so far. It is estimated that once the regulations are implemented, the impact on China's textile chemicals and textile and apparel exports will not be less than 10 billion US dollars.
In addition to increasing the intensity of setting up "technical barriers", the EU and the United States and other countries and regions have also created new "trade barriers" for China after the elimination of textile export quotas. In November 2003, the United States launched special safeguard measures for textiles, which imposed new import restrictions on three types of textiles exported to the United States. In the EU, after the cancellation of quotas for clothing and textiles in recent years, China’s exports of textiles and clothing soared by 188%, exports increased by 46%, and average prices fell by 50%. It is likely that the transition period will be adopted before 2005. Special safeguards for specific products, implementing new “trade barriers†that are more stringent than the United States.
2.3 pay more attention to the development of new dyes
In order to adapt to the needs of the international market situation and to change the disadvantages in the market competition, all the dye companies in the world pay more attention to the research and development of dyes, and put the development of new dyes into a more important position (Table 2).
It can be seen from Table 2 that in the past three years, an average of 168 new dyes have been developed each year, of which less than half of the new structure dyes are used, and others are improvements to old varieties, such as new dosage forms, new uses, and new products. The new dyes developed mainly focus on the green dyes that meet the environmental and ecological requirements of OekoTexStandard100, ie the dyes with “six no†characteristics: no carcinogenic aromatic amines and no cracking to produce carcinogenic aromatic amines, no allergenic dyes, no Excessive heavy metals, formaldehyde that does not exceed the standard, no adsorbable organic halides, no environmental pollution or low waste. Of course, various color fastness, coloring rate, liftability and vividness of dyes are still pursued, and their focus is on active and dispersed dyes, which are used in cellulose fiber and polyester fiber. Dyeing and printing of the main textile fibers. That is to say, the development of new dyes focuses on the coloration of the main textile fibers.
For reactive dyes, it has the advantages of bright color, excellent wet fastness, convenient use and strong applicability compared with other cellulose fiber dyes, and the structure does not contain carcinogenic aromatic amines, although dyes are still present. It has low utilization rate, large electrolyte consumption during dyeing, large amount of salty colored sewage and difficult to handle, but it is still the best choice for dyes for cellulose fibers, so it is currently developed and developed in the world dye market. One of the focuses. Mainly concentrated on the "five high and one low", that is, the development of new reactive dyes such as high fixation rate, high color fastness, high liftability, high levelness, high reproducibility and low salt dyeing [3,4] . For example, DyStar's new reactive dye ReaNovaCA, which was developed in 2000 and 2001, has a fixation rate of about 90%, moderate affinity, suitable transferability, high solubility in alkaline media, good alkali resistance and Excellent washability and other characteristics. It is suitable for low-salt and low-alkali dyeing, and has no problem of adsorbing organic halides. It has uniform affinity, reactivity and good detergency when color matching. The company's ProcionXL+ dyes are a new class of reactive and deactivated reactive dyes. The valence bonds formed between the fibers and the fibers exhibit the same fastness and excellent stability as the Procion HEXL dyes. High level RFT (primary) production. For example, the SumitinHF dye introduced by Sumitomo Corporation of Japan is a new type of double reactive active dye with high fixation rate (85% or more), high liftability, short dyeing time, short cleaning process and reproducibility. Excellent, good color fastness, excellent dyeing fabric dyeing adaptability and low salt dyeing. With it, it can reduce the drainage load, reduce raw materials and management costs, and improve production efficiency. The Intracron CDX series of dyes developed by Yorkshire are also a class of highly reproducible multi-reactive dyes with a wide range of chromatographic ranges to meet the ever-increasing fastness performance requirements of textile users, giving a combination of high light fastness and repeatability. The stability of the oxidative washing is good, and this is a problem that is often difficult to solve in the three primary colors composed of C.I. Reactive Black 5. They also have low sensitivity to dyeing parameter changes and excellent compatibility, reducing the amount of salt used in dyeing. Synozol Reactive Yellow K3RS, Reactive Red K3BS and Active Aquamarine KBF recently developed by Gyeongren Corporation of Korea are for the leveling of C.I. Reactive Yellow 145, C.I. Reactive Red 195 and C.I. Reactive Blue 222. New reactive dyes developed for problems such as poor sex and reproducibility. The company's Synozol KHL dye has better light fastness. The Rifafix Black EXFConc. dye developed by Lee & Co., Ltd. of Korea has high lifting power, good light fastness and excellent extractability.
It is particularly worth mentioning that Ciba has recently developed the CibacronS type dye. They are composed of 2 to 3 color bodies and 2 to 3 active groups. Unlike conventional linear dyes, they are arranged in a plane, the molecules are tight and elastic, have moderate affinity, good dispersibility, and excellent water washing. Sexuality, over 90% fixation rate and extremely high lifting power. Among them, Cibacron Deep Red SB has a lifting power three times higher than that of general reactive dyes. Deep dyeing with this type of dye shows excellent wet rubbing fastness and washing fastness. In addition, it should be pointed out that Reyol Fluorescent Yellow FL developed by DyStar in 2001 is the world's first fluorescent reactive dye for cellulose fibers. It has extremely bright colors and excellent color fastness. This is a reactive dye. A breakthrough in history.
In recent years, countries have been active in the research and development of reactive dyes for hair. The new varieties include Sumifix WF dye, RealanWN dye, and Lanasol CE dye. Most of them contain two active groups such as vinyl sulfone, which can be used to replace chromium mordant dyes.
Due to the industrialization of ultra-fine denier polyester fibers, the growth of polyester fibers for tourism, and the increase in the amount of polyester fabrics used in sportswear and automobiles, disperse dyes have become one of the most active dyes in the world dye market. Mainly concentrated on the "three highs and three lows", namely high washing fastness, high heat transfer fastness, high environmental performance and low nylon and polyurethane fiber staining, low cost [5,6]. For example, Ciba has developed the Terasil WW dye in the last two years, a new type of disperse dye with a phthalimide azo structure. It has good migration fastness and excellent fastness to washing on polyester fiber and its blended fabric; it also improves its high fastness even under strict washing conditions (such as 60 °C washing). The resistance to reduction of the original washable blue, navy blue, black and blue red disperse dyes; overcomes the pH sensitivity of most traditional washable ruby ​​and red disperse dyes. Similar disperse dyes include Clariant's ForonSWF dye, DyStar's DianixSF dye, DianixXF dye, and the like. The Dianix PAL dye developed by DyStar is suitable for the dyeing of blended fabrics composed of polyester fibers and acetate fibers. It has excellent homochromaticity, excellent reproducibility and excellent resistance to nitrogen oxides (NOX) fading and chlorine fastness. . Ciba's Terasil W type dyes are also suitable for the dyeing of polyester/spandex blend fabrics, which are easily removed on the spandex. KaylonPolyester Yellow Brown 3RL (EC) 143, developed by Nippon Kayaku Co., is a new yellow-brown disperse dye that can be used to replace the allergenic dye C.I. Disperse Orange 76. The high-strength black disperse dye KayalonPolyester Black ECX300 made from it is an allergenic environmentally-friendly black disperse dye that completely replaces the original allergic black disperse dye KayalonPolyester Black EXSF(E)300. The company's Kayalon Polyester Black BRNSFPaste 100 is a new black disperse dye suitable for acid medium dyeing, high light fastness and sublimation fastness and capable of removing oligomers.
According to the above knowledge, the current leading position in the development of new dyes is still the Western European dye company, whose development expenses account for 3.5% to 5.0% of the company's income (China's dye enterprises are less than 1% of the company's income) and control 75% of the global dye patent technology.
2.4 Constantly adapting to the new requirements of the textile industry
3 The latest development of China's dye industry development
As mentioned earlier, a welcome result of the successful reform of the world dye industry is to further establish China's position as a global dye production and supply center [7]. In the past three years, China's dye production has grown at an average annual rate of 20.87%, and export trade has also developed at an average annual rate of 3.64%, which has promoted a significant increase in the economic efficiency of the dye industry. Among them, sales revenue is 24.43% per year. increase. Profits increased at an average annual rate of 44.2%, reaching 885 million yuan in 2003; the sum of profits and taxes increased at an average annual rate of 31.9%, reaching 1.40 billion yuan in 2003.
3.1 The market is active and new products are constantly
In 2003, China's dye production reached 542,000 tons, accounting for about 55% of the world's dye production. Among them, the growth rate of reactive dyes is the largest, the annual output is close to 90,000 tons, accounting for 16.6% of the total dye production in China; the disperse dyes continue to maintain steady growth, with an annual output of more than 250,000 tons, accounting for about 47% of the total dye production in China. In addition, the development speed of new dye varieties in China has accelerated markedly in the past three years, and new dyes have emerged. All foreign dye types have been put into industrial production in China. According to preliminary statistics, there are 224 new dye varieties developed in the past three years. Among them, 55 new acid dyes are the most widely added new varieties of textile dyes, accounting for 24.6% of the total number of new dyes.
3.1.1 Development of new hair color bodies
Among the existing dyes in China, azo structure color bodies account for 75% to 80%. The new coloring requirements of the 94 world textile industry include new requirements for dyes for new textile fibers. Such as polylactic acid fiber (CargillDow), Tencel A100 fiber (Courtaulds), Corterra fiber (Shellchemicals), T400 (DuPont textiles and interiors PTT), blended fabric composed of polyester fiber and polyurethane fiber, blended fabric composed of polyester microfiber and nylon microfiber Etc., there are new requirements for dyes. For example, DyStar's Disperse Yellow Brown CVSE, Palanil ECO Ruby CC and Palanil Dark Blue 3RT can be used for medium dark dyeing of polylactic acid fibers; DispersolFlavineXF, Dispersol Ruby CB150 and Trial Blue 01 can be used for high light fastness of polylactic acid fibers. Degree dyeing; MiketonECO yellow CCE, MiketonECO red CCE and Trial blue 01 can be used for light-colored high light fastness dyeing of polylactic acid fiber. Ciba recommends Teratop dyes with high light fastness and high wash fastness, which can be used for the dyeing of polytrimethylene terephthalate fibers, ie PTT fibers, when used in combination with UV absorber CibafastHLF, the light fastness of dyes. Can be upgraded to level 1. In addition, there are new requirements for dyes introduced by new printing and dyeing technologies. In particular, digital inkjet printing technology is very beneficial to the requirements of individualization, fashion, small batch, fast delivery and low pollution, and has attracted the attention of the entire textile industry. The corresponding inkjet printing inks have been continuously introduced into the market. Such as Ciba's CibacronMI (Reactive Dyes), LanasetSI (Acid Dyes), TerasilDI (Disperse Dyes for Polyester Direct Printing), Terasil TI (Disperse Dyes for Polyester Transfer Printing), Irgaphor TBTHC and Irgaphor SPD (all pigments); DyStar The company's JettexR (reactive dye), JettexA (acid dye) and so on. Some structures of azo groups can be biologically mutagenized to produce carcinogenic aromatic amines, so the research and development of non-mutagenic, non-carcinogenic color bodies has become a focus of the development of new dyes. In addition, research on the development of biomimetic dyes has been carried out on natural dye color bodies, and research and development of fluorescent dye color bodies, photochromic dye color bodies and ultraviolet absorption color bodies have been strengthened for functions. In the field of textiles and high technology.
3.1.2 Improve the fixation rate
At present, whether it is a reactive dye or a disperse dye, some varieties in China have problems of low dye utilization. Increasing their sorption and fixation rates has become one of the main goals of reducing pollution, saving resources, and reducing costs.
3.1.3 Improve color fastness
Today, China's dyes are increasingly exposed to problems in terms of light fastness, wet rubbing fastness, perspiration fastness, heat transfer fastness and sweat light fastness. Improving these color fastness is An important issue to increase the added value of textiles.
3.1.4 Development of new commercial technologies
Water-soluble dyes generally have problems such as solubility, exhaustion rate, diffusion speed and leveling property in dyeing process; water-soluble dyes are not high in terms of hardware and software technology for post-processing, and there are also too coarse particles. Wide range of diameter distribution, not all converted into stable crystal form and poor dispersion stability at high temperature, which requires effective development through the development of new commercial technologies.
3.2 Export growth, even new highs
The new development trend of the world dye industry has created a good opportunity for China's dyes. In the past three years, China's dye export volume has grown rapidly, and it has become the world's first dye exporter. Its export volume exceeds more than a quarter of the world's dye trade volume, showing three characteristics:
3.2.1 Exports continue to increase, but export prices are lower
In the past three years, China's dye exports accounted for one-fifth of the world's dye production, which fully demonstrated the status and importance of China's dyes in the world market, but the price of export dyes is not high, and it is decreasing year by year (Table 3). Both are lower than the world market average price. The reason is that apart from the downturn of the three major economies in the United States, Japan and Europe, the variety and quality of dyes in China are not suitable for the needs of the world market. Overproduction, disorderly competition in exports, and competitive price are also important reasons. .
3.2.2 The main export destination is Southeast Asia
In recent years, the destination of China's dye exports is mainly Southeast Asia, accounting for nearly 60% of China's total dye exports. For example, in 2002, the export volume was 120,600 tons, accounting for 59.4% of the total dye exports; in 2003, the export volume was 115,100 tons, accounting for 57.9% of the total dye exports; 10%.
3.2.3 Disperse dyes are the largest export dye category
In recent years, the amount of disperse dyes in China's exported dyes is the largest, with 98,800 tons in 2002 and 92,000 tons in 2003. Disperse dyes are also the highest dyes in China, with annual foreign exchange earnings approaching $230 million. Under the impact of the slowdown of the growth of the three major economic systems, China's disperse dye exports can maintain a high level, indicating that China's disperse dyes have strong market competitiveness and high market share in the world market.
3.3 The development of new bases grows
The new development trend of China's dye industry also fully reflects the changes in major production bases and the continuous growth of emerging bases. China's current major dye production base has changed from Jilin, Shanghai and Tianjin to Zhejiang, Jiangsu and Shanghai. The annual output of dyes in these three provinces (cities) accounts for 80% to 85% of the country's total, and dye exports account for more than two-thirds of the country's total. Especially in Zhejiang Province, its output has exceeded half of the country. Not only that, the three provinces (cities) also have 6 of the country's 10 key dye companies with annual output exceeding 10,000 tons, such as Zhejiang Longsheng Group Co., Ltd., Zhejiang Bauxite Chemical Group Co., Ltd. and Hangzhou Jihua Chemical Co., Ltd. Co., Ltd., the top three dye manufacturers in China, are world-class dye companies.
In the past three years, the absolute amount of dyes in China has increased by 235,200 tons, and the average annual growth rate has reached 20.87%. The export volume of dyes has also increased by 20,200 tons, with an average annual growth rate of 3.64%. The situation is very gratifying. Due to the new development of the world dye industry and the structural adjustment of China's textile industry, new fibers such as Tencel fiber, soybean fiber, ultra-fine fiber, fine-denier polypropylene fabric and various multi-component fabrics, as well as new printing and dyeing technologies such as digital inkjet printing The technology has been continuously developed, and the demand for dyes has increased accordingly. In addition, the recommended standard of China's textiles in 2004, the technical requirements for eco-textiles, and the mandatory standard for textiles in China on January 1, 2005, "Technical Specifications for Textile Products Safety" The formal entry into force, etc., all provide a new important market for the further development of China's dye industry. Although China's dye production currently accounts for about 55% of the world's total, the sales value is only 20% of the world's dye industry sales value, indicating that the technical content of China's dye industry is in urgent need of improvement, China's dye quality, variety, quantity and domestic and foreign There is still a large gap in the degree of market demand, which is reflected in the year-on-year increase in the import of dyes in China and the increase in the average price of most imported dyes (Table 4), and the average annual growth rate of dye imports has reached 12.51. % is the 3.44 times of the average annual growth rate of China's dye exports.
Undoubtedly, the quality improvement and development of China's dye industry is the most important application of high-tech, the extensive implementation of clean production, the universal adoption of international standards, the international integration of detection technology, and the vigorous development of green dyes. Improving the important content of "quality" is also the top priority of the development of China's dye industry.
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