Adjuvants and Additives

This report is a complete and comprehensive update of two previous reports entitled "Adjuvants and Additives in Crop protection", published by Agrow Reports in 2000 and 2003. Written by industry expert Alan Knowles, this report covers all aspects of crop protection product formulation and the use of additives and adjuvants in formulations and as tank mixes. Since the previous reports were published the pace of change in the international agrochemical industry has been accelerating rapidly. The effect of this change and its impact on the technology for pesticide formulations, additives and adjuvants, is described in this current update There are now only six major international agrochemical companies, the socalled 'Big 6'. Generic producers are now much more important to the business as a whole. The 'Big 6' companies carry out the bulk of the research aimed at discovering new compounds involving chemical synthesis, biological, toxicological and environmental testing. Of these companies only Syngenta continues to do significant research in the UK, while its headquarters are in Switzerland. The other two European companies, Bayer CropScience and BASF are based in Germany. The remaining three companies, Du Pont, Monsanto and Dow AgroSciences are based in the US Some other agrochemical companies, along with a few Japanese companies are still doing research to discover new agrochemicals, but in terms of global annual sales these companies are now in a so-called 'Second Division'. There is an increasing presence of Asian companies, notably from China and India, producing generic pesticides and formulations. However, a small number of organisations, especially in China, are beginning to do their own discovery research work. The status of all these companies worldwide is discussed fully in this report.

The value of the global agrochemical business at end user level was about US$ 33.6 billion in 2005. Forecasts point to decline from 2006 onwards, mainly due to economic and regulatory pressures, the introduction of cheaper generic products and the increasing planting of GM crops. It is estimated that the market value for generic and post-patent products currently represents about 70% of the global agrochemical market value A great deal of work has been done on understanding the role of surfactants, adjuvants and other formulation additives in the development of improved formulations, especially in terms of dispersion and emulsion stability, long-term shelf life, dispersibility of granules into water, and biological availability. Fundamental research in colloid and surface chemistry has led to a better understanding of the various properties and functions of surfactants and oil-based products in pesticide formulations and as tank mixes, so that now it is possible to 'tailor-make' surfactants and oil-based adjuvants for different functions in formulations and spray applications Many new formulation additives and adjuvants have been developed to meet the safety requirements of companies and regulators in relation to the user and to the environment.}

Pesticide products can now be designed to be target-specific at low dose rates, and with low toxicity to mammals and other non-target species. As the pesticide molecules themselves have become less toxic in recent years, there is increasing emphasis on the toxicity and environmental impact of additives and adjuvants used in formulations and as tank mixes Formulation and adjuvant technologies are now seen as 'enabling technologies' which can provide safe and effective products that are convenient to use. They can also modify the toxicity of active ingredients and improve their ability to target a specific pest. Formulation and adjuvant technologies are an essential part of the total 'delivery' system which can also include the packaging and application equipment. At a time when the discovery of new pesticide compounds is more difficult and a high risk and expensive operation, formulation and adjuvant technology can extend the useful patent life of active ingredients. It can also provide a competitive edge by improving product quality of existing formulations, by introducing a new formulation of existing active ingredients, and by enhancing the activity of formulations. Adjuvants can be added to the formulation in some cases, or added as tank mix adjuvants to improve biological activity after spray application Patenting of new active ingredients, formulations and adjuvants is essential to protect intellectual property rights in commercial markets where patents are protected. It is estimated that it can cost more than US$ 150 million to discover and develop one active ingredient, often taking up to ten years from initial discovery to first commercial sale of the product. The long development timescale significantly reduces the available patent life for commercialisation of new products. As with the R&D driven sector mergers and acquisitions have also occurred among the adjuvant and additive supplier companies, so that there are now about 10-12 major global players in the surfactants and adjuvants market.

The global adjuvant market is viewed as a significant growth opportunity for the agrochemical industry, notably for specialist tank mix adjuvant companies Estimates put the agrochemical adjuvant market value in the order of US$1 billion for 2001 and it is generally estimated to have risen to about US$ 1 billion in 2005 A truly accurate valuation is difficult due to the fragmented nature of the tank mix adjuvant market. Whilst the fundamental flaw of any survey is that by definition it is only possible to make estimates on tank mix products, this ignores the fact that many adjuvants are built into one-pack formulations This is generally the preferred approach from major R&D-based agrochemical companies. Gathering data on this significant aspect of adjuvant usage is complex. Built-in adjuvant products often follow the 'secret recipe' model, which poses dangers due to the use of analytical tools to reverse engineer-formulated products. The more robust approach is to link patented built-in options with an associated market advantage. Due to the tremendous pressure from end-users to provide them with fully built-in products especially outside the US, the total value of this segment is significant and largely hidden Looking at the tools available for making adjuvants, whether tank mix or built-in, this greatly relies on inert materials not specifically designed for the agrochemical industry.

Most of the surfactants and other inert materials share a large range of uses, for detergency, coatings, oilfield use and other industries. The actual consumption of surfactants by the agrochemical market is relatively small. For example, the use of surfactants with agrochemicals is estimated to account for about 4% of the world market for surfactants. Suppliers of inerts are therefore less focused on delivering new chemistries to crop protection when larger opportunities exist elsewhere While this may be viewed as a threat to the industry, it also represents an opportunity to the industry. As most of the materials researched to date were not aimed at the agrochemical industry, there must surely exist a large opportunity to invent new value-adding adjuvant materials Overviews of the current state-of-the-art of surfactants and adjuvants can be found in sections 5, 6 and 7. These are supplied by a number of international experts, some of whom are Executive Committee Members of the organising committee for the International Symposium on Adjuvants for Agrochemicals (ISAA) Crop protection product formulations are covered in Section 2 which includes summaries of all the important conventional and newer safer formulation types. Data from the BCPC Pesticide Manual show that emulsifiable concentrates (EC) and wettable powders (WP) are now reaching a plateau, while the number of water-based suspensions (SC) and emulsions (EW) are steadily increasing. One of the biggest increases is in the number of waterdispersible granules (WG). Other specialised formulations such as microemulsions (ME) and microcapsules (CS) are also becoming important Section 3 reviews all the surfactant types which are an essential part of pesticide formulations, while Section 4 deals with other additives included in all the major formulation types.
Tank mix adjuvants are discussed separately in Section 5 which includes an overview from Allen Underwood of Helena Chemical Company, US There is increasing interest in understanding the mode of action of adjuvants on crops and this topic is discussed fully in Section 6 with contributions from five international experts on the use of adjuvants for bioenhancement Future trends towards safer formulations, additives and adjuvants in crop protection are covered in section 7. It also reviews biopesticides as alternatives to chemical pesticides. Expert views on future developments are provided by four well known members of the industry Regulatory control of pesticides has been developed by government bodies over many years.

Nowadays increasing attention is being turned to the regulation of additives and adjuvants used in pesticide formulations or tank mixes. Section 8 reviews the situation in the EU, including the proposed new REACH regulations. Developments in the regulatory positions in US (EPA), Canada, Australia, Latin America, and China are also covered. The reasons for some additives now being questioned or banned are given, and alternative inerts are suggested The global markets for agrochemicals, additives and adjuvants are covered in chapter 9. Separate data are included for the market for surfactants used in agrochemical formulations and tank mixes Finally chapter ten gives details of recent company mergers and takeovers in the agrochemical and adjuvant industry. The section also includes full profiles of sixteen international companies involved in agrochemical adjuvants, additives, and consultancy services Acknowledgements A major techno-commercial report of the international business on adjuvants and additives for crop protection requires the input and cooperation of a large number of people from the industry. It is not possible to list all the individuals and companies contacted, but the author would like to thank many representatives of agrochemical and supplier companies for their willingness to provide information about their companies and products, and to share their views on the current situation and likely future trends of the business The author is particularly grateful to Roger Warrington, a UK agrochemical consultant, for his guidance and help throughout the project, especially for technical input on surfactants, adjuvants and additives The author would also like to thank the following experts who provided individual contributions to some of the Sections of the report:

Dr Terry Grayson, UK (retired, formerly with Shell Agrochemicals)
Dr Per Kudsk, Danish Institute of Agricultural Sciences, Flakkebjerg, Denmark
Dr Hans de Ruiter *, SURfaPLUS, Wageningen, The Netherlands
Dr David Stock *, Syngenta, Jealott's Hill, UK
Dr Allen Underwood *, Helena Chemical Company, Memphis, US

* Indicates Executive Member of the International Symposium on Adjuvants for Agrochemicals (ISAA) Society The key sources used in researching this report are listed in the References Other general sources of information included:

Agrow World Crop Protection News, 2003-2006
Agrow Magazine, 2006
Farm Chemicals International issues, 2005-2006
Crop Protection Monthly issues, 2005-2006
ISAA Proceedings, 2004
Company, government and other organisations websites