Contents:

CHAPTER 1 INTRODUCTION 11 1.1 Historical background 11 1.2 Scope of report 13 1.3 Formulation additives and adjuvants 15 1.4 Delivery systems for pesticide formulations 16 CHAPTER 2 CROP PROTECTION PRODUCT FORMULATIONS 17 2.1 Introduction 17 2.2 Formulation Objectives, Guidelines and International Codes 17 2.3 Conventional Formulations (Old Technology) 19 2.3.1 Dusts (DP) 19 2.3.2 Wettable Powders (WP) 20 2.3.3 Granules (GR) 21 2.3.4 Solution Concentrates (SL) 22 2.3.5 Emulsifiable Concentrates (EC) 23 2.4 Safer Formulations (New Technology) 25 2.4.1 Suspension Concentrates (SC) 25 2.4.2 Oil-in-water Emulsions (EW) 26 2.4.3 Capsule Suspensions (CS) 27 2.4.4 Water Dispersible/Soluble Granules (WG/SG) 29 CHAPTER 3 SURFACTANT ADDITIVES FOR FORMULATIONS 33 3.1 Introduction 33 3.2 Types of surfactants 33 3.2.1 Anionic Surfactants 34 3.2.1.1 Alkylbenzene sulphonates 34 3.2.1.2 Alkyl naphthalene sulphonates 35 3.2.1.3 Alcohol sulphates 35 3.2.1.4 Ether sulphates 36 3.2.1.5 Alkyl sulfosuccinates 36 3.2.1.6 Sulphonated naphthalene /formaldehyde condensates 37 3.2.1.7 Lignosulphonates 37 3.2.1.8 Polycarboxylates 39 3.2.1.9 Olefin sulphonates 40 3.2.1.10 Phosphate ethoxylates 40 3.2.1.11 Tristyrylphenol phosphates and sulphates 41 3.2.1.12 Taurates 41 3.2.2 Nonionic surfactants 42 3.2.2.1 Alkylphenol ethoxylates (APE) 43 3.2.2.2 Tristyrylphenol (TSP) ethoxylates 43 3.2.2.3 Alcohol ethoxylates 44 3.2.2.4 Aliphatic acid ethoxylates (PEG esters) 45 3.2.2.5 Sorbitan esters and ethoxylates 46 3.2.2.6 Castor oil ethoxylates 47 3.2.2.7 Amine ethoxylates 48 3.2.2.8 Polymeric surfactants 48 - Block copolymers 48 - “Comb” / graft copolymers 51 3.2.2.9 lkylpolyglycosides (APG) 52 3.2.2.10 Organosilicones 52 3.2.2.11 Cetylenic diols 53 3.2.3 Cationic Surfactants 54 3.2.3.1 Quaternary ammonium compounds 54 3.2.3.2 Amine salts 55 3.2.3.3 Amine oxides 55 3.2.3.4 Amine ethoxylates with low EO content 55 3.2.4 Amphoteric surfactants 56 3.3 Properties of surfactants 57 3.3.1 Adsorption and lowering of surface and interfacial tension 57 3.3.2 Micelle formation 57 3.3.3 Liquid crystal formation 59 3.3.4 Cloud point of nonionic surfactants 60 3.3.5 Krafft Point 61 3.4 Surfactant products and suppliers 62 CHAPTER 4 OTHER ADDITIVES FOR FORMULATIONS 63 4.1 Carriers and fillers 63 4.2 Solvents 65 4.3 Antisettling agents 70 4.3.1 Montmorillonite (Bentonite) Clay Minerals 70 4.3.2 Fumed silica 71 4.3.3 Polysaccharides 71 4.4 Antifreeze agents 72 4.5 Antifoam and defoamer 73 4.6 Polymers 73 4.7 Preservatives 74 4.8 Sequestrants 77 CHAPTER 5 TANK-MIX ADJUVANTS 79 5.1 Adjuvants for bioenhancement 79 5.2 Adjuvants to improve application properties (utility adjuvants) 80 5.3 Adjuvant Terminology 80 5.3.1 Activator 80 5.3.2 Wetting and spreading 80 5.3.3 Sticker 81 5.3.4 Extenders 82 5.3.5 Humectant 82 5.3.6 Compatibility agent 82 5.3.7 Antidrift agents 82 5.3.8 Antifoam/defoaming agents 82 5.3.9 Buffering agents 83 5.3.10 Inverting agents 83 5.3.11 Sequestering agents 83 5.3.12 Inorganic salts 84 5.4 Oil-based adjuvants 84 5.4.1 Crop oils 85 5.4.2 Crop oil concentrates (COC) 85 5.4.3 Properties of mineral oils used as adjuvants 85 5.4.4 Vegetable oils used as adjuvants 87 5.5 Overview of adjuvants used in tank mixes: information provided by Allen Underwood of Helena Chemical Company, Memphis, TN, US. Allen Underwood is an Executive Committee Member of the ISAA 89 CHAPTER 6 MODE OF ACTION OF ADJUVANTS 97 6.1 Introduction 97 6.2 Atomisation 98 6.3 Transport to target 99 6.4 Droplet impaction 100 6.5 Wetting and Spreading 102 6.6 Drying of droplets and deposit effects 103 6.7 Uptake and translocation 106 6.7.1 Contribution from Terry Grayson (retired), formerly with Shell Agrochemicals, Sittingbourne, UK 108 6.7.2 Contribution from Allen Underwood, Helena Chemical Company, Memphis, TN, US and Executive Committee Member of the ISAA 112 6.7.3 Contribution from David Stock of Syngenta, Jealott’s Hill, UK and Executive Committee Member of the ISAA 114 6.7.4 Contribution from Hans de Ruiter, SURfaPLUS, the Netherlands and Executive Committee Member of the ISAA 116 6.7.5 Contribution from Per Kudsk, Danish Institute of Agricultural Sciences, Denmark 117 6.8 Biological effect 118 6.9 Spray tank problems 118 CHAPTER 7 FUTURE TRENDS IN ADDITIVES AND ADJUVANTS 121 7.1 Safer formulation developments 121 7.2 Safer Additive and Adjuvant Developments 122 7.3 Biopesticides 126 7.3.1 Introduction 126 7.3.2 New biopesticides 127 7.3.3 Formulations and adjuvants 128 7.4 International Society for Agrochemical Adjuvants (ISAA) 129 7.4.1 Objectives ISAA 129 7.4.2 Organisation and membership 130 7.4.3 ISAA 2004 - Adjuvant use expands in new areas 130 7.4.3.1 New products 130 7.4.3.2 Spray drift 131 7.4.3.3 Herbicides 131 7.4.3.4 Insecticides/fungicides 132 7.5 Expert Views on Future Developments in Formulation and Adjuvant Technology 133 7.5.1 Contribution from Alan Knowles, FORM-AK Ltd, Formulation Consultancy Services, UK 133 7.5.2 Contribution from David Stock, Syngenta UK, and Exectutive Committee Member of the ISAA 136 7.5.3 Contribution from Hans de Ruiter, SURfaPLUS Netherlands, and Executive Committee Member of the ISAA 138 7.5.4 Contribution from Allen Underwood, Helena Chemical Company, US and Executive Committee Member of the ISAA 140 CHAPTER 8 REGULATION OF ADDITIVES AND ADJUVANTS 143 8.1 Introduction 143 8.2 Regulation of pesticide products in the European Union 144 8.2.1 Plant Protection Products Directive in EU 144 8.2.2 EU pesticide review programme 145 8.2.3 Regulation procedures for additives and tank mix adjuvants in EU countries 148 8.2.3.1 Belgium 149 8.2.3.2 Denmark 149 8.2.3.3 France 150 8.2.3.4 Germany 150 8.2.3.5 The Netherlands 150 8.2.3.6 Spain 151 8.2.3.7 Sweden 151 8.2.3.8 UK 151 8.2.3.9 ECPA queries plans for new Directive 91/414 Annexes 153 8.2.3.10 Phase-out of nonylphenol ethoxylate surfactants 153 8.2.3.11 Report on registration and use of tank mix adjuvants in nine EU countries 154 8.2.4 REACH Regulations 154 8.3 Regulation of pesticide products in US and Canada 156 8.3.1 Background 156 8.3.2 Categorisation of inerts 157 8.3.3 FQPA 159 8.3.4 Regulatory situation in individual states 159 8.3.4.1 California 159 8.3.4.2 Washington State 160 8.3.4.3 Other states 161 8.3.5 Adjuvant standards and certification 161 8.3.6 Canada 161 8.4 Regulation of pesticide products in other countries 162 8.4.1 Australia 162 8.4.2 Latin America 163 8.4.2.1 ANDEAN countries 163 8.4.2.2 Argentina 163 8.4.2.3 Brazil 163 8.4.2.4 Chile 164 8.4.2.5 Mexico 164 8.4.3 Asia 164 8.4.3.1 China 165 8.5 Moves towards harmonisation of regulation 165 8.5.1 Agrochemical data supply network mooted 165 8.5.2 Asia 166 8.5.3 Middle East 167 CHAPTER 9 GLOBAL MARKET FOR ADJUVANTS FOR AGROCHEMICALS 169 9.1 Introduction 169 9.2 Global market for agrochemicals 170 9.3 Global markets for adjuvants and additives 173 9.3.1 Global market 173 9.3.2 US market 174 9.3.2.1 Trends in US adjuvant markets 175 9.3.3 Europe 177 9.3.4 South Africa 177 9.3.5 Market value of surfactants used in adjuvants 177 CHAPTER 10 COMPANY NEWS AND PROFILES 179 10.1 Company News 179 10.1.1 Exwold and Crack merge (May 2006) 179 10.1.2 Croda takes over Uniqema (June 2006) 179 10.1.3 BASF takes over Englehard (June 2006) 180 10.1.4 Nufarm/Micap in micro-encapsulation deal (July 2006) 181 10.1.5 De Sangosse acquires Loveland (February 2005) 181 10.2 UK suppliers of adjuvants 182 10.3 Company profiles 183 10.3.1 Akzo Nobel Surface Chemistry AB 183 10.3.2 Clariant 191 10.3.3 Cognis 193 10.3.4 Croda 197 10.3.5 De Sangosse Ltd 199 10.3.6 FORM-AK Ltd 201 10.3.7 Helena Chemical Company 203 10.3.8 Huntsman LLC 205 10.3.9 Interagro (UK) Ltd 207 10.3.10 Intracrop 208 10.3.11 Lankem Ltd, 211 10.3.12 NPFC 211 10.3.13 Rhodia 213 10.3.14 Stepan Company 218 10.3.15 SURfaPLUS BV 222 10.3.16 Uniqema 223 REFERENCES 229 LIST OF TABLES Table 2.1 The main formulation types and their characteristics Table 2.2 Dust concentrate Table 2.3 Dust formulation Table 2.4 A typical formulation for a wettable powder is shown below: Table 2.5 Classification of carriers Table 2.6 A typical granule formulation is shown below: Table 2.7 A typical solution concentrate formulation is shown below Table 2.8 A typical emulsifiable concentrate formulation is shown below Table 2.9 A typical SC formulation is shown below: Table 2.10 Different polymer wall materials Table 2.11 A typical composition of a CS formulation made by interfacial polymerisation is as follows Table 2.12 A typical water-dispersible granule formulation is shown below Table 2.13 Comparison of Granulation Processes Table 3.1 Examples of the use of surfactants as additives (co-formulants) for particular formulation types are shown below: Table 3.2 Examples of some commercially available CaDBS are shown below: Table 3.3 An example of this type of product is: Table 3.4 An example of this type of product is: Table 3.5 An example of this type of product is: Table 3.6 Examples of ether sulphate suppliers / range products are shown Table 3.7 Examples of alkyl sulfosuccinate suppliers are shown Table 3.8 Examples of suppliers / range products are shown: Table 3.9 Examples of suppliers and range products are shown: Table 3.10 Examples of range products are shown below. Table 3.11 Examples of Suppliers / range products are shown: Table 3.12 Examples of Suppliers / range products are shown: Table 3.13 Examples of Suppliers / range products are shown: Table 3.14 Examples of products and suppliers are as shown: Table 3.15 Examples of Suppliers / range products are shown: Table 3.16 Examples of suppliers and range product TSP ethoxylates Table 3.17 Physical Properties of Linear Alcohol Ethoxylates Table 3.18 Examples of suppliers and range products are shown: Table 3.19 Examples of range products and suppliers are as shown: Table 3.20 Examples of suppliers / range products are shown: Table 3.21 Suppliers and trade names include the following: Table 3.22 Examples of suppliers and range products are shown: Table 3.23 Examples of suppliers and range products are shown: Table 3.24 Examples of Suppliers / range products are shown: Table 3.25 An example of this type of product is: Table 3.26 An example of this type of product is: Table 3.27 An example of a “comb” surfactant is: Table 3.28 An example of this type is: Table 3.29 An example of this type is Table 3.30 An example of this type of product is: Table 3.32 Surface tensions for water/air interface (mN/m) Table 3.33 Critical Micelle Concentrations of some common surfactants Table 3.34 Cloud Points of Some Nonionic Surfactants Table 3.35 Examples of surfactant suppliers and product ranges (trade names) available. Table 4.1 Some fillers used in WP and WG formulations Table 4.2 Some carriers used in granule formulations Table 4.3 Absorptive capacities of some granular carriers Table 4.4 Number of particles per gram for attapulgite at various mesh sizes Table 4.5 Properties of some commonly used solvents for EC formulations Table 4.6 Phytotoxicity ratings for some solvents Table 4.7 Naphthalene content of some aromatic solvents Table 4.8 Vegetable oil methyl ester solvents Table 4.9 Examples of polar solvents used in liquid agrochemical formulations Table 4.10 Antisettling agents used in aqueous colloidal formulations Table 4.11 Antifreeze solutions in water Table 4.12 Examples of some antifoaming and defoaming agents Table 5.1 Examples of extenders are as follows: Table 5.2 Defoaming agents Table 5.3 Examples of micronutrients in chelate form include the following: Table 5.4 Physical properties of mineral oils of significance in adjuvants Table 5.5 Composition of some vegetable oils used in adjuvants Table 6.1 Contact angles for water droplets on field plants Table 6.2 Effect of Surfactants on Dried Deposit Areas. Table 6.3 Solubilisation Ratios of Some Surfactants with a Triazole Fungicide. Table 6.5 Effect of Surfactant on Uptake of a Triazole Fungicide Table 7.1 Formulations Listed in Pesticide Manuals 10th, 12th and 13th Editions Table 8.1 Active ingredients supported or lost in EU review (May 2006) Table 8.2 Data requirements by category for registration of adjuvants in EU countries Table 9.1 Global agrochemical market by region, in selected years (US$ millions) Table 9.2 Global agrochemical market by pesticide type, in selected years (in US$ dollars) Table 9.3 World rankings of the big six agrochemical companies, 2005 Table 9.4 Growth of US adjuvant market from 1992 to 2005 in US$ millions Table 9.5 Surfactants used in agrochemical adjuvants by region, US$ millions. Table 10.1 Major UK suppliers of spray adjuvants for bio-enhancement in 2006. Table 10.2 The 3 major UK suppliers of bio-enhancing adjuvants in 2006 Table 10.3 UK adjuvant categories Table 10.4 Cognis AgroSolutions - Formulation surfactant additives Table 10.5 Croda’s main range products relevant to agrochemicals are shown below. Table 10.6 Details of range product adjuvants are shown below Table 10.7 De Sangosse auxiliary spray products Table 10.8 Helena Adjuvant Products by Type Table 10.9 Product range for the agrochemical industry Table 10.10 Adjuvants for bio-enhancement Table 10.11 Utility adjuvants Table 10.12 Adjuvant product range for bio-enhancement of active ingredients Table 10.13 Anionic Surfactants Table 10.14 Nonionic surfactants Table 10.15 Antifoam agents Table 10.16 Synthetic polymers Table 10.17 Performance concentrates and blends (North America) Table 10.18 Natural biopolymers Table 10.19 Other speciality products Table 10.20 Stepan Core Technologies Table 10.21 Stepan Products: Functionality and Chemistry LIST OF FIGURES Figure 2.1 Microcapsules prepared by Interfacial Polymerisation Figure 3.1 Structure of dodecylbenzene sulphonates Figure 3.2 Structure of alkylnaphthalene sulphonates. Figure 3.3 Structure of alcohol sulphates Figure 3.4 Structure of ether sulphates Figure 3.5 Alkyl sulfosuccinates Figure 3.6 Sulphonated naphthalene / formaldehyde condensate Figure 3.7 Structure of lignosulphonates Figure 3.8 Sulphonation of lignin Figure 3.9 Polycarboxylate surfactants Figure 3.10 Olefin sulphonates Figure 3.11 Phosphated ethoxylates Figure 3.12 Phosphated and sulphated tristyrylphenol ethoxylate Figure 3.13 Taurates Figure 3.14 Alkylphenol ethoxylates Figure 3.15 Structure of tristyrylphenol ethoxylates Figure 3.16 Alcohol ethoxylates Figure 3.17 PEG mono- and di-esters Figure 3.18 Structure of sorbitan esters Figure 3.19 Structure of sorbitan ester ethoxylates (mono or triester) Figure 3.20 Castor oil ethoxylates Figure 3.21 Amine ethoxylates Figure 3.22 ABA block copolymers Figure 3.23 BAB block copolymer Figure 3.24 BAB block copolymer (PHS/PEG/PHS) Figure 3.25 BA block copolymers Figure 3.26 Styrene / maleic anhydride copolymer Figure 3.27 “Comb” or graft copolymer Figure 3.28 Alkylpolyglucosides (APG) Figure 3.29 Organosilicones Figure 3.30 Acetylenic diols Figure 3.31 General structure of a quaternary ammonium surfactant Figure 3.32 Some examples of quaternary ammonium surfactants Figure 3.33 Laurylamine acetate Figure 3.34 Lauryl dimethyl amine oxide Figure 3.35 Amine ethoxylate (2EO) Figure 3.36 Solubilisation of active ingredient within surfactant micelle Figure 3.37 Liquid crystalline phases Figure 3.38 Krafft Point of ionic surfactants Figure 4.1 Charged plates of montmorillonite clay particles Figure 4.2 Gelling properties of Montmorillonite (Bentonite) mineral clays Figure 4.3 Fumed silica as antisettling (gelling) agent. Figure 4.4 Xanthan gum as antisettling (gelling) agent Figure 4.5 Isocyanates used in capsule suspensions Figure 5.1 Wetting and spreading of spray droplets on leaf surfaces Figure 5.2 Formation of rainfast spray deposit on leaf surface Figure 5.3 Composition of mineral oils Figure 6.1 Atomisation from a spray nozzle Figure 6.2 Deposition of droplets at target site Figure 6.3 Effect of Surfactants on Contact Angles on Plants Figure 7.1 Typical alkylphenol and aliphatic alcohol ethoxylates Figure 7.2 Typical Alkylpolyglucoside Adjuvant

Summary:

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$1 billion for 2001 and it is generally estimated to have risen to about US$ 1.5 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

Companies Mentioned

- Akzo Nobel Surface Chemistry AB - Clariant - Cognis - Croda - De Sangosse Ltd - FORM-AK Ltd - Helena Chemical Company - Huntsman LLC - Interagro (UK) Ltd - Intracrop - Lankem Ltd - NPFC - Rhodia - Stepan Company - SURfaPLUS BV - Uniqema