アジュバントおよび添加剤市場

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.

Table of Contents

• 1.1 Historical background
• 1.2 Scope of report
• 1.3 Formulation additives and adjuvants
• 1.4 Delivery systems for pesticide formulations

• 2.1 Introduction
• 2.2 Formulation Objectives, Guidelines and International Codes
• 2.3 Conventional Formulations (Old Technology)
  • 2.3.1 Dusts (DP)
  • 2.3.2 Wettable Powders (WP)
  • 2.3.3 Granules (GR)
  • 2.3.4 Solution Concentrates (SL)
  • 2.3.5 Emulsifiable Concentrates (EC)
• 2.4 Safer Formulations (New Technology)
  • 2.4.1 Suspension Concentrates (SC)
  • 2.4.2 Oil-in-water Emulsions (EW)
  • 2.4.3 Capsule Suspensions (CS)
  • 2.4.4 Water Dispersible/Soluble Granules (WG/SG)

• 3.1 Introduction
• 3.2 Types of surfactants
  • 3.2.1 Anionic Surfactants
    • 3.2.1.1 Alkylbenzene sulphonates
    • 3.2.1.2 Alkyl naphthalene sulphonates
    • 3.2.1.3 Alcohol sulphates
    • 3.2.1.4 Ether sulphates
    • 3.2.1.5 Alkyl sulfosuccinates
    • 3.2.1.6 Sulphonated naphthalene /formaldehyde condensates
    • 3.2.1.7 Lignosulphonates
    • 3.2.1.8 Polycarboxylates
    • 3.2.1.9 Olefin sulphonates
    • 3.2.1.10 Phosphate ethoxylates
    • 3.2.1.11 Tristyrylphenol phosphates and sulphates
    • 3.2.1.12 Taurates
  • 3.2.2 Nonionic surfactants
    • 3.2.2.1 Alkylphenol ethoxylates (APE)
    • 3.2.2.2 Tristyrylphenol (TSP) ethoxylates
    • 3.2.2.3 Alcohol ethoxylates
    • 3.2.2.4 Aliphatic acid ethoxylates (PEG esters)
    • 3.2.2.5 Sorbitan esters and ethoxylates
    • 3.2.2.6 Castor oil ethoxylates
    • 3.2.2.7 Amine ethoxylates
    • 3.2.2.8 Polymeric surfactants
      • .....Block copolymers
      • .....“Comb” / graft copolymers
    • 3.2.2.9 lkylpolyglycosides (APG)
    • 3.2.2.10 Organosilicones
    • 3.2.2.11 Cetylenic diols
  • 3.2.3 Cationic Surfactants
    • 3.2.3.1 Quaternary ammonium compounds
    • 3.2.3.2 Amine salts
    • 3.2.3.3 Amine oxides
    • 3.2.3.4 Amine ethoxylates with low EO content
  • 3.2.4 Amphoteric surfactants
• 3.3 Properties of surfactants
  • 3.3.1 Adsorption and lowering of surface and interfacial tension
  • 3.3.2 Micelle formation
  • 3.3.3 Liquid crystal formation
  • 3.3.4 Cloud point of nonionic surfactants
  • 3.3.5 Krafft Point
• 3.4 Surfactant products and suppliers

• 4.1 Carriers and fillers
• 4.2 Solvents
• 4.3 Antisettling agents
  • 4.3.1 Montmorillonite (Bentonite) Clay Minerals
  • 4.3.2 Fumed silica
  • 4.3.3 Polysaccharides
• 4.4 Antifreeze agents
• 4.5 Antifoam and defoamer
• 4.6 Polymers
• 4.7 Preservatives
• 4.8 Sequestrants

• 5.1 Adjuvants for bioenhancement
• 5.2 Adjuvants to improve application properties (utility adjuvants)
• 5.3 Adjuvant Terminology
  • 5.3.1 Activator
  • 5.3.2 Wetting and spreading
  • 5.3.3 Sticker
  • 5.3.4 Extenders
  • 5.3.5 Humectant
  • 5.3.6 Compatibility agent
  • 5.3.7 Antidrift agents
  • 5.3.8 Antifoam/defoaming agents
  • 5.3.9 Buffering agents
  • 5.3.10 Inverting agents
  • 5.3.11 Sequestering agents
  • 5.3.12 Inorganic salts
• 5.4 Oil-based adjuvants
  • 5.4.1 Crop oils
  • 5.4.2 Crop oil concentrates (COC)
  • 5.4.3 Properties of mineral oils used as adjuvants
  • 5.4.4 Vegetable oils used as adjuvants
• 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

• 6.1 Introduction
• 6.2 Atomisation
• 6.3 Transport to target
• 6.4 Droplet impaction
• 6.5 Wetting and Spreading
• 6.6 Drying of droplets and deposit effects
• 6.7 Uptake and translocation
  • 6.7.1 Contribution from Terry Grayson (retired), formerly with Shell Agrochemicals, Sittingbourne, UK
  • 6.7.2 Contribution from Allen Underwood, Helena Chemical Company, Memphis, TN, US and Executive Committee Member of the ISAA
  • 6.7.3 Contribution from David Stock of Syngenta, Jealott' s Hill, UK and Executive Committee Member of the ISAA
  • 6.7.4 Contribution from Hans de Ruiter, SURfaPLUS, the Netherlands and Executive Committee Member of the ISAA
  • 6.7.5 Contribution from Per Kudsk, Danish Institute of Agricultural Sciences, Denmark
• 6.8 Biological effect
• 6.9 Spray tank problems

• 7.1 Safer formulation developments
• 7.2 Safer Additive and Adjuvant Developments
• 7.3 Biopesticides
  • 7.3.1 Introduction
  • 7.3.2 New biopesticides
  • 7.3.3 Formulations and adjuvants
• 7.4 International Society for Agrochemical Adjuvants (ISAA)
  • 7.4.1 Objectives ISAA
  • 7.4.2 Organisation and membership
  • 7.4.3 ISAA 2004 - Adjuvant use expands in new areas
    • 7.4.3.1 New products
    • 7.4.3.2 Spray drift
    • 7.4.3.3 Herbicides
    • 7.4.3.4 Insecticides/fungicides
• 7.5 Expert Views on Future Developments in Formulation and Adjuvant Technology
  • 7.5.1 Contribution from Alan Knowles, FORM-AK Ltd, Formulation Consultancy Services, UK
  • 7.5.2 Contribution from David Stock, Syngenta UK, and Exectutive Committee Member of the ISAA
  • 7.5.3 Contribution from Hans de Ruiter, SURfaPLUS Netherlands, and Executive Committee Member of the ISAA
  • 7.5.4 Contribution from Allen Underwood, Helena Chemical Company, US and Executive Committee Member of the ISAA

• 8.1 Introduction
• 8.2 Regulation of pesticide products in the European Union
  • 8.2.1 Plant Protection Products Directive in EU
  • 8.2.2 EU pesticide review programme
  • 8.2.3 Regulation procedures for additives and tank mix adjuvants in EU countries
    • 8.2.3.1 Belgium
    • 8.2.3.2 Denmark
    • 8.2.3.3 France
    • 8.2.3.4 Germany
    • 8.2.3.5 The Netherlands
    • 8.2.3.6 Spain
    • 8.2.3.7 Sweden
    • 8.2.3.8 UK
    • 8.2.3.9 ECPA queries plans for new Directive 91/414 Annexes
    • 8.2.3.10 Phase-out of nonylphenol ethoxylate surfactants
    • 8.2.3.11 Report on registration and use of tank mix adjuvants in nine EU countries
  • 8.2.4 REACH Regulations
• 8.3 Regulation of pesticide products in US and Canada
  • 8.3.1 Background
  • 8.3.2 Categorisation of inerts
  • 8.3.3 FQPA
  • 8.3.4 Regulatory situation in individual states
    • 8.3.4.1 California
    • 8.3.4.2 Washington State
    • 8.3.4.3 Other states
  • 8.3.5 Adjuvant standards and certification
  • 8.3.6 Canada
• 8.4 Regulation of pesticide products in other countries
  • 8.4.1 Australia
  • 8.4.2 Latin America
    • 8.4.2.1 ANDEAN countries
    • 8.4.2.2 Argentina
    • 8.4.2.3 Brazil
    • 8.4.2.4 Chile
    • 8.4.2.5 Mexico
  • 8.4.3 Asia
    • 8.4.3.1 China
• 8.5 Moves towards harmonisation of regulation
  • 8.5.1 Agrochemical data supply network mooted
  • 8.5.2 Asia
  • 8.5.3 Middle East

• 9.1 Introduction
• 9.2 Global market for agrochemicals
• 9.3 Global markets for adjuvants and additives
  • 9.3.1 Global market
  • 9.3.2 US market
    • 9.3.2.1 Trends in US adjuvant markets
  • 9.3.3 Europe
  • 9.3.4 South Africa
  • 9.3.5 Market value of surfactants used in adjuvants

• 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 include the following:
• 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

• 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