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H.G. Hauthal*

CESIO 2004 Dynamic Surfactants and Nanostructured Surfaces for an Innovative Industry
Keywords: Surfactants, detergents, raw materials, oleochemicals, GTL technology, industrial application, emulsifiers, personal care, nanostructured surfaces, environment, ecology, legislation, wellness, sustainable development, market data

Framework Conditions for a

Introduction

Sustainable Chemical Industry

The chemical industry is one of the top industries in 11 of the former 15 EU member states. With an employment of 1.7 million (plus 3 million indirectly) sales of 528 billion Euro (with pharmaceuticals) were achieved in 2002. The trade surplus amounted to 70 billion Euro. Against this background E. Voscherau, Vice Chairman of BASF and President of CEFIC, asked in his Plenary Lecture for better Framework Conditions for a Sustainable Chemical Industry in Europe. His policy recommendations are

he World Surfactants Congress came back to Germany: After the first CESIO event in 1984 in Munich the 6th CESIO Congress Surfactants make the world go round took place in Berlin and around 1000 people attended this high-level meeting perfectly organized by TEGEWA and its former chairman of many years, Lothar Noll. Besides eight Plenary Lectures in five Sections A Raw Materials and Processing, B Structures and Properties, C Industrial Applications, D Household, I & I and Personal Care, and E Environment, Toxicology and Regulatory Affairs 100 oral presentations were given. The scientific program was rounded up by more than 110 posters. The exhibition offered a broad forum for initiating, renewing, and strengthening of personal contacts. The 6th CESIO Congress was opened by Arno H. Stegk, President of CESIO, who also chaired the Plenary Lectures.

Go for the Lisbon goal and make Europe the most dynamic knowledgebased region in the world by 2010! Establish a new industrial policy to improve competitiveness without interventional measures (chemicals policy as a test case). Create a climate that promotes innovation. Orientate environmental legislation towards sustainable development and give equal weight to all three aspects environmental, social and economic. Avoid regulatory solo-runs in Europe. Deliver less bureaucracy and better (not more) regulation. Use the most efficient and cost-effective means to achieve environmental goals. Base political decisions on sound science.

Instead of the EU Enterprise Commissioner E. Liikanen some remarks on Shaping a Competitive Environment for European Industry were given by P. Hennessy, Director, Environmental Aspects of Enterprise Policy, Resource-based and Specific Industries, EU Directorate General Enterprise. Three steps are necessary to address the new challenges including the EU enlargement: Ensuring that industry is not overburdened with regulation, making sure that all the EU policies help to reinforce industrial competitiveness, and developing the sectoral dimension of industrial policy. ... we not only need a healthy environment for a healthy economy; we also need a healthy economy for a healthy environment, he said. The Challenge for Our Industry: Changing World Demographics was analyzed by S. van Straelen in another Plenary Lecture that also highlighted new ways to engage the consumer. The Global Surfactant Market The global surfactant market volume size is about 12 million tons (2003), with an overall rough value of 13 billion Euro. The regional split shows North America to be the biggest surfactant market in the world with 35%. Asia-Pacific follows next with 29%, Western Europe consumes 23%, the rest of the world accounts in value for 13%. The split of the global surfactant market by end-user application is shown in Fig. 1, by suppliers in Fig. 2. The global household detergent market had a value in 2002 of 29 billion Euro.

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Split in Value in 2003 of global surfactant market

Market shares by value in 2003 of global surfactant market

Fig. 1 The global surfactant market by end-user application (Source: U. Lehner, Henkel).

Fig. 2 The global surfactant market by suppliers (Source: U. Lehner, Henkel).

Just three global players together dominate 62% of the market (P&G 29, Unilever 22, and Henkel incl. Dial 11%). Reckitt Benckiser and Colgate with 3% each of this market are much smaller but active in many countries. After presenting these data U. Lehner, Henkel KGaA, in his Plenary Lecture discussed Surfactants Surfing Around the World Requirements for the Surfactants Industry The Market Partners Point of View. Clustering the demands from consumers in three different claim dimensions for the product segment of heavy-duty detergents results in performance, convenience, and aesthetics. These future demands can only be solved in a close cooperation between suppliers and manufacturers. Product cycles are getting shorter and shorter because innovations are more rapidly copied, foremost by private labels. Striving for innovation within the economic boundaries is difficult enough but additionally, there is a growing number of laws, regulations, and directives (European Detergents Regulation, Biocidal Products Directive, Dangerous Preparation Directive). The consumer expectations in the emerging countries of South America, Africa, and Asia are more basic than in Western countries but include clear performance expectations for household detergents. Because the washing machine penetration is very low, for instance, only 15% in India compared to 95% in Germany quality perceptions such as good foam

Surfactants volume forecast for the household detergent sector (base 2001 = 100%)

Fig. 3 Estimated future demands will be in Asia-Pacific (Source: U. Lehner, Henkel).

characteristics, skin compatibility as well as pleasant perfume are important for detergents. A general development for many emerging markets is the replacement of soap and detergent bars by powder detergents that are twice as expensive. Fig. 3 shows the future demands for surfactants in Asia-Pacific compared to the industrialized countries. Personal care products are considered to be essentials by consumers. Thus, these products are somewhat insensitive to overall economic change. Western Europe with 38, North America with 25, and Asia-Pacific with 24% of the world market of cosmetics and toiletries clearly dominate more than an 80% share of

this market, worth more than 153 billion Euro in 2003. The incombinable came true: In 2003, the innovation of the year was a facial washing gel combining a high cleansing efficacy with a very low skin irritating score. In the global market for industrial cleaning in the food and beverage industry (about 3.5 billion Euro) there are only two global players Ecolab and Johnson Diversey Inc., the others being thousands of small local or regional companies. Industrial cleaning is based on businessto-business relationships. The client demands integrated solutions encompassing chemicals, dispensing equipment, software, staff training, and support ser-

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vices. Acting as a global player in this market means that the business partners have to be global, too. The market for metal cleaning amounts to approx. 650 million Euro. Bigger and very small suppliers share this market among themselves. Henkels share is approx. 27%, followed by the direct competitors Chemetall and Kluthe. There is a further demand for new high-performance surfactants, especially for such products which are low-foaming under high pressure and at low temperatures. As D. Ferrari, Huntsman Performance Products, in his Plenary Lecture The Surfactant Value Chain pointed out the surfactant industry is facing unprecedented pressures around raw materials prices, exacerbated by extreme volatility in gas pricing, and has been fighting this two-headed price and volatility dragon for three years. The value chain has to change with regard to efficiency, sourcing, rationalization (consolidation), and innovation. Safety remains a fundamental requirement in everything that is done. Raw Materials and Processing In 2002, the worldwide chemical industry used 16.8 million metric tons or 14% of the total production of oils and fats, which was 120 million (2003: 124.3 million) metric tons (Fig. 4). More than 10 million tons are processed into soap. Around 4.5 million tons are used in oleochemical processes. According to Cognis and Sasol data the world capacity for fatty alcohols amounts to 2.15 million metric tons in 2002 (Table 1). The development of the world detergents alcohol capacity is shown in Fig. 5, the total fatty alcohol market by application in Fig. 6. 75% are used as detergent alcohols. The development of the fatty acids global capacities from 1985 to 2006 is shown in Fig. 7, the fatty acids end use in Fig. 8. Typical fatty acid derivatives in a shampoo formulation are depicted in Fig. 9. The world surfactants capacity by ethoxylation and sulf(on)ation is given in Fig. 10. The world surfactants consumption is summarized in Table 2. Compared to the Henkel data cited above here a more conservative scenario is depicted.

Fig. 4 World production of oils and fats 2002, mill. mt (Source: P. Renaud and B. Brackmann, Cognis).

Fig. 5 The development of world detergents alcohol capacity, mill. mt (Source: B. Brackmann, Cognis, and C.-D. Hager, Sasol).

Fatty alcohols Natural Petrobased Coal-based

million tons 1130 900 120

since 1931 1963 2002 (Sasol)

Table 1 World capacity for fatty alcohols (Source: B. Brackmann, Cognis, and C.-D. Hager, Sasol).

In Western Europe and North America the principal demand is supplied by four surfactant groups LAS, AE, FES and FAS.

A different distribution is still valid for Asia, where LAS is, mainly for price reasons, the dominating surfactant (Fig. 11).

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As J. Vaughan, Sasol Olefins & Surfactants, pointed out, the Gas to Liquids, or GTL technology is being developed by a number of the major international oil and gas companies, essentially to monetize stranded gas. The primary products from such plants are clean fuels and low-sulfur diesel in particular. Central to the emergence of GTL technology is Fischer Tropsch (FT) technology, which previously has already given rise to a new source of fatty alcohols from coal as a raw material. GTL plants will not only produce low-sulfur diesel but also significant quantities of paraffins and other feedstocks suitable for surfactant intermediates. These new feedstocks are a challenge to the surfactant industry to innovatively take advantage of these opportunities. Several GTL technology companies have aligned themselves with gas resource holders and other partners and have announced GTL studies as well as projects. It is expected that the first of these GTL plants will be operational by 2006 if all goes according to their project plans. A comprehensive Shell study revealed that GTL n-paraffins have no adverse effect on both homogeneous and heterogeneous alkylation processes. Also, LAS made from Shell GTL paraffins is adequately biodegradable and its surfactancy and detergency performance is identical to commercially available LAS. From Shells point of view, taking the cost-effectiveness of the GTL paraffins compared to kerosin-derived paraffins into account, by the end of this decade GTL technology will largely replace kerosine extraction technology to meet the growth in n-paraffin demand for LAB. With all this GTL paraffin potential coming onto the market, it is probably worthwile considering alternate and even more efficient ways to activate the paraffin for use in surfactants or direct conversion of paraffins to the desired intermediate. In the focus of manufacturing and transportation safety, one of the topics of the Raw Materials and Processing Section A: once more the safety in production and distribution of ethylene oxide and the safe design and operation of ethoxylation processes as well as the TUIS system as well-proven emergency response.

Fig. 6 Total fatty alcohol capacity by application (Source: B. Brackmann, Cognis, and C.-D. Hager, Sasol).

Fig. 7 Development of fatty acids global capacities 1985 to 2006 (Source: K.H. Nottinger, Cognis).

Fig. 8 Fatty acids end use 2002 (Source: K.H. Nottinger, Cognis).

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The fixed bed alkylation process for the manufacture of linear alkylbenzene for the first time implemented in 1995 has come from a concept to a successful reality. This reliable and flexible technology produces a high 2-phenyl type of LAB using standard olefin feedstock with low diolefin and aromatic content. Wellness and Sustainability The wellness and sustainability megatrends will have a decisive influence on the future and because of this on the behavior of the consumer, stressed A. Trius in his Plenary Lecture Wellness, Sustainability and a Specialty Chemical Company A Contradiction in Terms? (co-author: B. Brackmann), Cognis. Manufacturers will have to be prepared for the changes that will take place early enough so as not to miss the boat. This does not just apply to manufacturers of consumer goods such as food, clothing and household items. Also trivial things such as washing, rinsing and cleaning agents, cosmetics and lubricants, engines and many other things will have to be adjusted to these trends in future, in order to be able to maintain or expand their position in the market. The early strategic orientation of a chemical company that calls itself a specialty chemical producer is extremely important here. Solutions that enable the customer to manufacture future-orientated products that correspond with the future consumer wish in good time will have to be found. These products also have to suit the megatrends wellness and sustainability, in order for everybody to gain in future. The skill of the supplier, the specialty chemical manufacturer, lies in early recognition of the mood of the times, development of the necessary customer solutions and in making the necessary investments in order to be able to continue working profitably. New Surfactants At CESIO 2004 some new surfactant molecules were presented: selectively methyl branched C15 to C16 alcohol sulfates (Neodol 67 AS, Shell Chemicals) that pro-

Fig. 9 Typical fatty acid derivatives in a shampoo formulation (Source: K.H. Nottinger, Cognis).

Fig. 10 World surfactant capacity by ethoxylation and sulf(on)ation 2002, mill. mt (Source: B. Brackmann, Cogis, and C.-D. Hager, Sasol). Surfactant Soap Anionics Linear alkylbenzene sulfonate (LAS) Branched alkylbenzene sulfonate Fatty alkyl ether sulfate (FAES) Fatty alkyl sulfate (FAS) Nonionics Alcohol ethoxylates (AE) Nonylphenol ethoxylates (NPE) Quats Amphoterics Others*
* including lignin and petroleum sulfonate, and tall oil derivatives

million tons 9.0 4.5 2.9 0.2 0.8 0.6 1.7 1.1 0.6 0.5 0.1 2.4 18.2

Table 2 World surfactants consumption 2003 (Source: B. Brackmann, Cognis, and C.-D. Hager, Sasol).

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vide increased solubility and improved hydrophobe performance; LAS with controlled methyl branching in the hydrophobic chain; alkyl polyglucoside carboxylate (1) as a new anionic surfactant (Plantapon LGC Sorb, Cognis); tridecanol ethoxylates based on dimeric hexene (less gel phase problems, readily biodegradable, BASF); and cleavable ortho ester type surfactants, an interesting alternative for the application in industrial processes (Akzo Nobel). Future surfactant innovations are dry olefin sulfonates (Ballestra), sucrose esters (Procter & Gamble) and inulin-based surfactants for personal care applications (Orafti Non-food). New polymeric surfactants based on inulin are also suitable for the stabilization of emulsions, nanoemulsions and multiple emulsions (INUTEC Surfactants, Orafti Bio-based Chemicals) (2). The well-known but scarcely offered sarconisates and glutamates obtained by Nacylation of amino acids with fatty acid chlorides were recommended as a class of versatile surfactants with key advantages in such fields of application as dental care products, shaving products, shampoos, alkaline cleaners, carpet shampoos, dishwasher detergents, and metal working fluids (Schill & Seilacher). Structures and Properties The Structures and Properties Section B comprised new surfactant structures already cited above, new methods of surfactant characterization such as timeresolved fluorescence quenching and cryo-transmission electron microscopy, surfactant characterization outside the HLB system, exploiting synergies in surfactant mixtures and modeling of industrially relevant surfactant formulations, phase behavior and rheology including rheological properties of viscoelastic surfactant solutions, the influence of guest components in rheology and shear induced structures in surfactant lamellar phases, micellar and rheological properties of some highly viscoelastic zwitterionic surfactants and the high-throughput microemulsion phase diagram generation. Other topics were the dynamics of nearzero energy emulsification, the industri-

Fig. 11 Major surfactant markets by region (Source: B. Brackmann, Cognis, and C.-D. Hager, Sasol).

al application of the dynamic surface tension, the relation between macroscopic foams and single foam films, and surfactant-templated nanomaterial synthesis. Emulsifiers and Emulsification,

Dynamic Surfactants, and Surface Modification by Surfactants

The field of emulsifiers and emulsification was one of the key issues of the In-

dustrial Applications Section C as well as the dynamic properties of surfactants and the surface modification by surfactants. Beside a review on the state of the art of emulsion technology analytical centrifugation for rapid emulsifier selection and evaluation of emulsion stability was demonstrated. Surfactants find wide application in the manufacturing process of leather. Washing, cleaning, rewetting, dispersing, degreasing and emulsifying are the different activities of surfactants used in the

KRSS at CESIO 2004

With the first truly hand held bubble pressure tensiometer PocketDyne KRSS showed a real alternative to the existing laboratory instruments. The well-known bubble pressure tensiometer BP2 now determines diffusion and adsorption constants of surfactants in addition to dynamic surface tension values. The fully modular contact angle measuring system DSA100 determines surface free energy of solids, surface and interfacial tension of liquids as well as interfacial rheological properties by a unique combination of oscillating/expanding drop module. In case one needs to find out the right concentration range for determining the CMC value, the right choice is the Processor Tensiometer K100 series. It can be used to determine the CMC value automatically without having an idea of the concentration range. Thanks to two dosing units the volume of liquid added is aspirated again immediately after mixing. This way the whole liquid volume is kept constant. In case of a high throughput application KRSS offers the Delta 8 tensiometer. It can measure the CMC value for 8 different substances in parallel in about 2 minutes. In a cooperation with company AlCove, KRSS GmbH offers to solve customer requests by molecular modeling.

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individual steps of leather making. It could be shown that new surfactants based on a C10 alcohol are an ecologically and economically viable replacement for APEOs. Carbon dioxide has potential as a substitute for the currently most utilized drycleaning solvent, perchloroethylene. The limited solvency of CO2 for polar molecules can be overcome by the addition of miscible surfactants such as alcohols, polysiloxanes and alcohol ethoxylates. Most of the water-based knowledge on nonionics can be transferred to the CO2based systems using the newly developed HCB concept the hydrophilic CO2philic balance. Multivariate data analysis enables the prediction of adjuvant performance from the surfactant properties. Industrial processes are becoming faster and faster. Fast diffusion of amphiphiles to interfaces and the formation of interfacial films to lower the interfacial energy are the fundamental molecular mechanisms which have to be optimized for all high-speed spraying and wetting processes. Processes in which new interface is generated in fractions of a second are significantly influenced by the dynamic behavior of the surfactants involved. Thus, the dynamic properties of surfactants play a more and more important role for a profound understanding of their industrial application. An important example is the flotation de-inking in the recycling of waste paper. A higher level of process quality control can be achieved by the in-line analysis of surfactant properties. This was shown in a metal cleaning process. Surfactant molecules have long been used for surface modification in order to invoke hydrophobic surfaces, e.g. in flotation, or hydrophilic surfaces, such as in the stabilization of dispersions. In this context, surfactants play an important role in the textile industry, especially in the production and processing of fibers. Polyampholytes are shown to be suitable for the surface modification of fiber-reinforced plastics. Polymeric dispersants or surface-active polymers can be prepared by grafting hydrophobic chains to a hydrophilic backbone, grafting hydrophilic chains to a hydrophobic backbone, and alternating hydrophilic and hydrophobic seg-

L.U.M. GmbH at CESIO 2004

L.U.M. GmbH Berlin Specialist for rapid and efficient characterization of concentrated dispersions and manufacturer of analytical instruments for dispersions analysis draw a favorable balance of their participation in the CESIO conference and exhibition. At the exhibition L.U.M. GmbH presented its newest generation of dispersion analysers the Complete Dispersion Laboratory LUMiSizer. This new device enables the characterization of stability of dispersions (emulsions, suspensions), their particle size as well as the evaluation of the efficiency of dispersants, emulsifiers, flocculants and demulsifiers by multisample analytical centrifugation (12 samples simultaneously). L.U.M. GmbH used the opportunity to contact potential new customers and discuss with specialists from all over the world new methods and options to solve their current problems. During the conference program L.U.M. presented a paper entitled Rapid emulsifier selection and evaluation of emulsion stability by analytical centrifugation in the Industrial Applications Section. A poster demonstrated the efficiency of multisample analytical centrifugation for selection of additives, their optimum concentration and composition with examples of carbon black dispersions, lime dispersions and emulsification.
(1) www.lum-gmbh.com (2) www.AppliedColloidsSurfactants.info/1_1.html (3) T. Sobisch, D. Lerche, 2004 http://preprint.chemweb.com/chemeng/0405001

ments in the chain. Phenomenological results in their application were correlated to fundamental parameters such as contact angle, interfacial tension and work of cohesion. Coating additives normally do not trigger new developments in coatings but they can be the crucial factor in making a new and innovative coating system successful in the market. Other examples for surface modifications are glass fiber sizing and the anticorrosion properties of gemini surfactants in the , -alkanediyl dimethyl alkyl ammonium bromide series. Nanostructured Surfaces

New Cleaners Wanted

In his Plenary Lecture New Surfactant Structures: The Key for Chemical Nanotechnology and New Processes M. Antonietti, Max Planck Institute of Colloids and Interfaces, Golm, Germany, stated that with its key role in chemical technology and biology, we regard the han-

dling of surfaces with appropriate molecules for all purposes as key know-how for the next generation of colloid chemical experiments and products. It was shown that new surfactant structures carry the promise to expand the performance profile of nowaday surfactants to handle also more critical surface stabilization problems, e.g. the efficient stabilization of very large surfaces or the closure of the cohesion energy gap by multipolarity and adaptive construction. It is with good reason foreseeable, Antonietti concluded, that such surfactants will allow to shape new world scale applications, such as nutrition, building materials, nanocomposites, insulating nanofoams, or in the redesign of pharmaceutical actives. Chemical nanotechnology is deep down based on the handling of interfaces, and surfactant science will have its significant share. One of the first products the customer came into contact with nanotechnology were easy-to-clean-coatings on glass and sanitary ware. In the last years, most companies offered these easy-to-clean-

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coatings only on demand, but since 2003 some companies have started to deliver first series with functional coatings. These nanotechnology-enhanced products have begun to revolutionize the cleaning behavior of people. Self-arranging coatings consisting of modified nano-silica stick extremely well on glass and ceramics but offer at the same time an almost 100% anti-stick surface against water, grease or soil. The consequence of this trend is that the paradigms in the detergent industry must shift, because new surfaces which need to be cleaned and taken care of also mean new requirements for the cleaners, new problems and new products. The priorities of the cleaner of the future could rather be to preserve and to support the coated surface than simply to remove soil. Today, in many cases the cleaner compositions are not suitable for cleaning coated surfaces, because they either do not wet the surface properly, are mechanically and chemically too aggressive or lead to residues which affect the function of the coating. In the sanitary and glass ware business the hydrophilic and the hydrophobic approach for easy-to-clean surfaces compete with each other. It does not matter which coating principle will finally make it in the market. The key point is that nanotechnology begins to change the customers desire for an intelligent cleaner into a desire for an intelligent surface. A very interesting field in the future will be the combination of detergents and nanostructures. Nanogate is currently developing cleaner compositions, which during cleaning render the cleaned surface either water-repellent or hydrophilic. Moreover, these cleaners can also be used to coat originally uncoated surfaces with a semi-permanent hydrophilic or hydrophobic easy-to-clean effect which lasts for some months. Molecular modeling simulations were used as a novel technique to characterize nanostructures. Surface-modified aluminas serve as organic nanodispersions. From Closed Loop Cleaning to

Two Weaknesses of Traditional Surfactants in the Context of Nano-Operations Wrong polarity design: Most surfactants show something which is called the cohesion energy gap, that is they are composed of a very polar and a quite unpolar moiety only. This implies that many surfaces and molecules cannot be appropriately addressed, as they find no counterpart in the molecular structures. In addition, self-adjustment to the surface is impossible due to molecular layout. Wrong geometry design: For Nano, a layer thickness of 3 nm to be effective is an incredible waste of material. Model experiments with target structures indicate that the same job can be done with 0.3 nm thickness, that is a tenth of surfactant load. Possible solutions: Biomimetic approach with flat stiff structures (cholic acid systems, saponines, deferoxamines, or didepsides), or short polymeric structures as stabilizers (proteins, oligosaccharides), double hydrophilic copolymers, hydrophilic-biophilic stabilization or chimera polymers. (According to M. Antonietti)

presented. One of them was the increasing legislative, customer and consumer pressure on the formulator of Retailer Brand Cleaning Products. From this side it is perceived that the strength and depth of these constraints are not fully understood by base raw material manufacturers. This increasingly difficult environment makes it a necessity that manufacturers and formulators find bet-

ter ways of working together. A closed loop cleaning process with both water and chemical (detergent) reuse was presented. A preliminary analysis of the different formulations used indicated that an all-nonionic formulation may be best suited to this recycling process. For the sustainable central processing of home laundry which is of great interest also in developing countries with large

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Tel: +9 63 -11- 6 94 09 40, Fax: +9 63 -11- 6 94 01 01 Please contact Marketing dept:

Wellness Activities
In the Household, I&I and Personal Care Section D a broad spectrum of topics was

Stephen.sweid@ujscpi.com Direct Tel: +9 63 -11-6 9410 83 Kinda.elias@ujscpi.com Direct Tel: +9 63 -11-6 9410 80

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urban population centers a microfiltration process was proposed. This step is key to effectively removing contaminants from the water while allowing some reuse of detergent ingredients. Although methyl ester sulfonates (MES) have been manufactured since 1991 this surfactant has not gained widespread use because of some technical issues arising in MES application to laundry powder detergent. Recently, a novel sulfonation process for C16/C18 methyl ester sulfonate from palm oils and some types of easy-to-handle delivery forms were developed. With the emergence of hydrophobe branching one should pay attention to the surfactant performance as a function of this branching. In this context detergent alcohols ranging from 99% linear to 99% branched have been evaluated. Hydrophobe branching dramatically affects foaming, leading to reduced performance in dishwashing as branching increases. A similar effect has been observed in liquid hand-soap formulations. Fabric detergency is improved by increasing branching, since the branched surfactants are more soluble than the essentially linear homologs. Textiles play an important role in providing us with holistic feeling of well-being. They protect us like a second skin from harmful external influences like sunshine and rain, they regulate our temperature and moisture balance, and they decorate our body, thus imparting additional beauty and attractiveness and pampering us with tactile stimuli. The senses which are most activated when perceiving textiles are of course vision and tactile feel. As a consequence, a tailor-made sensory assesment has been developed for spray and softener applications, which is focused on optical and haptic parameters. Furthermore, for objectively measuring emotional states of mind via psycho-physiological parameters the so-called Objective Emotional Assessment (OEA) has been developed. Beside key benefits derived from silicones such as thread lubrication and fabric softening, more recently, there are attempts to translate more of the known textile industry technology into consumer laundry benefits. Examples are improvements in fabric dewatering, fabric

Table 3 Classification of the Industrial and Institutional (I&I) market by business sector and application (Source: G. Clark, Johnson Diversey).

elasticity, shape retention and perfume release. The exploitation of these technologies is applicable primarily in fabric conditioners but development of innovative and cost effective solutions for powder and liquid detergent applications is a logical and important extension. Zinc ricinoleate is a powerful means for complexing nucleophilic malodor molecules. The results of molecular modeling have led to the development of a zinc ricinoleate-arginine blend with added benefits such as water solubility and low stain risk. A classification of the Industrial and Institutional (I&I) market by business sector and application area is given in Table 3. On a global scale, one can identify the following trends:

companies attempt to benefit from the synergies of centralized operations.

Increased awareness towards food safety, emerging diseases and bio-terrorism. An aging population requiring safe health care and an increase in the number of long-term care facilities.

An increased need for greater productivity and operational efficiency. The requirement for greater productivity demands fool-proof, extremely simple and low- or no-maintenance cleaning and sanitation systems. Migration towards global account management. In the area of food services, central kitchens are rapidly proliferating as

The challenges facing the I&I industry require an intimate collaboration between the I&I customer, the I&I companies and the chemical industry. A new approach to formulate cleaning products with microemulsions was presented as well as tests for optimizing products and formulations with lowfoaming surfactants as rinse aids.

Personal Care The CESIO papers in the field of personal care covered expectations and innovations in surfactants for personal products, the application of new surfactants cited above, dermatological and toxicological aspects as well as application technologies in, for instance, skin care.

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The addition of the mild co-surfactant sodium cocoyl glutamate (SCG) to sodium laureth sulfate (SLES) containing daily shower products resulted in a significant reduction of SLES adsorption on human skin which improves skin care. SCG itself adsorbed only in neglible amounts on the skin from SLES/SCG mixtures. Multifunctional building blocks have proven in gemini surfactant application for personal care and beyond. Sodium dicocoylethylenediamine PEG-15 sulfate is Sasols example of a well-balanced gemini surfactant as key component in highly flexible building blocks an emulsifier/dispersant (CLH) with behenyl alcohol, and glyceryl stearate citrate,

and an cleansing/dispersant building block (CLF) with sodium lauroyl lactylate. The next innovation step can be summarized under the heading easy processing (room temperature, no homogenization) an emulsion concentrate that can be filled with any oil and becomes selfemulsifying. The latest version is an even more flexible concentrate which allows the use of any oil and forms highly stable nano-emulsions. Since the paradigma of absolutely linear fatty alcohols and their derivatives for cosmetic application has been overcome it could be shown that carefully selected oxo alcohols and their derivatives are suitable also in this area.

Structured surfactant formulations (SSF) have been utilized for almost twenty years in many different products, applications and markets. The main feature of these systems has been their ability to suspend insoluble, functional particulates, thus preventing their sedimentation in mobile liquid formulations. Traditional SSF systems comprise surfactants that form close-packed lamellar or spherulitic structures in the presence of electrolytes. Recent advances include non-aqueous structured systems capable of suspending water-sensitive materials such as peroxygen bleach and activators, electrolyte-free structured systems for potential pharmaceutical appli-

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cations, and sugar-structured surfactant systems which form clear gels with excellent suspending properties and enhanced visual effects. The design of new surfactant packages for skin care products enables the improvement of enhanced water resistance of sunscreen formulations, segregation of active ingredients in multiple emulsions, less irritating cleansing products and lighter feeling oil continuous creams and lotions. Numerous thickeners are available to cosmetic formulators in order to enhance the viscosity of foaming cosmetic products going from classical hydrocolloids to polymeric high molecular weight (MW) surfactants and low MW nonionics or diethanolamine free alkanolamides. Although there are so many raw materials to choose from, the direct replacement of the well-proven Cocamide DEA remains a difficult task. In a comparative study the superiority of an alternative from point of view of workability and viscosity build-up performance in a formulation could be shown: an easy-tohandle liquid product based on Cocamide MIPA and Laureth-4 that gives a similar viscosity profile as Cocamide DEA at all tested conditions. Environment, Toxicology,

Regulatory Affairs
In the focus of the Section E (Environment, Toxicology and Regulatory Affairs) were Product Stewardship, the new Chemicals Policy (REACH), Risk Assessment of Surfactants, the new EU Detergents Regulation, and Environmental Properties of Surfactants. Coordinated measures of industry and authorities have proven as a successful alternative to administrative regulations. The instrument of regulation is essential for basic demands such as the biodegradability of surfactants. Agreements generally allow a faster implementation, are easier to modify and enable the involvement of stakeholders according to their importance for the area to be ruled. Beside regulations and agreements the German Cosmetic, Toiletry, Perfumery and Detergent Association (IKW) resorted to the instrument of recommendations

to lay down rules on environment-related advertisements. A recommendation offers an adequate scope for estabishing a code of conduct, which is factually wellfounded and ethically postulated. As a case study of the evaluating surfactants based on their impact on the environment the so-called Greenlist process of SC Johnson & Son was analyzed. This process has stimulated innovation with more sustainable product design by providing information, training and motivation. The EC sponsored OMNIITOX (Operational Models and Information Tools for Industrial Application of Ecotoxicological Impact Assessments) detergent case study revealed that different LCIA (Life Cycle Impact Assessment) methods result in different product rankings regarding potential impacts on aquatic ecotoxicity. Therefore, the challenge for OMNIITOX is to develop an agreed method, which overcomes the situation of diverging results. The Japan Surfactant Industry Association (JSIA) has just started a new program named SRA (Surfactant Initial Risk Assessment) plan to arrange the already gained information for the full range of surfactants. JSIA considers the exchange of experiences worldwide very important for sustainable development. It is well-known that in October 2003 the European Commission adopted a proposal for a European Parliament and Council regulation on the Registration, Evaluation, Authorisation and Restrictions of Chemicals (REACH). According to this proposal the industry would be obliged to register all marketed chemicals above 1 ton annually within 11 years following the entering into force of the new regulation. A minimum data set would be required for chemicals between 1 and 10 tons and additional information the extent depending on the tonnage would have to be provided for chemicals exceeding 10, 100 and 1000 tons. Above 10 tons, industry would have to draw up a Chemical Safety Report which includes a risk assessment. The results of this assessment would have to forward to the down stream users transformed in the traditional Data Safety Sheet in order to enable them to meet their responsibilities. If implemented in its current form REACH will have a highly negative eco-

nomic impact on the entire economy in the EU. This was stressed in Plenary Lectures as well as in contributions of VCI officials. In particular, supply chains which rely on specialized products such as surfactants for specific applications will be affected. From the VCIs point of view the following steps are necessary in the legislative procedure to achieve a balanced and workable regulation:

Impacts of the proposed provisions in particular on the competitiveness of the European industry, on ecomnomic growth, employment and innovation must be examined thoroughly by a neutral party before the proposal for a Regulation goes into the final phase of the legislative procedure. The workability of the REACH system and efficiency of its procedures must be fully examined and tried out by companies and public authorities. This should be done in Europe-wide pilot projects jointly with the Commission, competent national authorities and the concerned companies.

As to comprehensive risk assessments and targeted risk assessments the data requirements may differ another driver to foster international cooperation. A good example for international safety assessments is the LAS product chain (Table 4). A key conclusion from this activity is that there is an extensive database of information on these materials, and overall the data and 35 years of safe use demonstrate low concern (little risk) for potential health or environmental effects. Although no risks associated with the use of LAS have been found, LAS is still discriminated by criteria for ecolabelling. Furthermore, the causative agent for much environmental damage has been often rashly and erroneously attributed to surfactants and their degradation metabolites present in the aquatic environment, sludge, sediment or seawater. In spite of the fact that the industry has carried out a lot of research work and risk assessments addressing the various envi-

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ronmental compartments, surfactants have remained the subject of attention due to a combination of their inherent environmental properties, their strong presence in consumer products and their large production volume. Bioconcentration factors increase with increasing hydrophobicity. Considering the hydrophobicity dependence of the uptake rate constants as well as the surfactants propensity to biotransformation is a viable (and currently explored) option for providing a realistic estimate of the bioconcentration potential of surfactants in the environment. The risk assessment activities related to amine oxides are a good example for the growing international cooperation between the US, Japan, and Europe in this field. Another example for working within a consortium and extensively exchanging information within value chain is the development of risk assessments for the family of alcohol-based surfactants (ERASM/HERA/HPV initiatives). The new EU Detergents Regulation modernizes the EU legislation in two important respects. First, it replaces the earlier tests for primary biodegradability with tests for ultimate biodegradability and extends the scope of the legislation to all types of surfactant. Second, it introduces labelling requirements for detergents for the protection of human health and of the environment. A number of open issues have been identified in the Regulation with deadlines for their resolution. One of these issues is the anaerobic biodegradability of surfactants. A study on this subject has been carried out for the Commission by the Fraunhofer Institute for Environmental, Safety and Energy Technology UMSICHT. A decision on whether to proceed to a legislative proposal will be made following evaluation of the report by the appropriate Commission Scientific Committee. Any such legislative proposal must be made within five years of the date of publication of the Regulation. An ERASM (AISE-CESIO) Expert Panel concluded in 1999 that anaerobic biodegradabilty does not have the same environmental relevance as aerobic biodegradability and should not be used as a pass/fail property for the environmental acceptability of surfactants

Institution or Initiative International Council of Chemical Associations High Production Volume (HPV) assessment and the OECD Screening Information Data Set (SIDS) programs

Products included benzene, linear alkylbenzene (LAB), LAB alkylate bottoms, LAS, paraffins LAB sulfonic acids, LAS-related materials LAS

US Environmental Protection Agency (EPA) HPV assessment program AISE-CESIO Health and Environmental Risk Assessment (HERA) of detergent ingredients in Europe

Table 4 International safety assessments of the LAS product chain.

which are readily biodegradable under aerobic conditions. Key findings since the ERASM report confirm this conclusion. Data from the literature are not appropriate to predict the ultimate biodegradability of surfactants today. Particularly in the case of polymeric surfactants several parameters many more than in the past may be varied and adapted to finally combine high performance with ultimate biodegradability. EO/PO block copolymers are known to fail primary biodegradation requirements and also ready biodegradation tests of the OECD 301 series. Therefore, they have increasingly replaced in detergent formulations. New data surprisingly shows that polypropylene glycols (PPGs) with molecular weights up to 2500 do fulfill the criteria for ready biodegradability. As a result, a number of EO/PO block copolymers with varying compositions and molecular weights have been retested and, like the PPGs, passed the criteria. There is no proven explanation for this phenomenon. Actual theories focus on adaptation of the microorganisms that has been facilitated by an increasing exposure to structurally related chemical compounds in the aquatic environment over a prolonged period of time. Metabolic studies enable ready biodegradability classification of classes of fatty amine derivatives characterized by hydrophilic moiety. Ecotoxicity studies on the nematode, C. elegans, have shown that the cationic exchange capacity of sediments reduces cationic surfactant

toxicity. Field studies on the adsorption/ desorption of LAS in agricultural soils revealed that LAS leaching was limited only to the first few cm layer of the soil. 7th World Surfactants Congress For the second time, the next World Surfactants Congress will take place in Paris from June 21 to 25, 2008.

References
(1) H.G. Hauthal, A New Anionic Surfactant Alkyl Polyglucoside Carboxylate, SFW Journal 2004, English version, 130 (9), 86, 88); (2) K. Booten, B. Levecke, Polymeric, carbohydratebased surfactants and their use in personal care applications, SFW Journal 2004, English version, 130 (8), 10-16

*Authors address: Prof. Dr. Hermann G. Hauthal Rosenstrasse 20 06237 Leuna Germany Email: HGHauthal@t-online.de

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