COVER STORY
WASH DAY Laundry detergent makers say they test products for effectiveness as well as environmental impact.
GOING GREEN Pushed by Wal-Mart, legislators, and the public, the CLEANING PRODUCTS industry embraces sustainability MICHAEL MCCOY, C&EN NORTHEAST NEWS BUREAU
ONE WOULD NOT EXPECT a Procter & Gamble laundry detergent to share advertising space in the New York Times Magazine with expensive watches and designer clothing. But this is not just any detergent; it's an environmentally friendly one. Over the past year, the environmental impact of consumer products has gone from being a fringe issue raised mainly by activist groups to a mainstream concern confronted by P&G, Wal-Mart Stores, General Electric, and other marquee names of corporate America. The leaders of these companies no doubt have a genuine desire to improve the environmental profile of their products. But they also know green sells, and firms perceived as being kind to the environment look as good to the wellheeled readers of upscale magazines as they do to the investment community. Because laundry detergents are bought in large volumes, mixed with water, and sent down the drain, they have been front
and center in the environmental discussion. Raw materials are being scrutinized and in some cases phased out. Suppliers are being asked to come up with new, more environmentally sound ingredients to help consumer goods companies head off scrutiny or present a greener product lineup. The P&G ad, for Tide Coldwater, is aimed at an environmentally conscious audience. It points out that if everyone in New York City washed laundry in cold water for just one day, the energy saved would be enough to light the Empire State Building for an entire month. It then suggests that Tide Coldwater, introduced in early 2005, can help accomplish this goal. P&G is the world's largest laundry detergent company, and when it speaks, suppliers of surfactants and other raw materials listen. Thus, for Tide Coldwater, P&G's surfactant suppliers designed a hydrophobic surfactant system that solubilizes oily soils in cold water. And its enzymes suppli-
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ers developed proteases and carbohydrases that are effective on insoluble dirt residues in cold water. In turn, P&G and other consumer product companies must heed Wal-Mart, which has the second highest annual sales of any publicly traded company in the world. And Wal-Mart spoke loudly last fall when it announced two environmental initiatives that could profoundly affect cleaning products. In September, at the Clinton Global Initiative in New York City, Wal-Mart launched a plan to measure its 60,000 worldwide suppliers on their ability to reduce packaging. It calculates that the plan will annually save 323,000 tons of coal and 67 million gal of diesel fuel from being burned. And it will keep some 677,000 tons of carbon dioxide out of the atmosphere. Then in October, the company started a program to encourage the use of "preferred" ingredients in detergents and other
COVER STORY
chemical-intensive products. Wal-Mart said it would work with suppliers to substitute 20 "chemicals of concern" over the following two years. It announced the first three chemicals in October, one of which was nonylphenol ethoxylates, or NPEs, a surfactant class found in many cleaning products. Wal-Mart's initiatives came at a time when cleaning product makers and their raw material suppliers were already reeling from a string of initiatives that are changing the way they develop their products. These include the European Union's detergents directive and its REACH chemical regulation plan, the Environmental Protection Agency's Design for the Environment program, and a state-level ban of phosphates in automatic dishwashing detergents. But Wal-Mart's size and direct influence on the industry give its two initiatives a particular impact. And because it is a private company, Wal-Mart can immediately present its changes to suppliers and consumers without the deliberative process that government agencies must follow. "The retailers are one step closer to the consumer and can, as Wal-Mart has proven this year, have a dramatic influence on consumer perception," says Kevin Beairsto, business manager for fabric and home care at National Starch & Chemical's Alco Chemical division. "Removal offillersand other chemicals due to packaging and environmental concerns poses formulation challenges to detergent manufacturers and ultimately to us as ingredient suppliers." Corporate rather than government scrutiny of d chemical ingredients is a * potentially game-changing development for cleaning product companies. "Corporations, such as the retailers, like to move fast," points out Ernie Rosenberg, president of the Soap 8c Detergent Association, the main trade group for the U.S. cleaning products industry. "A deliberative process with stakeholder participation doesn't give you a fast process."
road, but for consumer products, that may be irrelevant." NPEs provide an instructive example of how listing, even in the absence of government action, catalyzes change. The surfactants also demonstrate how an unwanted development for one company or product is a business opportunity for other companies and products. NPEs and other alkylphenol ethoxylates (APEs) have long been under scrutiny. According to a Sierra Club report published in November 2005, they are unlike any other cleaning agent because they break down into more toxic, less biodegradable metabolites that display estrogenic properties, such as nonylphenol itself. The APE Research Council, an industry group, contends they are safe. Thomas Stephens, global business manager for cleaning and care at Dutch chemical maker Akzo Nobel, notes that Europe effectively banned NPEs in the 1990s for all down-the-drain applications. No legal prohibitions exist in the U.S., but EPA's Design for the Environment program recognizes companies that voluntarily phase out the manufacture and use of NPEs. Not surprisingly, they have been on the decline. A recent Consumer Reports study concluded that no major U.S. brand of laundry detergent contains NPEs. Sharon J. Mitchell, vice president of R&D for P&G's global fabric care business, says her company has never formulated fabric and home care products with NPEs, "as we realizedfromthe beginning that these chemicals could not be supported for safety at the volumes that would be required." In institutional cleaning products, where NPEs have persisted, key player JohnsonDiversey announced last summer that it would eliminate them by the end of 2006. Yet, according to the Sierra Club report, more than 260 million lb of NPEs were consumed in the U.S. alone in 2004, and observers say they are heavily used in Asia for textile processing and other applicaLIKE THEM or not, lists such as Wal-Mart's tions. Companies such as Dow Chemical, Huntsman Corp., and Rhodia say they are 20 chemicals of concern, in Rosenberg's view, could prove to be more important safe and continue to manufacture them. arbiters of the chemical industry's product "Wal-Mart's going to do what Wal-Mart's lineup than any traditional regulation. going to do," says David Parkin, Hunts"Once it's on a list, public pressure and man's vice president for intermediates. "We retailer pressure is what hits the chemical," still believe NPEs are an effective cleanhe says. "It may get regulated down the ing agent and will provide them." At the WWW.CEN-0NLINE.ORG
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PERCEPTIVE Eunjoo same time, Parkin Kim, a chemist in acknowledges that Degussa's Hopewell, some companies Va., laboratories, are shunning them, evaluates softness and he says Hunts- and fragrance retention benefits of man is prepared to ingredients offered assist them with by the company. replacements such as methyl ester ethoxylates and blends of alcohol ethoxylates and ethanolamines. In fact, while it continues to produce a chemical that concerns the likes of Wal-Mart and P&G, Huntsman last year launched a business unit charged with enhancing its practice of green chemistry that reduces the use or generation of hazardous products. For cleaning products, Parkin says Huntsman is investigating the manufacture of propylene glycol from natural glycerin. It is using a new catalyst to combine palm-kernel-derived methyl esters and ethylene oxide to produce methyl ester ethoxylates with strong performance in cleaning applications. "We are about providing flexibility to our customers," he says. "Although we have a good capability to develop green chemistries, there is a large market of NPE users that continue to see them as effective cleansers." Rhodia, another NPE producer, has been researching NPE alternatives for the past five years, according to Pascal Metivier, vice president for innovation and technology at thefirm'sNovacare unit. 'We systemati-
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COVER STORY
cally try to pursue replacements," he says. "But ultimately, the customer decides." In the agrochemical market, where surfactants are used as emulsifiers and wetting agents, Rhodia has completely replaced NPEs with blends of other surfactants, Metivier says. Sales to detergents and other industries continue to fall, he notes, but some
NEW FORMULA The reemergence of highly concentrated detergents poses formulation challenges for ingredients suppliers. ^ ^ ^ ^ ^
hang on to them because they are . J , inexpensive and effective. "Replacing NPEs is easy. Replacing NPEs at the same cost is not," he says. At Akzo Nobel, which also produces NPEs, Stephens says the company is developing replacements by drawing on its experience in Europe. "We have gone through the trial and error of what works and doesn't work," he says. NPEs contain nonylphenol, a hydrophobe that is attracted to oily materials, and ethylene oxide, a water-loving appendage that keeps the molecule in solution. Although the cleaning products industry's initial direction in NPE replacement was toward linear alcohol hydrophobes, Stephens says Akzo has found branched hydrophobes to be effective without the excessive foaming often associated with linear alcohols when they are ethoxylated. A new narrow-range ethoxylation technology also lowers foaming in both linear and branched products, he adds. While NPEs are on the wane in the U.S. mostly due to corporate initiatives, phosphate builders for automatic dishwashing (ADW) detergents are under pressure from good old-fashioned government action. Phosphates provide several functions in detergents, including hard-water neu-
tralization, redeposition prevention, and buffering. But concerns about phosphorus-induced eutrophication in lakes and rivers led to a series of state-level bans in the 1990s that took phosphates out of most U.S. laundry detergents. ADW products were spared, though, and today many of them contain 4-8% phosphorus. The State of Washington revoked that reprieve last June with the passage of an ADW phosphate ban intended to protect the Spokane River. It will go into effect on July 1,2008, in three counties said to have phosphate problems and in 2010 in the rest of the state. Whereas laundry detergent phosphates were replaced with citrates, zeolites, and other builders without major cost and performance compromises, detergent makers contend that phosphates are key to dishwasher detergent performance and that their absence will be noticed by consumers. Thomas Muller-Kirschbaum, senior vice president for R8cD, technology, and supply chain with HenkePs laundry and home care business, says Henkel launched a phosphate-free ADW product in Germany about 10 years ago.' We lost market leadership and had to go back to phosphates to take the lead again," he says. U.S. ADW detergent makers surely don't relish the prospect of coming up with a separate formula for Washington state or, worse, watching the ban spread throughout the West and across the country. Some specialty chemical companies, though, see the ban as a business opportunity whose arrival was inevitable. "We have been telling people for some time that you can take phosphates out of ADW products and get comparable performance," says Nilesh Shah, global research director for process chemicals and biocides at Rohm and Haas. According to Shah, effective phosphate replacement technology had been languishing on Rohm and Haas's laboratory shelves until the Washington state ban emerged. At its heart is Acusol 425N, a water-soluble acrylic polymer that, the company says, can
remove food soil and keep it dispersed while controlling the deposition of carbonate scale on glassware and utensils. At Alco, another specialty polymer supplier, Beairsto sees both pros and cons in an ADW phosphate ban. On the one hand, a number of Alco's polymers are used in current ADW formulas to prevent the filming caused by calcium phosphate scale. But Beairsto isn't surprised by the ban and, like Shah, says Alco has had zero-phosphate ADW projects under way for several years now. "We have developed several technologies that can help mitigate the negative effects of the removal of phosphates," he says. At the specialty chemical company Croda, which acquired the surfactants maker Uniqema last September, Sales Development Manager Rob Pifer points to the Synperonic NCA series of alkoxylated copolymers, detergent boosters that allow formulators to reduce or remove the need for builders. Initially developed for the European market, the series complies with the new European Detergents Directive mandating surfactant biodegradability, he says. Like NPEs, phosphates are effective cleaning agents unlikely to be replaced by a single ingredient. But the right combination can address ecological and toxicological concerns and still achieve the necessary functional properties, according to Tony Latella, detergents sales director in North America for BASF's performance chemicals business. He says a blend containing BASF's Trilon biodegradable chelating agent, Plurafac surfactants, and Sokalan polymers can "actually add utility and help boost product performance compared to many phosphates." Chemical companies are also positioning their ingredients to replace formaldehyde releasers, solvents, and other cleaning product components that may not be regulated but are seen as undesirable just the same. Shah says Rohm and Haas isothiazolone biocides are gaining as replacements for formaldehyde-releasing biocides such as dimethyl dimethylol hydantoin and i-(3-
Environment-oriented requests by customers have become a new part of the customer-supplier relationship. WWW.CEN-0NLINE.ORG
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chloroallyl)-3,5?7-tnaza-i-azoniaadamantane chloride, also called quaternium 15. Among solvents, one target is ethylene glycol butyl ether, a solvent commonly found in spray cleaners. Although EPA took EGBE off its list of Glean Air Act-regulated pollutants in 2004, it is still considered a volatile organic compound by the influential California Air Resources Board. According to Akzo Nobel's Stephens, 1% of the company's Berol 226, a blend containing nonionic and cationic surfactants can replace the EGBE and NPE that are in many spray cleaners. One big U.S. brand made the switch in the 1990s, he says, reducing VOC emissions and increasing the product's ability to emulsify and remove gritty particulate matter. "It's one of those rare times we have shown we can do the job better for less money," he says. ALTHOUGH BANS and regulations are real events with real repercussions, cleaning industry players insist they aren't merely being reactive. From cold-water formulas to new concentrated detergents to ingredients that come from renewable
resources, fabric care companies and their raw material suppliers are trying to make sustainable products that satisfy the public's new environmental sensibility. "We work with suppliers to ensure that all new raw materials meet stringent P&G safety criteria," says Mitchell, the P&G vice president. "P&G safety scientists are involved in this process right from the beginning, sometimes even before the actual materials are synthesized." Above and beyond basic safety, Mitchell says, P&G often uses a "life-cycle assessment" tool to determine the water, packaging, and energy consumption associated with its products. New products that have benefited from this tool include Tide Coldwater, a single-rinse Downy fabric softener, and compact laundry detergents soon to be available in North America. The company advises Wal-Mart on the retailer's sustainability initiative, Mitchell adds, and is in its Chemical-Intensive Products Network. P&G even backs particular ingredients to help it reach environmental goals. For years, Mitchell says, the company has worked with leading enzymes suppliers to develop en-
zymes that enable it to use less surfactants and other chemicals. "We are also increasing the level of naturally based surfactants in our products," she says, "using alcohols from natural oils to reduce the level of petrochemically based surfactants we use." P&G's competitors are flying the sustainability flag as well. Henkel, a European laundry detergent leader, was one of the first companies to recognize a poorly biodegrading ingredient some 50 years ago when it removed branched alkylbenzene surfactants from its detergent formulas, according to Muller-Kirschbaum. In the past decade, he adds, Henkel has removed suspect dyestuffs from its detergents, replacing them with food-grade and other more benign dyes. And although all detergent companies have their roots in natural soaps, MullerKirschbaum says Henkel has stayed more true to them than most. Today, about 35% of the surfactants it uses in laundry detergents and household products come from renewable resources, he explains. "We feel prepared to say to Wal-Mart that we are a benchmark in our industry, especially in the use of renewables."
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COVER STORY
Recent Henkel environmental initiatives in Europe include the launch last year of a new detergent, Persil Color, developed to work well at low temperatures. According to Muller-Kirschbaum, its effectiveness stems from a specially tailored stain-removal polymer, improved enzymes, and a reworked surfactant system.
Similarly, Henkel's latest ADW product, Somat 7, is formulated to clean as well at 40 °C as previous products did at 55 °C, for a 20% energy savings. Ingredient suppliers say environmentoriented requests by customers such as P&G and Henkel have become a new part of the customer-supplier relationship. Accord-
NATURAL VERSUS SYNTHETIC
Oleochemical And Petrochemical Makers Square Off Synthetic or natural, petrochemical or oleochemical: Which is better? It's a simple question but, clouded by rhetoric and hard-to-measure claims, one without an easy answer. The contentiousness of the topic came across clearly last October at the 6th World Conference on Detergents in Montreux, Switzerland, during a talk by M. C. Menon, vice president of marketing at Pan-Century Oleochemicals, a Malaysian producer of palm-oil-derived chemicals. Standing in front of an auditorium of cleaning products executives, Menon flatly stated that detergent alcohols derived from palm oil are more biodegradable than those from petroleum and that palm-oil-based surfactants will eventually drive synthetics out of the market. At a subsequent questionand-answer session, several conference attendees challenged his first claim, noting that numerous studies have shown raw material origin to have no impact on a product's biodegradability. But the exchange showed that makers of synthetic ingredients are on the defensive in a way their oleochemical competitors aren't. Speaking with C&EN after the talk, Rob van der Meij, Shell Chemicals'global business manager for alcohol and
alcohol derivatives, emphasized that Shell's ethylenebased Neodol alcohols meet all biodegradation standards. "There's a lot of media buzz about natural," he said. "But natural feedstocks go through steps such as esterification, hydrogenation, ethoxylation, and summation" before they are in a form suitable for use in consumer products. He also noted that the palm oil industry's environmental profile is not exactly squeaky clean. Rain forest destruction and orangutan habitat encroachment are endemic in Indonesia and Malaysia, the world's largest producers of palm oil. Retailers such as the British chain Morrisons have found it necessary to join the Roundtable on Sustainable Palm Oil to ensure that the palm oil used in their products is from verifiable, sustainable sources. Although renewables may be no panacea, chemical companies with the right raw materials access and chemistry know-how are promoting such products as preferred ingredients for cleaning product formulation. DuPont, for example, is now marketing Bio-PDO, the corn-sugar-derived propanediol it began producing last fall in a joint venture with the sugar refiner Tate & Lyle. In a press release an-
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ing to Rhodia's Metivier, customers have always been interested in reducing costs and gaining attributes that allow them to make new marketing claims. "What is new in the past two years is the very aggressive stance of customers on green issues," he says. In particular, ingredient suppliers are helping customers develop detergents that
nouncing the plant's opening, DuPont urged producers of detergents, cosmetics, and antifreeze that are using a synthetic glycol to "consider replacing it with our new renewable ingredient.'' Ann M. Wehner, vice president of sales and marketing for DuPont Tate & Lyle Bio Products, says customers in
the detergents and personal care industries are curious about this new ingredient although she doesn't have any big contracts to report yet. "We've had an awful lot of excitement from an awful lot of folks," she says. "For someone who's sold chemicals for years, it's a lot of fun to sell." Kevin Beairsto, business manager for fabric and home care at Alco Chemical, says the company has been drawing on the natural polymer capabilities of its parent company, National Starch & Chemical, to create "materials that are not only more biodegradable than petrochemicals but are also based on renewable resources." He adds that Alco is already
JANUARY 29, 2007
working with detergent industry customers to replace ingredients built on petroleum-based feedstocks. Even within the renewables arena, there can be a hierarchy of acceptability. Degussa has long produced cationic surfactants based on tallow. In a new wrinkle, says Dave Del Guercio, director of the firm's household care business in North America, the company is successfully marketing several vegetableoil-based catkmics to kosher and other customers seeking to avoid animal ingredients. "They are not always for mainstream marketers," he acknowledges. Indeed, outside of niche markets, it's not dear how important renewable raw materials are to consumer product companies. Last summer, the consulting firm Colin A. Houston & Associates completed a study on the battle between petroleum- and tropical-oil-based detergent alcohols. Almost all current alcohol investment is of the tropical variety, and the study predicted that tropical oils' share of the world market would rise from 61% in 2005 to at least 65% by 2010. Joel H. Houston, president of the consulting firm, figures that some companies are in fact eager to purchase a product with natural origins. But with petroleum prices high and prices for tropicaloil-based alcohols falling, to him the purchase decision is a simple matter of economics.
perform in cold water as well as traditional products. At the 6th World Conference on Detergents in Montreux, Switzerland, in October, Per Falholt, executive vice president for R&D at the enzymes producer Novozymes, made the case for cold-water washing using detergent enzymes. He described a life-cycle assessment of adding extra protease, lipase, and amylase enzymes to a laundry detergent while dropping the wash temperature from 40 °C to 30 °C. Wash performance improved by almost every measure, he reported, and the energy savings of making the change in Europe would be equivalent to the output of two major power plants. Falholt said Novozymes is now working on enzyme packages for washing at 20 °C. The energy-saving companions to lowtemperature detergents are highly concentrated products that answer Wal-Mart's call for less packaging. Unilever was thefirstbig detergent maker to hit the market, with its All Small & Mighty liquid, launched in February 2006. According to Unilever, a 32-oz bottle of the new All can wash as many loads of laundry as 100 oz of traditional detergent. Unilever says its annual manufacturing and shipping savings will amount to 500 million gal ofwater, 26 million gal of diesel, and 150 million lb of plastic. Concentrated detergents were rolled out in the U.S. about 15 years ago with limited success, and most of them disappeared. Patrick Cescau, Unilever's chief executive officer, told attendees at the Montreux detergents meeting that the company had been concerned the new attempt at concentrates might lead U.S. consumers to think they are getting less for their money. To combat this impression, Unilever formed a partnership with Wal-Mart under which the retailer agreed to promote the new All to increase consumer confidence and get sales moving. "You can nowfindAll Small 8c Mighty in supermarkets across the U.S.," Cescau said. In Europe, where powdered detergents prevail, dosages have been on the decline as well, to about half the volume prevalent in the early 1990s, notes HenkePs MullerKirschbaum. He adds that HenkePs Dial subsidiary in the U.S. has developed a concentrated version of its Purex liquid detergent that will appear on store shelves soon. Dave Del Guercio, director of Degussa's household care business in North America, points out that many ingredient suppliers developed concentrated detergent formulas during the market's earlier flirtation
with the format. In Degussa's case, the focus is on hard-surface cleaners and fabric softeners, where the company is a leading supplier of ester-type quaternary ammonium cationic surfactants. THE CHALLENGE of formulating concentrated cleaners is pretty straightforward, Croda's Pifer says: "How do you produce a heavy-duty product with less water in the formulation?" One of Croda's responses is Monateric 1188M, a low-toxicity additive that helps keep high-concentration formulas stable. One result of higher surfactant concentration in liquid detergents is increased viscosity, BASF's Latella notes. Depending on the surfactant phase, formulators may be faced with unfavorable rheology, or flow properties, especially when the liquid is being poured out of the bottle. Latella says BASF's nongelling Lutensol XL and XP nonionic surfactants can help address dissolution and stability problems associated with concentrated liquids. Rohm and Haas's Shah doesn't see formulation problems in household concentrates as much as in industrial cleaners that contain phosphates, carbonates, and other ingredients with limited solubility. "Stability becomes an issue and rheology modification can become necessary," he says. "You need to modify the liquid phase to make these cleaners work." Do consumers know or care about the changes the cleaning products industry is making to create more environmentally improved products? Will green detergents sell? On the one hand, detergentsfromthe self-proclaimed "nontoxic" household products maker Seventh Generation are starting to show up in mainstream supermarkets. Farther down the aisle, though, Unilever's All Small 8c Mighty bottles don't mention energy and product savings. The emphasis is on convenience, and interested consumers must go to the detergent's website to learn about the environmental benefits. Alco's Beairsto, for one, thinks consumer sentiment—or at least legislative sentiment—is moving toward more environmentally friendly products. "The real test of their conviction will come when consumers realize that the new products may either cost more or work less effectively than the products they currently use," he says. "Our challenge is to provide environmentally friendly technologies that deliver the benefits consumers have come to expect at a cost they are willing to pay." •
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WELL-STOCKED Choosing the right aroma chemical is a big part of effective fragrance delivery.
SPECIAL DELIVERY Getting fragrance onto clothes presents a challenge for DETERGENT COMPANIES and their suppliers MICHAEL MCCOY, C&EN NORTHEAST NEWS BUREAU
CLOTHES SHOULD SMELL GOOD after they are washed, yet cleaning a garment and keeping a fragrance on it usually are incompatible from the surfactant's perspective. As Kumar Vedantam, director of technology and applications at Givaudan Fragrances, explains, delivering fragrance to washed clothes faces a fundamental stumbling block. "In the cleaning process," he says, "what you want the product to do is remove oily and particulate soil that gets deposited on a substrate during use." Fragrances, however, are also typically oily materials. "You expect your product to remove one set of oils and deposit another," Vedantam says, "but the surfactant doesn't distinguish between them." Efforts to overcome this problem are yielding sophisticated solutions that belie how mundane laundry is. Take for example a paper published last July by researchers from Unilever and University College London's department of biochemical engineering, which described biotechnology befitting high-end drug discovery (Biotechnol. Bioeng. 2006,94,625). In the paper, the scientists describe a new, low-cost class of antibodies with affinity for one or more molecular surfaces. But rather than lay out use of these antibodies in drug delivery or therapeutics, the paper proposes adding them to detergent so they can deliver perfume to laundry in the wash.
Although the antibody work is by no means commercial, it shows the extent to which detergent companies such as Unilever are willing to go to coax fragrances and other active ingredients to deposit on the surface of clothing rather than disappear down the drain with the wash water. After all, consumers appreciate a pleasant-smelling bottle of detergent, but it's the scent of a washed and folded garment that leaves a lasting impression and creates a loyal customer. Targeted delivery of fragrance and other cleaning product ingredients is being pursued by four segments of the detergents industry: fragrance manufacturers, delivery technology specialists, specialty chemical companies, and consumer product makers. All are aware that their task is frustratingly quixotic. Michael Popplewell, vice president of delivery and material technology with International Flavors & Fragrances (IFF), puts the challenge this way: "You are trying to deliver a molecule with a process that's really designed to remove molecules." As if that wasn't enough, Popplewell notes a second challenge: After washing comes drying, often by heating, and fragrance molecules tend to evaporate along with the water. Faced with this pervasive loss of fragrance, the industry's first line of attack is to tailor the scent molecules themselves. WWW.CEN-0NLINE.ORG
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According to Popplewell, hydrophobic compounds are more likely to deposit on clothes than hydrophilic ones, because they are less likely to dissolve in the wash water. And high-molecular-weight molecules have the best chance of surviving the clothes dryer. But even with the most robust molecules, Vedantam notes, up to 90% of the fragrance added to a detergent can be lost during washing. Givaudan and its competitors combat this problem with proprietary fragrance molecules that possess what he calls high odor value. These molecules give off a scent that is discernible even at nanogram or microgram quantities, he says. Dallas Hetherington, business manager for encapsulation and delivery systems at Alco Chemical, a division of National Starch & Chemical, agrees that odiferous molecules offer a degree of effectiveness. "But you still lose a great deal of fragrance down the drain, which can get costly," he says. Plus, such an approach restricts the detergent formulator to a limited palette of aroma chemicals. Thus, the second line of attack is encapsulation, or some other form of molecular tethering, to control the delivery of fragrance to clothing. For IFF, the main weapon on this front is Celessence International, a British fragrance encapsulation company it acquired in 2003. Celessence's claim to fame is a controlled-release system that is applied to fabrics and other substrates at the textile mill or garment factory. Fragrance releases gradually over time as the products are used. For example, pillows marketed by the British retailer Marks & Spencer retain their vanilla or lavender and chamomile scent thanks to Celessence technology. SINCE 2003, Popplewell says, IFF and Celessence researchers have modified the system so it can be employed in rinse-off applications such as laundry detergents and fabric softeners. He says a customer has launched a laundry detergent incorporating the technology and that other applications are in the works. At Givaudan, in-house R&D efforts have yielded a number of encapsulation and other controlled-release technologies in recent years. In 2003, the company launched Granu-
COVER STORY
scent, an encapsulation technique that protects volatile fragrance materials in a dry environment and then releases them upon contact with moisture. Although its large particle size was designed for powdered laundry detergents, Granuscenfs biggest application has been in a completely different market that Vendantam wouldn't disclose. An older encapsulation technology, Permascent, is being used to protect fragrances in powdered detergents, he adds. Releasing fragrance from a liquid medium is trickier, Vedantam acknowledges, because soluble encapsulants can't be used. One Givaudan solution is a controlled-release system based on liquid crystals composed of water, fragrance oil, and surfactant that have properties halfway between a solid and a liquid. IN DEVELOPMENT for about six years and the subject of three patents, the crystals latch onto textiles in the wash, survive the drying process, and emerge to release their fragrance over time. Customer feedback has been positive, Vedantam says, and commercial launch is being readied. A second new delivery system from Givaudan is a family of pressure-activated microcapsules that release their scent from washed and dried garments in response to movement or friction. Vendantam says these materials are akin to the coacervation encapsulants used in carbonless paper and scratch-and-sniff magazine inserts. But because Givaudan designed them for laundry applications, they are able to withstand a high-pH environment and exposure to enzymes and bleaches. They have successfully completed consumer tests and are now in the scale-up phase, he adds. Although fragrance companies such as IFF and Givaudan seem to be pursuing controlled-release technology quite aggressively, Sam Shefer, vice president of Salvona Technologies, argues that they are not necessarily the best sources of such rarified know-how. Based in Dayton, N.J., Salvona is a specialist in developing and commercializing ingredient delivery systems for food, health care, consumer care, and fabric and household care. Early in his career, Shefer was a chemical engineering professor at Massachusetts Institute of Technology. He later worked for biomedical and consumer
HydroSal, that is aimed primarily at the personal care market but has fabric care applications as well, Shefer says. As he describes it, HydroSal starts with 100-nm polymeric spheres that can be infused with fragrance or other ingredients such as whitening or antibacterial agents. The nanospheres are then coated a with a 5-nm-thick polymeric layer to I provide encapsulation. 0 This polymer system stays intact in water or alcohol-based personal care and cleaning products and then on the target textile after it is dry. But when the system comes into contact with water or moisture a second time, the outer film swells and slowly releases the encapsulated ingredient, Shefer says. Like Salvona, several traditional specialty chemical companies also consider controlled release as a core competency. Alco and National Starch, for example, offer techniques of their own devising even as they continue to develop the Salvona portfolio, according to Alco's Hetherington. In fact, he says Alco has built upon the Salvona technologies with what he calls "new art" as part of an effort since last year to expand Alco's core competency of such TNI N M I KNOWS Research executive delivery systems development group. firms lies in perfumery. Veiahtaw smells This group also markets starch-based Plus, he suspects they are a tewei washed encapsulation technology developed ambivalent toward any with detergent by National Starch, such as dissolvtechnology that will allow eantaihinga customers to use less of Qivaudan fragrance able films that entrap cleaning ingredients in a dry film format. their products. "There is not much motivation to do International Specialty Products this," Shefer observes. (ISP) is also active in controlled-release technology, offering its homegrown In contrast, he says Salvona has received Microflex microemulsions, based on alkyl 15 controlled-release patents and has 80 pyrrolidone and vinyl pyrrolidone polymore pending. The company employs mers that deliver hydrophobic actives such 17 people to develop and manufacture as fragrances and biocides. its systems, which it sells in 16 countries At the same time, the company has worldwide. "To develop this technology expanded its controlled-release portfolio you need specialized people," he says. "It's with the acquisition of two European ena profession." capsulation experts. In 2004, ISP bought In 2003, Salvona licensed a package of Hallcrest, a British developer of water20 controlled-release technology patents soluble polymer-based encapsulants. Then to Imperial Chemical Industries and its last August, it purchased the consumer National Starch and Alco subsidiaries for products encapsulation business of the use in fabric care. Since then, the company German firm geniaLab and entered an aliihas come up with a new technology, called
product companies, including IFF; nine years ago, he helped found Salvona. Shefer says his review of controlled-release patent literature of the past five years found an unimpressive level of activity on the part of fragrance companies. He claims to be unsurprised by this rinding, as the
It's the scent of a washed and folded garment that leaves a lasting Impression and creates a loyal customer. WWW.CEN-0NLINE.ORG
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THALESNano
ance with geniaLab to develop new encapsulated products for the fabric care, personal care, and home care markets. Frank Fusiak, North American director of marketing and business development for ISP's performance chemicals business, points out that Hallcrest's coacervation technology is geared to delivering hydrophobic liquid ingredients, whereas geniaLab's JetCutter technology is aimed at delivering solids. Both Hallcrest and geniaLab, Fusiak says, made their names in the personal care market. Since the acquisitions, ISP has been expanding their reach into home and fabric care as well as industrial and institutional applications. "ISP's success," he says, "comes from its ability to bring technologies to businesses in which they are not normally found." Most cleaning product manufacturers depend on third-party technology for their specialized ingredient-delivery needs. However, a few giants such as Unilever, Henkel, and Procter & Gamble have their own internal development efforts as well. For example, P&G has developed specialized techniques to deliver fragrances and softening agents to fabrics and to enhance the "fragrance experience" of selected automatic dishwashing products, according to Sharon J. Mitchell, vice president of R&D for the company's global fabric care business. The company is exploring improved deposition of additional ingredients as well, she adds. Mitchell says P&G's Tide with Febreze, Tide Simple Pleasures, and Gain Joyful Expressions all employ "specific delivery technologies" to enhance fragrance. Although she won't disclose chemistry specifics, she outlines three steps to efficient fragrance delivery: a technology that is stable in liquid detergents, a perfume accord tuned to maximize the efficiency of the delivery technology, and a technology that gets the fragrance to the fabric in a form that will facilitate release at the appropriate time. Meanwhile at Henkel, Thomas Muller-Kirschbaum, senior vice president for R&D, technology, and supply chain for the laundry and home care business, says his researchers explore targeted delivery of everything from fragrances to enzymes to bleaches to special fabric care ingredients. And not just in laundry detergents, either. He points to Henkel's 1999 launch of an automatic dishwasher detergent that used a wax encapsulate to release a rinse aid when the water temperature reached about 60 °C. Since then, Henkel has developed a wider palette of technologies to release rinse aids, water softeners, and shine additives in its autodish products. FOR LAUNDRY PRODUCTS, one Henkel strategy is what MullerKirschbaum calls a precursor approach, in which a fragrance molecule is linked to an organic molecule for protection. In the laundering process, the two halves slowly split apart through hydrolysis or other means, thereby gradually releasing the fragrance. Precursor technology based on silicic acid esters that bear fragrance molecule appendages won Henkel's 2004 Research/Technology Invention award. The technology received its first patents about 10 years ago and is used today to deliver fragrance in Henkel products worldwide, Muller-Kirschbaum notes. The company since has developed second-generation molecules, he adds, and today is working on the third generation. Although Henkel has succeeded in developing commercially viable fragrance delivery technologies, Muller-Kirschbaum cautions that the company has by no means solved the problem. "We are in some ways ahead of where we were five years ago," he says, "but I think the whole industry has a way to go." • WWW.CEN-0NLINE.ORG
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ThalesNano's H-Cube™ The Next Generation in Hydrogenation
FEATURES The H-Cube™ represents the first in a new wave of continuousflow hydrogenation reactors. Utilising water electrolysis to generate hydrogen, a catalyst cartridge system (CarCart™) and a continuous-flow mechanism, the H-Cube makes hydrogenation safer, more efficient, and easier to perform. • • •
A continuous-flow of substrate is combined with hydrogen, generated in-situ through electrolysis of water The hydrogen/substrate mixture can be heated up to 100°C and pressurised up to 100 bar (1450 psi) The mixture is then passed through a packed catalyst cartridge (CatCart™) where the reaction takes place
Whithin two minutes, product emerges for fast reduction and optimisation. Reductions varying in scale from 10mg-100g can be performed on the same compact reactor. H-Cube™ is capable of hydrogenating a wide range of different functional groups, for example: • • • •
Nitro reductions Alkene and alkyne saturation N- and O-debenzylations Nitrile reductions
Heterocycle saturation Mine reduction Desulfurization Dehalogenetion
ADVANTAGES Safe • No gas cylinders or other external hydrogen source • No catalyst filtration or direct catalyst handling • Easy catalyst exchange Efficient • Analyse reaction results after two minutes • Perform up to 50 different validation conditions in a day • Higher reaction rates with increased phase mixing • Easy to use, touch-screen controlled Convenient • Compact size can be used in standard laboratory fumehood • No special training or skills required to operate • Can be coupled to the ThalesNano Hydromate or standard • Liquid-handling robots for an automated synthesis process If you require further information on the instrument, or wouid like to have a demonstration scheduled, please contact: ThalesNano Inc. Zahony utca 7 H-1031 Budapest, Hungary Tel: + 3 6 1 8 8 0 8 5 0 0 Web: www.thalesnano.com Email:
[email protected] JANUARY 29, 2007
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