The Greening Game

TAKE A WALK down the aisles at WalMart or a neighborhood supermarket and it becomes clear that the cleaning product landscape is changing. Laundry detergents, dishwashing detergents, and spray cleaners have always promised to rid the home of dirt and grime. But now many products vow to protect the environment as well.

Niche marketers such as Seventh Generation and Method Home have for several years offered products formulated to be more environmentally sustainable. During 2008, the major cleaning product companies also got into the act. With the help of their raw material suppliers, they introduced a range of goods that demonstrate the diverse ways they are responding to consumer demand for greener cleaners.

After shaking up the market for hard-surface cleaners early in 2008 with the launch of its Green Works brand, Clorox expanded the line to include hand dishwashing liquids and cleaning wipes. And on bottles of some Shout and Scrubbing Bubbles products, SC Johnson started touting that its ingredients are cleared by the Environmental Protection Agency's Design for the Environment program.

Church & Dwight took its Arm & Hammer Essentials brand beyond just a laundry detergent with plant-based surfactants to include spray cleaners with an environmentally friendly twist: Rather than buy a fresh container that is mostly plastic and water, consumers needing more cleaner can purchase a small capsule of concentrate and, using tap water, refill their old bottle at home.

Henkel launched the Terra Activ line of cleaners in Germany, while its Dial subsidiary added a fabric softener to its Purex Natural Elements laundry detergent in the U.S. And Colgate-Palmolive debuted Palmolive Eco automatic dishwashing detergent, which claims to be the first mass-marketed automatic dishwashing detergent brand to eliminate phosphates.

"For us what was significant in 2008 is that the sustainable elements of this market became structural in the U.S.," says Francois Scheffler, industry marketing manager for care chemicals at BASF, a major supplier of ingredients to the cleaning product industry. "Before 2008, the evidence was anecdotal."

THE NEW OFFERINGS target consumers who, more and more, want to know what's in the cleaners they buy. In response to public pressure, the Soap & Detergent Association (SDA) and two other consumer product groups recently launched an initiative to provide more information about what's in the box or bottle. Starting in January 2010, association members will voluntarily post ingredients on product labels or on company websites.

"The consumer is becoming more educated, and the Internet is doing a lot to make that happen," says Andrew Douglass, market innovation director with Novecare, the home and personal care ingredients division of specialty chemical maker Rhodia.

Marketers of household goods are certainly aware that the public wants environmentally sound products. Earlier this month, more than 12 of them formed a partnership with the American Chemical Society's Green Chemistry Institute aimed at sharing knowledge and experience in green chemistry and engineering (C&EN, Jan. 5, page 12).

YET COMPANIES and their ingredient suppliers are taking a surprisingly diverse range of approaches to the sustainability challenge. Some are emphasizing more compact packages, and others are pushing ingredients derived from renewable resources. Still others say formulas that lower the temperature of water required for cleaning are the way to go.

Procter & Gamble, the 800-lb gorilla in the laundry detergent aisle with its Tide line, is noticeably missing from those promoting cleaners based on natural ingredients. Lauren Thaman, a public affairs specialist who handles sustainability issues for P&G's fabric care business, explains that this is because the company wants to see science behind its sustainability claims.

"We're committed to having a science-based approach to sustainability," Thaman says. "Just because it's natural doesn't mean it's sustainable. We have taken a life-cycle analysis approach to ensure we are making claims that are meaningful and measureable."

In laundry products, P&G's main sustainability efforts have been in concentrating its detergents to save on transportation and packaging costs and in launching detergents such as Tide Coldwater and Ariel Cool Clean that save energy by cleaning well at lower wash temperatures. In both cases, P&G says it can quantify its new products' reduced environmental footprint.

"I'm not going to comment on whether or not our competitors are doing that," Thaman says, "but I will tell you that until being able to say something is 'natural' means it is more sustainable, we will not do that."

BASF's Scheffler makes a similar point regarding the cleaning product raw materials BASF makes. "Using a synthetic product that reduces water or energy use by the consumer is as equally sustainable as a product based on a renewable vegetable source," he says.

Scheffler points to Lutensol M, a new BASF surfactant made by ethoxylating 2-propylheptanol, a branched alcohol. The company says it conducted an "eco-efficiency analysis" that concluded Lutensol M production causes fewer emissions into wastewater and consumes less energy than other surfactants. Moreover, because of its good emulsifying properties, the new surfactant allows the formulation of laundry detergents that work well at low wash temperatures, BASF says.

Likewise, Pascal Juery, president of Rhodia's Novecare division, cites products such as his firm's Mirapol Surf S, an acrylic-based polymer that makes surfaces more hydrophilic. When added to automatic dishwashing detergent formulas to provide better rinsing, Mirapol Surf S can replace surfactants at just 1% or even 0.1% of the original quantity, Juery says.

"Using a synthetic material to reduce a product's overall chemical content is a valid approach to sustainability," he maintains. Rhodia is also developing "natural-synthetic" hybrid ingredients such as Rhodoclean, a surfactant that links ethylene oxide or propylene oxide to β-pinene extracted from pine oil.

ALTHOUGH COMPANIES such as P&G may have sound scientific reasons to stay off the "all-natural" bandwagon, they have image-based motives as well. Anders Lund, marketing director for detergents at Novozymes, the world's largest manufacturer of enzymes, notes that large corporations have built up a lot of consumer trust in their brands, and they are loathe to put it at risk.

"Some of the bigger brands are worried that their brand equity can get diluted if they focus solely on sustainability," Lund says. "The ones with the most to lose are the most conservative. That doesn't mean they aren't doing anything, but they may not be as aggressive in communicating it." Rather, it's the companies with a smaller market share that tend to trumpet their natural or sustainable products.

Lund's observation bears out at Henkel, a leading European detergent manufacturer. Henkel has taken a chance in the U.S. with the Purex Natural Elements line, but Purex is a second-tier brand that doesn't have the same reputation as Tide does. In Europe, where Henkel's Persil is the gold standard, the company hasn't launched a green version.

Going all-natural would compromise the performance of Henkel's brands, according to Thomas Müller-Kirschbaum, senior vice president for R&D, technology, and supply chain with Henkel's laundry and home care business. Still, he says, the company is committed to improving the sustainability of its products, particularly in the realm of low-temperature performance.

Europe has a history of using high wash temperatures, and in the 1970s, close to half of all laundering was done in near-boiling water. This figure is only 8% today, Henkel says, but cool-water washing is still rare there. As of 2006, the company says, less than 5% of laundry was washed at 20 ºC. It expects that figure to rise to at least 20% by 2020.

Last April, Henkel launched a reformulated Persil line designed to "clean better than ever" at 20 ºC. According to Müller-Kirschbaum, the new Persil formula was made possible with an enzyme system developed under a four-year partnership between Henkel and Brain, a German firm that discovers enzymes and other bioactive compounds. The result was a new mixture of proteases and other enzymes specifically evolved to work at lower temperatures.

Similarly, Henkel is improving the low-temperature performance of its best-selling Somat automatic dishwashing detergent brand. In 2008, the firm launched Somat 7, a detergent with seven distinct functions, including performance at 40 ºC that was previously obtainable only at 60 ºC.

For Somat 7, Henkel looked twice to outside technology partners. It developed a new enzyme in an exclusive cooperation with an unnamed collaborator. And it turned to a competitor to license an activator that helps the detergent's sodium percarbonate bleach work well at the lower temperature. Under its open innovation policy, Müller-Kirschbaum says, Henkel not only cooperates with raw material suppliers and research institutes but also licenses innovations from its rivals.

While Henkel used low-temperature effectiveness to improve the sustainability of its marquee European brands, the company also created a new brand aimed at consumers with what it calls lifestyles of health and sustainability, or LOHAS. Terra Activ, a line of hard-surface and hand dishwashing products, was launched in October. On average, the company says, 85% of each formula in the Terra Activ line is based on renewable raw materials.

LOHAS consumers are willing to pay extra for sustainability, but they won't sacrifice performance, according to Müller-Kirschbaum. This is why Henkel chose the 85% target rather than the 99% all-natural claim that Clorox makes for its Green Works line in the U.S. "What we saw in our development work was that if we went in the direction of 99%, we would come to areas where we sacrificed performance," he says.

So far, Müller-Kirschbaum adds, consumers are receptive to Henkel's products with high natural-ingredient content. He says the company plans to launch a Terra Activ laundry detergent in the first half of 2009 and also broaden the Natural Elements brand in the U.S.

SUCH PLANS are good news for chemical companies that have been expanding their arsenals of cleaning ingredients that are partially or wholly based on natural raw materials. Seeing a trend that isn't likely to go away, chemical makers are both increasing their use of renewable feedstocks and developing new ingredients that overcome the environmental shortcomings of some stalwart cleaning chemicals.

It was one year ago that Dow Chemical made its foray into renewable raw materials for cleaning products with the Ecosurf line of surfactants based on chemically modified seed oils. Carlos Silva Lopes, global marketing director for Dow's fabric and surface care business, says Dow will launch a second-generation Ecosurf line at SDA's annual conference, held this week in Boca Raton, Fla.

The new surfactants will offer an improvement in performance and formulation flexibility over the original Ecosurf, according to Lopes. He says they are tailored for hard-surface products such as bath, tub, and kitchen cleaners.

Evonik Industries, the world's largest supplier of fabric softener active ingredients, has long manufactured a naturally derived product. Its softener actives are based on tallow or, increasingly, vegetable oil. Although consumer goods companies have no desire to highlight tallow, an animal fat, on their labels, they are interested in the "renewable carbon" content of the ingredients they buy.

David Del Guercio, Evonik's household care business director for North America, says the company has responded to the clamor for renewable carbon content by developing a dossier that categorizes its products by, among other things, their renewable carbon index (RCI). These indexes are obtained by dividing the number of carbons derived from renewable sources by the total number of carbons. For example, Evonik's Varisoft DS 350 VEG, a vegetable-based softener active, has an RCI of 0.9. In other words, 90% of the product's carbons are renewable.

Customer interest in enzymes, another renewable cleaning ingredient, has surged over the past two years, if Novozymes' results are any guide. Although detergents are the Danish firm's biggest market, for much of this decade, the market wasn't growing very fast. Then, in 2007, detergent enzyme sales shot up 10%. Last year, sales were on track for 14% growth—impressive for the detergent industry, which typically expands by only 1 or 2% per year.

"Novozymes has always believed in detergents," says Lund, the marketing director, "but only in the past two years has it paid off." He attributes the growth mostly to customers who turned to enzymes as a safe harbor when prices for conventional ingredients started becoming highly volatile.

But customer demand for more sustainable ingredients has also been a driver, Lund says. In recent years, Novozymes has developed new enzymes such as Stainzyme, Polarzyme, and Liquanase that are specifically designed to work in cold water. "We can prove that compared with other ingredients, enzymes work better at low temperature," he says. Moreover, although laundry detergent makers traditionally add enzymes for their stain-removal capabilities, Lund says his customers are discovering that enzymes impart basic detergency as well.

Novozymes sees enzymes as potential replacements for phosphates, which are being banned from laundry detergents in several European countries and will be phased out of automatic dishwasher detergents in the U.S. by mid-2010 under an industry agreement. According to Lund, detergent makers can replace phosphates and surfactants with a multienzyme mixture without loss of performance.

Also exploring phosphate replacement is AkzoNobel, which became a bigger player in cleaning chemistry after its 2008 acquisition of ICI. Soon after the deal, company managers combined Akzo's surface chemistry business with ICI's Alco Chemical specialty polymers subsidiary to create a major supplier of cleaning product ingredients.

The combined company can supply 75% of the active ingredients in most cleaning formulas, according to John Cate, global business director for fabric and cleaning applications at AkzoNobel Surface Chemistry. "No one else can do that," he says.

Researchers from the two halves of the business are now joining forces to tackle the phosphate phaseout. Today, the firms' specialty polymers are added to phosphate-containing automatic dishwashing products to disperse calcium phosphate and other salts. For tomorrow's phosphate-free formulas, Cate says, scientists are developing dispersing agents based on polymers and AkzoNobel chelating agents such as glutamic acid diacetic acid, which is derived primarily from corn or other renewable resources.

Some automatic dishwashing detergent makers don't worry about phosphates because they don't use them in the first place. Case in point is the household goods maker Seventh Generation, which is in the vanguard in trying to create products with renewable, sustainable ingredients.

Seventh Generation launched its automatic dishwashing detergent in 2001, using citric acid to play the buffering and hard-water softening role of phosphates. The company has since moved on to a new challenge: going more natural by weaning itself from the effective, but nonbiodegradable, acrylic polymer dispersing agents that it now buys from Rohm and Haas and replacing them with plant-based substitutes.

For the past few years, Martin H. Wolf, Seventh Generation's director of product and environmental technology, has been working with the Dutch chemical company Thermphos on carboxymethylinulin, a dispersing agent based on chicory root. Wolf had hoped to launch a reformulated automatic dishwashing detergent in 2008, but he is now targeting 2009.

LIKEWISE, some companies believe they've gone natural if they reformulate their laundry detergents with surfactants made by reacting coconut-based alcohols with ethylene oxide. Seventh Generation did that a while ago. It's now working to move beyond ethylene oxide—both because it is a petrochemical and because ethoxylation yields minute amounts of the possible carcinogen 1,4-dioxane as a by-product.

Wolf and his colleagues have been working with specialty surfactant suppliers such as Cognis, Croda, McIntyre Group, Stepan, and Win Chemical to replace the ethoxylated alcohols with sodium cocosulfate, an alkyl sulfate based on coconut oil. It hasn't been easy, Wolf acknowledges. Alkyl sulfates are less soluble than ethoxylates, must be used at higher concentration to achieve the same degree of cleaning, and can irritate the skin, he explains.

Still, Wolf hopes to launch new versions of Seventh Generation's laundry detergents and hand dishwashing liquids later this year. In addition to eliminating 1,4-dioxane, the company will have switched to a surfactant with an RCI of 1, versus only 0.75 with an ethoxylated natural alcohol.

Seventh Generation is also eliminating a chlorine-containing preservative from its liquid cleaning products. Although Wolf has a long-term goal to move to a substitute derived from renewable raw materials, for now he is content to switch from a triazine to a blend of methyl and benzyl isothiazolinones.

Without a doubt, the product improvements Wolf is pursuing matter only to a small group of people who are very concerned about the environmental impact of the products they buy. Yet there's also no doubt that a growing group of consumers is aware that the pleasantly colored cleaners under their sinks are actually mixtures of potent chemicals with varying degrees of impact on Earth.

Consumers are becoming more savvy about the products they buy, according to Lauren G. Heine, a consultant and senior science adviser to Clean Production Action, an advocacy group. "I think our definition of 'safe' has changed," she says. "What may be safe for occasional use in the home isn't necessarily safe when the entire life cycle is considered and when a lot of homes are using it and discharging it to the environment."

While at the nonprofit GreenBlue, Heine initiated the development of CleanGredients, an Internet database of environmentally friendly surfactants. Launched with the backing of EPA's Design for the Environment program, the database today contains surfactants from all major chemical companies. CleanGredients is now debuting a companion database for solvents and is readying one for fragrances.

"At first some people thought it would be a blacklist," Heine recalls of industry reaction to the surfactants database when it first came out. "But after awhile they realized it was a way to identify greener chemicals and open market opportunities."

Indeed, a market opportunity is how most players in the cleaning product industry see sustainability these days. Pointing to the spate of new spray cleaners on store shelves, Rhodia's Douglass marvels at how environmentally friendlier products are shaking the industry up. "Hard-surface cleaners was probably the least interesting market out there, and look at what Clorox has done to it," he says.

"Fabric and home care companies see an opportunity to bring innovation to market based on the sustainability initiative," Douglass adds. "They are reinventing the industry and making it exciting again."