Advertisement

If you have an ACS member number, please enter it here so we can link this account to your membership. (optional)

ACS values your privacy. By submitting your information, you are gaining access to C&EN and subscribing to our weekly newsletter. We use the information you provide to make your reading experience better, and we will never sell your data to third party members.

ENJOY UNLIMITED ACCES TO C&EN

Business

Greener Cleaners

Consumer demand for environmentally friendly cleaning products has changed the game for chemical suppliers

by Michael McCoy
January 21, 2008 | A version of this story appeared in Volume 86, Issue 3

STAIN buster
[+]Enlarge
Credit: Henkel
In addition to being environmentally sound, cleaning products must clean.
Credit: Henkel
In addition to being environmentally sound, cleaning products must clean.

COVER STORY

Greener Cleaners

THIS MONTH, Clorox, a company almost synonymous with the environmental lightning rod chlorine, is going national with what might seem like an unlikely product line: a family of natural cleaners sold under the Earth-friendly name Green Works.

That a consumer products giant like Clorox would venture into the market for so-called green cleaning products says a lot about how much the home care industry has changed in the past two years. Once solely the province of fringe players, green or sustainable cleaners are attracting the interest of big corporations in America and elsewhere. In such products, companies see both a growing market and a way to burnish their environmental credentials.

This new interest is proving to be a wake-up call to chemical companies that supply the cleaning products industry. Simply providing ingredients that are safe and effective-long the chemical industry's primary goal-may not be enough anymore to satisfy customers who want to market their products as green.

"The suppliers that are going to be in the lead in coming up with ways for customers to formulate products with evident sustainability benefits" will be the winners, observes Ernie Rosenberg, president of the Soap & Detergent Association (SDA), the main trade group for the U.S. cleaning products industry.

Products such as Clorox's that contain natural or naturally derived ingredients are just one way in which cleaning product makers are trying to respond to the clamor for environmentally friendly products.

On a second front, they are reducing packaging and avoiding certain ingredients at the behest of retailers. In 2006, for example, Wal-Mart Stores asked vendors to stop sending it products that contain three suspect chemicals, including alkylphenol ethoxylate (APE) surfactants, and it has pledged to extend the list to 20 "chemicals of concern." Similarly, the consumer products maker SC Johnson ranks its raw materials by toxicity and tries to avoid those that don't measure up.

A third response is to develop products that generate less carbon dioxide during manufacturing and use and thus have a lower environmental footprint. An early entrant in this game from firms such as Procter & Gamble, Henkel, and Unilever is the new generation of concentrated laundry detergents now being rolled out. As marketers like to point out, they require less packaging material and can be shipped with fewer CO2-emitting trucks.

Much of the burden of meeting the environmental goals of cleaning product companies falls on the chemical companies that supply them. They are feverishly working to come up with new ingredients that are both environmentally friendly and keep cleaners performing in the way that consumers have come to expect.

Ironically for cleaning product makers, just as they are striving to improve the environmental profile of their wares, they are being more closely scrutinized by activists and government regulators. Media-savvy activists have learned how to garner press attention with reports on toxic ingredients that put retailers and consumer product makers on the defensive. The government, meanwhile, is taking a closer look at the environmental claims made by retailers. On Jan. 8, the Federal Trade Commission held the first of a planned series of hearings in preparation for an update of its environmental marketing guidelines, known as the Green Guides.

FOR THEIR PART, chemical companies say they are overwhelmed by retailers, consumer product makers, governments, environmental certification organizations, and activists that all mean different things when they use terms such as green, natural, and sustainable.

Andrew Douglass, market innovation director for home and personal care at the Novecare division of specialty chemicals maker Rhodia, notes the dizzying array of U.S. and European organizations seeking to certify consumer products for environmental acceptability. The list includes EcoCert, Eco-Label, EcoLogo, Green Seal, GreenGuard, CleanGredients, Nordic Swan, the Environmental Protection Agency's Design for the Environment program, and more.

According to Douglass, it's hard for Rhodia or any other company to keep up with the changing requirements of so many certification organizations, all of which are vying to become the gold standard. "My job as innovation director is to think about what green will mean in five years' time," he says. "What's clear to me is that it's very fast moving and not particularly designed. We are being buffeted by the rules."

Moreover, while certification firms rank products on biodegradability, toxicity, sensitization, and other easily measurable parameters, they typically haven't established ground rules for what constitutes a natural or naturally derived ingredient. Yet chemical makers say "natural" is what many of their customers are clamoring for these days.

"The big issue with sustainability and green today is that there are no unifying definitions," says Frank Fusiak, North American marketing director for International Specialty Products' performance chemicals unit. "That puts a lot of strain on the chemical supplier."

While the cleaning product marketers such as P&G and Unilever have their own definitions of environmental terms, David Del Guercio, director of Evonik Industries' household care business in North America, notes that "some companies don't have a definition and are asking us for our definition." He says Evonik is developing an ingredient dossier that will categorize its products in terms of their natural content so customers can make decisions about what works in their formulas.

An added complication is that environmental standards vary from region to region. "What is green chemistry in Brazil may be totally different in the U.S. or China," points out Carlos Silva Lopes, global marketing director for Dow Chemical's new fabric and surface care business. Launched last fall, the business offers a service called rapid formulation development that, according to Lopes, can help cleaning industry customers quickly respond to changing government and retailer demands.

Suzanne Thompson, vice president of R&D for Clorox's cleaning division, says her company noted the lack of industry-wide definitions—plus the public's perception of Clorox as a bleach maker—and responded with a set of strict environmental standards for its new cleaners. "We decided that because we are Clorox we had to set a higher bar for ourselves," she says.

Among the company's stipulations was that more than 99% of its ingredients be natural and based on plants or minerals. In addition, they must be biodegradable, nontoxic to fish, and formulated without animal testing. Green Works' toilet bowl cleaner, for example, contains lactic acid, citric acid, alkyl polyglucoside (APG) surfactants, and lemon oil. "It's not that easy to find ingredients," Thompson says. "The industry is still young."

Indeed, according to Clorox, natural products represent less than 1% of the total cleaning category. Jessica Buttimer, marketing director for the Green Works line, says growth has been limited by consumers' concerns over product performance and price. "Many natural cleaners are double the price of traditional brands but in the end do not clean well," she says.

TEST TAKER
[+]Enlarge
Credit: Evonik
Evonik chemist Eunjoo Kim uses a static meter to evaluate towel softness.
Credit: Evonik
Evonik chemist Eunjoo Kim uses a static meter to evaluate towel softness.

In entering the green cleaning products category, Clorox will be going up against niche players such as Method Home and Seventh Generation that, although smaller corporations, are well-entrenched and attract a loyal clientele. Seventh Generation, for example, enjoyed 28% growth in 2006 and is approaching $100 million in annual sales.

SDA's Rosenberg, for one, sees an interesting battle brewing. "It will be a challenge for the green companies," he says. "They had a niche to themselves to a large degree, and now they're going to have to compete with some of the most competent marketing companies in the world."

Interestingly, rather than knock the new competition, Martin H. Wolf, Seventh Generation's director of product and environmental technology, offers kudos to Clorox for Green Works. "We've always said we want to make the world a better place," he says, "and if we've created a path for others to follow, then we're succeeding." Seventh Generation's challenge, he adds, is to stay ahead of the competition technologically and environmentally.

Even among purveyors of natural products, Wolf's firm does seem to offer strong credentials. Both Seventh Generation and Clorox use APGs as surfactants in their hard-surface cleaners, and Wolf acknowledges that the products are similarly effective. But unlike Green Works' spray cleaner, Seventh Generation's product does not contain synthetic dyes or ethanol, a volatile organic compound.

Creating an effective hard-surface cleaner is relatively easy for corporate R&D chemists. The chemistry challenges are greater with products such as laundry and automatic dishwasher detergents that must clean highly soiled fabrics and surfaces without the assistance of elbow grease.

Formulating a laundry or autodish product that is effective and economical, yet environmentally benign, requires tough choices. For example, because APGs are fairly expensive, Seventh Generation has turned to palm or coconut oil-based detergent alcohols that have been modified with ethylene oxide and other petrochemicals. In the industry, such products are known as naturally derived. And in its autodish line, the company uses sodium polyacrylate, a dispersing and antispotting agent that is synthetic and doesn't biodegrade.

Wolf says the company is not happy with this state of affairs. It is investigating surfactants such as the inorganically modified sodium cocosulfate as a way of reducing the petrochemical content of its detergents. It's also taking a new look at APGs, which, being made from coconut oil-based alcohol and glucose, are entirely from renewable resources. "We're starting to think that it may be worth the price as part of differentiation and to make our products more sustainable," he says.

In the autodish arena, Seventh Generation has been testing carboxymethylinulin, a novel dispersing agent that is based on the chicory root. Acquired last year by Thermphos, the product was developed by chemical maker Solutia and the Dutch food ingredients company Cosun. Wolf says his company anticipates incorporating carboxymethylinulin into its autodish products later this year.

Although the big cleaning products companies are aware that some consumers want natural ingredients, for the most part, they haven't made the leap into that market niche.

IN ADDITION TO Clorox, an exception is Henkel's Dial subsidiary in the U.S., which recently launched a version of its budget-priced Purex detergent that is billed as containing 100% naturally derived cleaning ingredients and natural fragrance extracts. The closest P&G comes is in versions of its Tide laundry detergent called Pure Essentials, which contains baking soda or citrus extracts but doesn't otherwise seem particularly natural.

Thomas Müller-Kirschbaum, senior vice president for R&D, technology, and supply chain with Henkel's laundry and home care business, says his company uses environmentally sound ingredients in all its products. He notes that Henkel was one of the first to drop poorly biodegrading branched alkylbenzene and APE surfactants, and that it has worked to get the share of surfactants based on renewable raw materials in its detergents and cleaning products up to 36%.

Yet Henkel isn't willing to sacrifice performance for the sake of natural ingredients, particularly with its premium brands. The company learned the hard way in the early 1990s, Müller-Kirschbaum recalls, when it launched a version of its Persil laundry detergent containing APGs and a fatty acid sulfate, both renewable surfactants. "It was environmentally sound, but it was a compromise performance-wise and it didn't do well," he says.

CHEMICAL COMPANIES that supply the cleaning industry are trying to come up with new ingredients that allow their customers to market high-performance products that also can make environmental claims. "It's clearly the major driver for any specialty chemical supplier supplying this market today, mainly driven by both Wal-Mart and Home Depot," declares ISP's Fusiak.

Fusiak says ISP stumbled into one opportunity in 1999 when it acquired a business that extracts alginates from seaweed. The main market for alginates is the food industry, but Fusiak says customers in the home and fabric care industry are becoming interested in them as natural ingredients that can sequester metals, provide gelling, and control flow properties.

Dow, a company traditionally associated with surfactants and other cleaning product ingredients based on synthetic chemistry, has been emphasizing its use of raw materials that come from renewable resources.

For example, Dow is one of the world's largest producers of propylene glycol, which is often used to thicken household and personal care products. Last year, the company launched a new version of propylene glycol that is derived from natural glycerin instead of synthetic propylene oxide.

Advertisement

More recently, Dow came out with the Ecosurf line of surfactants, which is based on natural alcohols, mostly from palm kernel oil, that have been chemically modified. It is also debuting a new chelating agent, hydroxyethyliminodiacetic acid that, unlike competing chelants such as organophosphonates, is biodegradable.

"There is definitely a trend to green chemistry or naturally sourced ingredients," says Lopes, the Dow marketing director. "Our customers' customers—the consumers—are looking for products that are easy to use, more convenient, and also environmentally sustainable."

WET RUN
[+]Enlarge
Credit: Henkel
Henkel technicians put fabrics through the motions at the firm's Düsseldorf, Germany, labs.
Credit: Henkel
Henkel technicians put fabrics through the motions at the firm's Düsseldorf, Germany, labs.

Formulation chemists at cleaning product companies no doubt enjoy testing exotic new ingredients that come from renewable raw materials such as seaweed, chicory roots, or palm trees. Yet the unglamorous truth is that they spend more of their time assessing traditional synthetic ingredients and making difficult trade-offs involving chemical safety and product efficacy.

This decision-making is playing out now at Seventh Generation, where Wolf has been engaged in a quest for a better preservative for its cleaners. It began when a retailer approached the company with claims from a competitor that its products contain formaldehyde. Wolf was dubious but conducted his own tests and found that they did indeed carry trace amounts of formaldehyde. Further analysis determined that the formaldehyde was being released by preservatives, some added by surfactant suppliers and some by Seventh Generation itself.

The company directed its surfactant suppliers to switch to Rohm and Haas's Kathon CG, an isothiazolinone preservative that doesn't release formaldehyde. However, soon after the company made the switch in its own finished products, it began receiving reports of a bad smell, a sign that the preservative wasn't working well. The company subsequently switched back to its original preservative, a hydroxyethyl triazine known as Surcide-P.

Wolf points out that the levels of formaldehyde in Seventh Generation's products are less than what occurs naturally in many fruits. But he also knows that his products are bought by consumers who bristle at any amount of a chemical such as formaldehyde.

Thus, Seventh Generation has been working since mid-2006 to come up with a new preservative. Its partners in the effort are EPA's Design for the Environment team and McDonough Braungart Design Chemistry (MBDC), a consulting firm that works to reengineer products through what it calls cradle-to-cradle design.

James Ewell, director of projects at MBDC, acknowledges the fundamental challenge of coming up with an environmentally friendly version of a product meant to kill organisms that live in a harsh environment. As part of their work for Seventh Generation, Ewell and colleagues vetted the traditional preservatives used in food and drugs to determine whether they are effective in cleaning products. Many times they weren't, he says.

In addition, they investigated some interesting nontraditional options. One is to instill cleaners with beneficial microbes that suppress unwanted ones. Another is to build microbial protection into product containers with elemental silver technology being offered by the start-up company Agion Technologies. MBDC is preparing a request for proposals that will be sent to potential preservative suppliers.

Ewell cautions that cleaning product formulas are moving targets and that well-intentioned ingredient changes can have unexpected consequences. For example, adding sugar-containing APGs increases a product's renewable content but also introduces a new food source for bacteria, in turn necessitating higher preservative loading. "As much as people in the sustainability community want to talk about win-win situations," he says, "you are often confronted with trade-offs."

Whereas it was a competitor that launched Seventh Generation into action, in other cases, governments or activist groups can be the catalysts for ingredient changes.

Notably, an initiative started by the State of Washington to remove phosphates from autodish detergents is on the verge of going nationwide. Phosphates are versatile ingredients that provide hard-water neutralization, redeposition prevention, and buffering. They were part of laundry detergent formulas for decades until the 1990s, when concerns about phosphorus-induced eutrophication in lakes and rivers led to a series of state-level bans.

Bowing to new pressure from Washington and other states, SDA has now agreed to support the removal of phosphates from autodish products by mid-2010. An exception, Rosenberg says, will be detergents used in industrial and institutional settings, where, the association believes, phosphates are critical to achieving adequate cleaning.

Last summer, meanwhile, the activist group Women's Voices for the Earth released a report called Household Hazards, which examined chemicals in common household cleaning products. It singled out monoethanolamine, quaternary ammonium compounds, glycol ethers, APEs, and phthalates as cleaning product ingredients that are linked to asthma or reproductive harm. At the end of the report was a list of products containing the chemicals of concern.

Whether or not in response to such outside pressure, big corporations are paying attention to their ingredient slates. The British household products maker Reckitt Benckiser, for example, detailed an ingredient removal program in its latest sustainability report. The firm said it had dropped APEs, monoethylene glycol ethers (except phenoxyethanol), and formaldehyde from all but one of its products by the end of 2006.

Ironically, manufacturers of targeted chemicals are often also the firms offering replacements. Dow, for example, is a prominent APE supplier, yet it pitches its new Ecosurf surfactants as alternatives to APEs. Likewise, Lopes says, Dow's new chelating agent is a potential replacement for phosphates or for nitrilotriacetic acid, another chelant marketed by the company. Banned in the U.S., NTA is still used in Europe but is being scrutinized by regulators there, he notes.

Rhodia, also an APE producer, markets a replacement called Rhodoclean, a surfactant that links ethylene or propylene oxide to β-pinene extracted from pine oil. In addition to having a renewable component, Douglass notes, Rhodoclean requires no companion foam control agent as do APEs and alcohol ethoxylate surfactants.

Lopes contends that Dow is moving as quickly as it can to upgrade the environmental profile of its products. "We are allocating our R&D dollars toward more sustainable chemistry," he says. "It's a journey in that direction. But from one day to another can you change totally to natural-sourced materials? The answer is, not really."

AS CHEMICAL MAKERS adjust, they stress that their customers also must be willing to invest time and money to make environmentally sound ingredient changes. For example, one of Evonik's main offerings to the cleaning products industry is cationic surfactants for fabric softeners. They are produced via chemical modification of animal fat, which is a renewable ingredient, albeit not the kind that is normally promoted on a product label.

Del Guercio points out that these cationic surfactants have traditionally been dissolved in ethanol or isopropanol. Evonik could reduce solvent use, but this would change the product form and require Evonik and its customers to invest in new transportation and handling equipment. So far, Del Guercio says, no such project has been launched.

Likewise, this year Evonik expects to launch two amphoteric/cationic surfactant blends that it says can replace APEs in many of the industrial cleaners where APEs are typically used. The firm also offers fatty amine ethoxylates that even exceed APE performance in some uses. However, Del Guercio concedes that the new products will cost customers more.

"Companies will have to bite the bullet and look at higher cost raw materials that will fit into their formulations," he says. Some industrial cleaning product companies, such as JohnsonDiversey, have already committed to remove APEs.

Even more knotty than navigating the trade-off between cost and greenness of individual ingredients is assessing a consumer product's overall sustainability, including its so-called carbon footprint. At Henkel, Müller-Kirschbaum says his company has already made most of the easy formulation decisions, removing ingredients such as poorly biodegrading surfactants, bioaccumulating nitromusk fragrances, and hazardous dyestuffs.

CO2 busters
[+]Enlarge
Credit: Henkel (right), P&G (left)
More concentrated detergent formulas leave smaller environmental footprints.
Credit: Henkel (right), P&G (left)
More concentrated detergent formulas leave smaller environmental footprints.

Today, the decisions are more difficult and can require a full analysis of a product's life cycle. For example, last year Henkel reformulated its Persil laundry detergent in Europe to commemorate the brand's 100th anniversary. One new ingredient in the powdered detergent is a polymer developed in collaboration with the specialty chemicals maker Clariant. According to Henkel, the polymer helps remove stubborn grease stains even at low wash temperatures.

Müller-Kirschbaum acknowledges that the polymer is a polyester that is neither natural nor biodegradable; however, it is nontoxic to aquatic organisms and can be easily removed from wastewater by adsorption. More important, he says, the polymer allows Henkel to promote Persil as effective at lower wash temperatures. If consumers take Henkel up on its proposition, the result will be less heating of wash water, less energy used in the home, and fewer tons of carbon dioxide released into the atmosphere.

"Even if the material that helps make this happen is not biodegradable, it improves our total sustainability and thus is a step in the right direction," Müller-Kirschbaum asserts. "If I could use a renewable material that is readily biodegradable, then I would, but that is not always possible."

Müller-Kirschbaum's reasoning reflects a growing recognition by consumer goods firms that their products contribute to global warming. These days, their corporate environmental reports emphasize efforts to reduce the amount of carbon dioxide emitted during the manufacture, and even the use, of their products.

Advertisement

In October, P&G announced new five-year sustainability goals that include 10% reductions in CO2 emissions, energy and water consumption, and waste per unit of production. The firm sees the new compact versions of its Tide, Cheer, Gain, Era, and Dreft laundry detergents as part of the plan. Smaller bottles use less fuel and warehouse space and reduce the amount of packaging by 22-43%, P&G says.

A month later, Reckitt Benckiser announced it would take a new tack in environmental improvement by tackling what it calls total carbon footprint, the amount of carbon dioxide emissions inherent not just in company factories but in ingredients, packaging, and consumer use and disposal. The company's goal is to reduce its total carbon footprint by 20% per unit of production by 2020.

Edward Butt, Reckitt's vice president for sustainability, says the company's approach is unique in the packaged goods industry and the only one that makes sense. Reckitt estimates that consumer use of its products, particularly when involving dishwashers and washing machines, accounts for 50-70% of the associated carbon emissions. Emissions related to the production of ingredients and packaging materials are 30-40%, while those due to product manufacturing are only 2-6%.

THE IMPACT of changes in consumer habits can be substantial. If 50% of European households lowered their dishwasher temperatures by 10° to 50-55 °C, Reckitt estimates 338,000 metric tons of CO2 equivalents would be saved every year, equal to the emissions of almost 100,000 midsized cars. Thanks to earlier energy-savings initiatives, Butt says, the firm's autodish detergents are already capable of working at the lower temperatures.

In contrast, Butt admits that Reckitt has only started to consider the carbon footprint of the ingredients it buys. Although he acknowledges he could shrink the footprint by switching from synthetic ingredients to ones made from renewable resources, he cautions that consumers would balk if quality were compromised in the process. "For consumers, performance is most important, followed by value. Other attributes, including environmental impact, are third," he says.

Like Henkel's Müller-Kirschbaum, Butt is adamant about maintaining the performance of Reckitt's products throughout any environmental improvement exercises. After all, Henkel and Reckitt are mass marketers that target the middle chunk of any country's population—people who aren't necessarily out to save the world.

Not an inspiring market, perhaps, but one, Butt says, that gives his company the opportunity to do more good. "There will always be a small part of the consumer landscape that is the green consumer," he says. "What's important is not moving just a few green consumers but moving all consumers in the right direction."

[Top of Page]

Article:

This article has been sent to the following recipient:

0 /1 FREE ARTICLES LEFT THIS MONTH Remaining
Chemistry matters. Join us to get the news you need.