Soaps & Detergents

Procter & Gamble's launch of Tide with a touch of Downy laundry detergent in late summer 2004 did more than just spark a race among other consumer product marketers to come out with their own detergent-plus-fabric-softener products. It also spurred the laboratories of specialty chemical companies to develop ingredients that these competitors could use in their planned two-in-one brands.

That's the way it goes in the fiercely competitive home and fabric care business. Selling an innovative product that consumers fall for is often the only way marketers can achieve good growth and decent profits. R&D executives at the leading consumer product companies know this and push their research teams to innovate, both on their own and with chemical company partners.

"This is the year of innovation at Henkel, especially in laundry and home care," says Thomas Müller-Kirschbaum, head of production and technology development for laundry and home care at Henkel, one of the world's leading consumer product companies. "Innovation, even more than before, is the top priority in our company."

Typically, when an innovator like Henkel has a hit with a new product, other firms are fast to follow with me-too versions. But the innovator often has special know-how or intellectual property (IP), and the followers must work with their ingredient suppliers to get around these roadblocks.

Such is the case today with Tide with a Touch of Downy. Sharon J. Mitchell, vice president of R&D for P&G's global fabric care business, says her company has developed a patent-protected formula in which the softener active ingredients work synergistically with the cleaning actives, rather than mutually inhibiting each other. Polymers and enzymes are used to create a "cleaning chassis" that is compatible with the softener system. The result, she says, is that "we have not yet found a competitive product that approaches the level of outstanding cleaning and softening offered by the Tide combo products."

Two-in-one detergents, or softergents, are not new and in fact were popular for several years in the early 1980s. At the time, recalls Floyd E. Friedli, then an R&D chemist with Sherex Chemical, nonionic surfactants like alcohol ethoxylates were the workhorse cleaning agents in laundry detergents and could be combined with the cationic dialkyl quaternary surfactants used in fabric softeners without complications.

Today, however, less expensive anionics-mainly linear alkylbenzene sulfonates-dominate detergents. Cationic fabric softeners can form insoluble complexes with these surfactants, and the incompatibility throws a wrench in softergent formulation. Compounding the problem, industry observers say, is P&G's huge patent estate surrounding the use of cationic fabric-softening agents in laundry detergents, preventing other firms from developing systems similar to the one it employs.

P&G told C&EN last year that the softener active in Tide with a Touch of Downy is an ion pair combination of an alkyltrimethylamine with a fatty acid. Good deposition of the new ingredient on fabric, the company said, is achieved with a "triple polymer system" developed with a chemical company partner.

The competing softergents on the shelves today-including Unilever's All Cleans and Softens, Church & Dwight's Arm & Hammer Plus a Touch of Softener, and Henkel/Dial's Purex Plus-must use other means to resolve compatibility issues.

According to Friedli, now a global account manager at Akzo Nobel Surfactants, a top producer of cationics, some manufacturers are using shorter chain monoalkyl quaternary surfactants (quats) or ethoxylated quats that are more hydrophilic and form either weak or soluble complexes with anionics. Other approaches include specialty polymers and amidoamines. "In all cases," Friedli says, "the resulting product gives some static reduction but not much softening compared with rinse-cycle fabric softeners."

Whatever the formula, it is typically the result of collaboration between chemical makers and detergent companies. Friedli, for example, says Akzo Nobel offers a number of these technologies and strives to continue improving the performance of softener ingredients.

The specialty chemical company Degussa, in its softergent work, first experimented with the cationics that the firm markets to the stand-alone fabric softener industry, according to Dave Del Guercio, director of Degussa's textile care business in North America. However, when the company started exploring the patent literature, it learned that many of the more obvious avenues were blocked.

"Sometimes, you have one consumer products company with tremendous IP in an area, and it stimulates innovation in other directions," Del Guercio says. In the softergent case, although Degussa rivals Akzo Nobel as the leader in cationic fabric-softening actives, it turned its attention to noncationic chemistry that it had developed for another industry.

Thanks to this work, Degussa is rolling out softening agents this year that will work in at least three softergent variations. Del Guercio points, for example, to the compact laundry liquids like Unilever's All Small & Mighty that are starting to show up on supermarket shelves. Such concentrated products can be unstable when formulated with the softeners found in many existing softergents, he says, but Degussa's chemistry avoids this problem.

Henkel's Müller-Kirschbaum says his R&D team readily developed powdered softergents using established technology based on bentonite clay. They were launched in mid-2005 in Central and Eastern Europe as Persil with a Touch of Silan, a name that combines Henkel's flagship detergent and softener brands.

While European consumers like powdered detergents, in the U.S., where Henkel has owned Dial Corp. since 2004, the preference is for liquids, which can't be formulated with a clay. Thus, to develop a softergent version of Dial's liquid Purex brand, Müller-Kirschbaum's chemists turned to colleagues in Henkel's cosmetics and toiletries business, which had earlier developed two-in-one shampoos that successfully combine cationic and anionic surfactants.

Müller-Kirschbaum acknowledges sizable IP obstacles around softergents, but he credits Henkel's R&D team for successfully navigating them. "Everybody has some islands in the big sea of IP," he says, "and it's important not to walk on other people's islands."

Softergents have been a particularly welcome development for Degussa and Akzo Nobel, the two biggest makers of fabric-softener actives, but other specialty chemical suppliers are trying to capitalize on them as well.

One is International Specialty Products, which has been evaluating two experimental nonionic fabric softeners in tests alongside the Tide with Downy product. Sotiri A. Papoulias, ISP's global marketing director for performance chemicals, acknowledges that nonionics are inferior softeners but says they can be formulated in modern detergents more easily. "These polymers seem to work well in synthetic fibers and are marginal with cotton," he says.

Another interested company is Rohm and Haas, a leading supplier of opacifiers and other additives for home and fabric care. Detergent marketers have been making the softergents opaque, probably to distinguish them from their translucent standard products, and this trend has bolstered opacifier sales, according to Nilesh Shah, the firm's global research director for consumer and industrial specialties.

Rohm and Haas also has a new dispersant technology that Shah claims can raise the cleaning efficiency of the two-in-ones. Based on ampholytic chemistry, the dispersants contain cationic and anionic moieties, he says, promoting compatibility with the softergents' two main surfactant families.

In addition to dispersants and opacifiers, Rohm and Haas markets biocides and rheology modifiers to the home and fabric care market. And for companies developing follow-on products, Shah says his research group is particularly adept at finding creative solutions while taking the patent landscape into account. "If Acme Soap Company comes to us and says 'we want to develop another two-in-one product,' we will take their ideas as a starting point and use our bag of tricks to create a unique package for them," he says.

Although the softergents are probably the most successful recent innovation to hit the laundry detergent aisle, they aren't the only one. Last January, just a few months after launching Tide with a Touch of Downy, P&G came out with a second new detergent, Tide Coldwater, designed to save money by working effectively in cold water. Dial followed quickly with a version of Purex reformulated for cold-water effectiveness.

P&G's Mitchell enumerates some of the challenges of developing an effective cold-water detergent. At low temperatures, soils remain solid and do not melt; thus they are hard to suspend and remove in the wash. In addition, at cold-water temperatures, typical chemical and enzyme reactions are slower, and commodity surfactants tend to precipitate, especially in the presence of soil or hardness.

"We've learned a lot about this challenge not only in our labs but also with our Japanese consumers who wash exclusively in cold water," Mitchell says. For Tide Coldwater liquid and powder, she adds, P&G also turned to several ongoing partnerships with chemical makers.

Both Tide Coldwater versions use a hydrophobic surfactant system that, according to Mitchell, solubilizes oily soils in cold water. She says this performance was achieved by customizing the surfactant molecule and adding a unique polymer system.

The liquid version uses a combination of protease and carbohydrase enzymes, developed in partnership with suppliers, that Mitchell claims are particularly effective on insoluble soil residues in cold water. The powder additionally contains high levels of a cold-water bleach activator, she says.

The U.S. cold-water detergent launches coincided with rising energy bills and heightened consumer awareness of the cost of heating wash water. P&G's website and advertising, for example, emphasize the $63 that consumers can save annually by washing in cold water.

Enzymes are key to the new formulas, but as Philippe Lavielle, vice president for fabric and household care at Genencor International, a division of Danisco, notes, cold-water enzymes themselves are nothing new and have been used in Japan and developing countries for some time. "Enzyme suppliers, and Genencor in particular, have been working on low-temperature activity for at least the past five years," he says.

Indeed, Genencor launched Properase, a protease enzyme effective in cold water, about five years ago. Then last year the company debuted Purafect Prime, a new protease that claims, among other things, improved soil removal at low temperatures ranging from 20 to 40 ^oC. Lavielle says Purafect Prime has been a huge success and is now the world's top-selling liquid protease.

Also last year, Genencor competitor Novozymes debuted Polarzyme, a powdered protease designed for cold-water cleaning. During the R&D process, the company mainly targeted hand washing of clothes in developing countries, but now it is also finding interest from energy-conscious detergent makers in the developed world, according to Peder Holk Nielsen, Novozymes's executive vice president of sales and marketing. "Our strategy has been overtaken by reality," he says.

The Tide and Purex launches notwithstanding, Nielsen sees consumer interest in cold-water detergents stronger in environmentally aware Europe. "In Europe," he says, "the consumption of energy for laundry washing is equivalent to [the energy produced by] 10 midsized nuclear power plants." Lowering washing temperatures to 20 ^oC from 40 to 60 ^oC today would save 80% of that energy, Nielsen adds.

Enzyme makers aren't the only ingredient suppliers capitalizing on the cold-water trend. Ciba Specialty Chemicals says its Tinocat TRS KB1-a manganese-based catalyst that activates percarbonate and perborate bleaches-caters specifically to low-temperature powdered detergent formulas, offering stain removal and antigraying effects.

According to Nicolas Spillmann, Ciba's global business head for fabric care, other Ciba technologies supporting low-temperature washing include Tinofix CL, a dye fixative offering dye-transfer inhibition, and the Tinopal line of fluorescent whitening agents that work over a wide temperature range.

With their Asian roots, the new cold-water detergents show how fabric care makers readily migrate ingredient chemistry from one geographic region to another. Another example, soon to hit U.S. supermarket shelves, is Purex with Renuzit, a detergent plus fabric freshener that incorporates an odor reduction technology first employed by Henkel in European detergent brands like Perwoll.

Purex with Renuzit is also an instance of the growing trend toward products that combine well-known brand names. Other examples include the Tide and Persil softergents and three extensions of P&G's Febreze odor enhancement line that came out in August: Tide with Febreze Freshness, Downy with Febreze Fresh Scent, and Bounce with Febreze Fresh Scent.

In fact, Dial's Purex with Renuzit is entering the same fabric freshener space that P&G carved out with its Febreze franchise. In contrast to Febreze, which uses cyclodextrin chemistry to reduce odors, the new Purex features Henkel's Neutralin technology, which combines a proprietary fragrance with zinc ricinoleate, an odor-reducing compound developed by Degussa's Goldschmidt unit.

P&G's cyclodextrins are corn-derived carbohydrates featuring roomy molecular cavities that can trap unwanted odors. According to Mitchell, they are in the firm's original Febreze spray as well as the Bounce with Febreze product. Febreze-containing Downy and Tide use other fabric-freshening technologies appropriate to their usage conditions, she says. P&G recently came out with Febreze Allergen Reducer, a spray that also contains an organic polymer intended to agglomerate allergens and make them less likely to become or remain airborne.

P&G's patent estate effectively blocks other firms from using cyclodextrins in odor reduction. But Müller-Kirschbaum favors Neutralin anyway, noting that cyclodextrins don't perform well in water-rich environments like laundry. And Degussa's Del Guercio points out that, unlike cyclodextrins, zinc ricinoleate works by chemically reacting with nitrogen- and sulfur-containing compounds, frequent sources of bad odor. Most fragrances don't contain sulfur or nitrogen and are unaffected, he says.

When zinc ricinoleate was originally developed, Goldschmidt chemists didn't think it would perform in laundry and fabric-softener applications. But Del Guercio says chemists at the firm's new textile and fabric care competence center in Hopewell, Va., worked to overcome stability, precipitation, and migration challenges and make the compound effective in a detergent.

Degussa is also offering its Tegosorb brand zinc ricinoleate to manufacturers of home and personal care products. Potential applications are as varied as underarm deodorants, pet litter, and fabric refreshment products.

Not surprisingly, like most suppliers of specialty chemicals to the fabric and home care business, Degussa works with both multinational consumer product giants and smaller companies that may not have the same internal R&D resources. "We deal with big companies that have specialized needs and smaller companies that require a different level of service," says Reinhold Brand, head of Degussa's care and surface specialties business in North America.

Likewise, Genencor's Lavielle says his firm doesn't limit itself to a certain class of customer. "The way we select a partner is according to their appetite for new products and innovation," he says. "Whether they are small or large is almost irrelevant." Partnering, Lavielle notes, often means developing customer-specific products. Depending on the depth and terms of the cooperation, the customer may have exclusive rights to any resulting molecules, or it may get rights just in certain geographies or product classes.

ISP, Papoulias says, works with the major firms while also monitoring trends in household and industrial cleaners on its own so it can develop products of interest to second-tier firms. His observation: "Major soapers tend to keep more projects or evaluations in-house, while the smaller ones are more likely to use your technical help to test a concept in a specific brand or product."

An ability to effectively serve multiple customers of different sizes is particularly important in the hard-surface-cleaning market, where numerous companies participate and no single firm dominates as P&G and Henkel do in the U.S. and European detergent markets, respectively.

Unique methods of achieving surface modification is a growing theme in hard-surface cleaning, and home care companies and their ingredient suppliers are using a surprising range of chemistries to leave household surfaces clean, free of spots and streaks, and resistant to subsequent soiling.

For example, the 2005 issue of In View of Tomorrow, Henkel's biannual corporate R&D magazine, includes a section on research into technology the company calls temporary surface hydrophilicity, which modifies a surface so that water can wet it uniformly and run off faster. Droplet marks don't form, the firm notes, and the surface stays clean longer.

Henkel launched a glass cleaner based on this idea in 2004, and by last year, all Henkel window cleaners contained the hydrophilic technology. Called Nano-Protect, it makes use of silica nanoparticles with a chemical composition similar to that of glass. During cleaning, the particles align themselves on glass and ceramic surfaces to form a uniform, invisible film. Their negative charge keeps nearby particles at a distance and makes the surface water-attracting.

Müller-Kirschbaum acknowledges one limitation to Nano-Protect: the possibility for particle aggregation in cleaning products that feature high surfactant concentrations. This is why Henkel has so far limited the technology to low-surfactant glass cleaners and to its Fresh Shower line of bathroom cleaners. However, Müller-Kirschbaum says the company is working to expand the technology to applications such as detergents and fabric softeners, where it could deposit ultrathin hydrophilic films on fabrics.

While inorganic nanoparticles are one route to surface hydrophilicity, several specialty chemical companies are achieving the surface effect with organic polymers. One is Rhodia, whose DryRinse polymer is behind the "no hand drying" claim that P&G makes for its Mr. Clean AutoDry car wash detergent.

According to Pascal Juery, vice president of Rhodia's global household and personal care business, the firm's business in hydrophilic surface modification polymers is growing at a double-digit annual rate, thanks in part to a constant flow of new polymers for new surfaces. Rhodia chemists are now tackling the hydrophilization of hydrophobic surfaces like plastics. "Plastic is more challenging," Juery says, "but the experience we have in surface modification means we can contemplate coming up with good solutions in this area fairly soon."

Although Rhodia collaborates with major companies like P&G, Juery says, the company is keen to work with smaller firms as well. He sees their ranks growing, particularly in the U.S., as the big household product marketers divest slower growing or niche brands to concentrate on their biggest sellers.

"The needs of the two kinds of customers are different," Juery explains. "What the big ones expect of a chemical company is a technical collaboration; they are not interested in a full package." But smaller companies generally need help with tasks such as formulation design and marketing claim substantiation. "We need to be in a position to assist smaller companies that often don't have the resources to run a full R&D program," he says.

Although Rhodia may be successful in specialty polymers for surface modification, competition in the sector is fierce. Rohm and Haas's Shah, for example, calls such polymers "our power alley," and points to Rohm and Haas products that use salt sequestration to prevent streaking on hard surfaces and spotting in automatic-dishwashing detergents.

Degussa recently launched a new surface protection product, Tegotop 105, based on the "lotus effect": the ability of plants like the lotus to repel water and dirt. The new product is one fruit of an internal research project, launched by the company's Creavis R&D arm, that brought together scientists from a number of Degussa business units.

According to Janet Kosiek, marketing and sales manager for Degussa's North American home care business, Tegotop 105 combines silica nanoparticles with specialty silicones. When sprayed onto a surface, the product imparts a nanostructured hydrophobic layer that repels water. Rain or plain rinse water that later hits the surface picks up any dirt in its path, Kosiek says, for a self-cleaning effect.

The list of appealing surface modification chemistries goes on. BASF has its Mincor-brand superhydrophobic dirt repellant, also based on nanotechnology, while Akzo Nobel offers Bindzil, which achieves surface hydrophilicity with nanoparticle silicas. ISP recently launched Easy Wet 20, an organic polymer blend that reduces streaking by lowering surface tension, and Ciba is developing specialty polymers that offer everything from soil release to UV stability to streakfree cleaning.

For specialty chemical company executives like Del Guercio, Papoulias, and Juery, the competition must seem fierce and daunting. But for Mitchell, Müller-Kirschbaum, and other leaders in home and fabric care R&D, the breadth of technologies that are available can only bring smiles to their faces.