Soaps and Detergents

Clorox Co.'s Clorox with Teflon Surface Protector line of home care products, it turns out, is not made with Teflon-brand fluoropolymers from DuPont. But the product line does contain other specialty polymers that modify household surfaces with a protective barrier, helping them repel soil and stains.

Thanks to the success of the Clorox line and products like Procter & Gamble's Mr. Clean AutoDry Carwash, surface modification is a hot theme in the home and fabric care business these days. And because consumer product companies often turn to outside suppliers for help in developing new products, specialty chemical makers to outside suppliers for help in developing new products, specialty chemical makers serving the business are accelerating R&D programs in surface modification.

Of course, imparting new products with surface-modifying characteristics is just one way that home and fabric care companies are trying to keep their competitive edge these days. Controlled delivery of fragrance and active ingredients is also a thriving area of research, particularly for heavy-duty laundry detergents. And while these firms look for ways to enhance premium products sold in developed countries, they are also working to adapt their cleaning chemistries to lower priced products sold in the developing world.

J. Keith Grime, vice president of R&D for P&G's global fabric and home care business, says the process that his business uses to develop products of all types relies increasingly on cooperation with outside partners. "We have an R&D strategy that combines internal core competencies with external capabilities," he says. "Once we have a target consumer need identified, we begin the search for the solution, whether that be internally, externally, or--usually--a combination of both."

According to Grime, combining this approach with cutting-edge techniques for understanding consumer needs has led to increases in both the rate and the scope of innovation at P&G's fabric and home care business. "Over the past two years, we have more than doubled the future value of our innovation pipeline," he says.

For Clorox, development of the Teflon Surface Protector line started in 2000, around the same time that the company was rethinking the way it goes about collaboration. As Wayne L. Delker, the firm's vice president of R&D, says: "A company our size needs access to powerful technology, but we realized we couldn't do it all on our own. We needed to learn how to identify technology outside Clorox."

Delker says the idea for a surface-protecting product arose from Clorox's core ability to understand consumer needs. "Then we started to use some surface science techniques to really understand what happens at a surface: How does dirt or soil or stain adhere to that surface, and what can you do on the surface to actually control and inhibit that mechanism?"

Clorox identified a set of partners that included DuPont and other specialty chemical companies. It worked with DuPont to determine a performance level consistent with the Teflon brand and then developed, with other partners, a nonfluoropolymer technology to deliver the surface protection effect.

The first product in the family, Clorox Bathroom Cleaner with Teflon Surface Protector, was launched early in 2003. It was followed later that year by a toilet bowl cleaner and a bathroom surface wipe. Delker says the line has been successful and that his R&D team is looking to extend the concept to other home care products as well.

At Henkel, the German household products giant, the focus on surface modification shows up most clearly in the automatic dishwasher (ADW) detergent segment. Thomas Mller-Kirschbaum, the firm's head of worldwide production and technology development for laundry and home care, says ADW innovation has been a tradition at Henkel since the early 1990s when the company developed the first tablet product, which it followed in subsequent years with two-in-one and three-in-one tablets.

Three-in-one ADW tablets contain cleaning agents, rinse aids, and water softeners. In 2003, Henkel added a fourth ingredient system to its Somat and Glist ADW products that provides glass protection. Then last year, it introduced a fifth component, an ingredient that delivers shine to the surface of glass, plastic, and steel washed in an automatic dishwasher.

Mller-Kirschbaum acknowledges that the glass protection ingredient--a zinc salt that helps prevent surface corrosion--is not a brand new invention. The shine-enhancing additive, on the other hand, is. Developed in cooperation with a chemical company partner, it's a nonionic ethoxylate/propoxylate surfactant in which the ratio of ethylene oxide to propylene oxide is key to achieving the desired effect, Mller-Kirschbaum says.

He points out that Henkel sought exclusivity from the partner company in exchange for an exclusive supply contract. In time, the partner will be free to offer the technology to Henkel's competitors, but by then, these firms won't be able to make a unique claim for their products. "This can be better for the partner than trying to get patent coverage," Mller-Kirschbaum says, "because invention applications take three to five years, and during that time competitors know what you are doing."

Despite such lures, specialty chemical companies continue to patent technology for the ADW market. Kevin Beairsto, marketing manager for detergents at Alco Chemical, a division of ICI's National Starch & Chemical, says his business launched several patented terpolymers in 2004 designed to improve the performance of a variety of fabric and hard-surface formulations. Following new product development with a customer, Beairsto says, Alco will often patent a molecule's composition while the customer will patent the molecule's use in the final product.

As it pursues ADW and other hard-surface markets, Alco is stepping up cooperation with National Starch's surface modification and corporate analytical groups to better understand the nature and energy of surfaces. "Otherwise, we're just playing a slow-moving, hit-or-miss guessing game," Beairsto says.

Alco is using the basic understanding it gains, he adds, to design molecules that are tailored to a specific surface and can create a barrier film that will adhere and provide a protective shield. He says Alco has developed "triggered release" chemistry with which specific cleaners can then remove the protective shield.

Tony Latella, director of BASF's consumer specialties business, says his firm's ADW focus is on specialty polymers that deliver multiple benefits. For example, in anticipation of possible restrictions on phosphates in ADW products, particularly in Europe, the firm has developed Sokalan CP42 polymer to deliver improved scale inhibition and antifilming properties relative to conventional polycarboxylates.

BASF is also developing hydrophobically modified polyacrylates for ADW that provide surface modification benefits such as glass corrosion inhibition, improved rinse, and dye-deposition prevention for plasticware.

Like Alco's Beairsto, Latella says BASF develops surface modification effects by drawing on its understanding of interactions between the treated surface, the applied technology, and the dirt or soil--an understanding that he considers one of the firm's core competencies.

SOMETIMES the result of this understanding is a bit unconventional. BASF worked with P&G to develop the melamine foam behind the new Mr. Clean Magic Eraser--a soft cleaning pad that removes surface stains like crayon and scuff marks with water alone.

According to P&G's Grime, the foam works on two levels: Macroscopically, it conforms to most surfaces to reach dirt that ordinary cleaning substrates can't. Microscopically, the surface of the foam consists of tiny cells and hooks that penetrate the surface being scrubbed, breaking up and removing dirt. Latella adds that the foam's functionality stems from both its composition and its unique manufacturing process.

For more conventional surface-cleaning products, BASF recently combined its surface science and nanotechnology know-how to develop a superhydrophobic dirt-repellant surface coating, sold under the Mincor trade name. And the company has developed a new polymer intended to prevent spotting from water hardness by imparting surface hydrophilization.

Surface hydrophilization is also the basis of Rhodia's proprietary DryRinse polymer. DryRinse is sold exclusively to P&G and is the ingredient behind the "no hand drying" claim that P&G makes for its Mr. Clean AutoDry Carwash detergent.

Herman C. Mihalich, Rhodia's vice president for home care, says the success of DryRinse and related polymers in the Surf S family has led Rhodia to expand the line. Over the past year, the firm has introduced polymers for different surfaces--such as glass, granite, and plastic--and for different cleaning chemistries--such as alkaline for kitchen cleaners, acidic for toilet bowl cleaners, and highly concentrated for industrial products.

According to Mihalich, all Surf S family members are designed to adsorb onto a surface in a controlled fashion and modify it with specific properties. In the case of DryRinse, a vehicle's surface is made hydrophilic so that rinse water sheets rather than beads, and spotting is avoided.

Ciba Specialty Chemicals also has a robust R&D effort in surface-modifying additives for hard-surface cleaners. At a briefing for reporters last month at the company's Tarrytown, N.Y., laboratories, Ciba scientists and business leaders provided an advance look at several products in development for hard-surface cleaning and other markets.

Scott Jaynes, who heads Ciba's R&D efforts in surface care, demonstrated two new families of soil-release polymers that contain cationic functionality for better surface binding.

One family is designed to be compatible with nonwoven wipe substrates yet still deposit effectively on a hard surface. The other is being developed for spray-cleaning applications. Jaynes said the high-binding polymers in this family adsorb to surfaces quickly during the spray/wipe cycle.

In addition to research into new ingredients, Ciba scientists are working to migrate technology from other parts of the company to the hard-surface arena. In the lab, Jaynes demonstrated the incorporation of UV absorbers and light stabilizers--traditional additives for coatings and plastics--into hard-surface products such as wood polishes and car waxes. Jaynes said Ciba is attaching such additives to polymer backbones to create molecules with dual functionality: UV protection from the additive plus surface modification attributes from the polymer.

Catherine Ehrenberger, head of Ciba's home and personal care business, said some of the nonwoven wipe additives have been in development for two years and should be launched commercially within the next year. Jaynes said several of the other products that he demonstrated are set for commercialization "in the near future."

At Degussa, surface modification modeled on the self-cleaning properties of the lotus flower was developed by the company's Creavis unit, which brings together R&D activities from business units across the company. The technology, called Lotus Effect, was transferred early last year to Degussa's Aerosil and silanes unit, which is now working with the firm's care specialties unit to develop specific applications for cosmetic and home care products.

John C. Dougherty, director of Degussa's personal and home care business in North America, says care specialties researchers are working to combine silica-based nanomaterials with special organomodified silicones to create a "lotus spray." This formulation can be used in home cleaners to protect both smooth and rough surfaces and to facilitate cleaning.

"We see this as an emerging technology," Dougherty says. "The lotus effect has been known for a while--the chemistry is straightforward--but the trick is in the application of it for our customers." Degussa has found some uses for the effect in high-end markets like electronics, he says, and work continues in consumer markets like hard-surface cleaning and hair care.

While exciting surface modification chemistry is being developed, specialty chemical executives acknowledge that hard-surface cleaning is a fairly low-volume market, particularly in the fast-growing nonwoven wipes segment. Rhodia, for example, has developed polymers for wipes used in both home and personal care. "The volume of product going into wipes is small, so it's a modest business," Mihalich points out. "There's not a lot of chemistry in there. It's mostly wipe."

The laundry detergent business, on the other hand, is slower growing but still a lucrative ingredient market. At the same time, the inefficiencies associated with a dilute wash liquor mean opportunities for companies that can offer ways to deliver fragrance and other expensive fabric care ingredients to where they are needed.

In this regard, specialty chemical companies are taking their cues from consumer product makers. Last month, one of the winners of Henkel's new Research/Technology Invention Award was a technology for fragrance delivery developed by an interdisciplinary team from the Henkel Fragrance Center, the firm's corporate research group, and its cosmetics/toiletries and laundry and home care R&D groups.

Mller-Kirschbaum says the new technology involves chemically linking fragrance compounds to a proprietary delivery molecule so that fragrance in a consumer product can deposit selectively on fabric or other substrates. Slow release of the fragrance is then triggered by humidity in the air.

TARGETED delivery does not come readily, however. As Mihalich points out, "It's easy to deposit things on fabric, but you typically deposit things like the soil you've just removed." Nevertheless, Mihalich says Rhodia is pleased with the results of the Generys active ingredient delivery technology program that it launched in 2002.

At International Specialty Products, the delivery technology portfolio includes Microflex--a microemulsion based on n-octyl pyrrolidone and a naturally derived surfactant--for delivery of hydrophobic ingredients such as fragrances or disinfectant. ISP added another technique last year when it acquired Hallcrest, a British specialist in coacervation-based encapsulation technology.

Although Hallcrest's microcapsules and liquid crystals traditionally have been used by personal care product makers, Sotiri A. Papoulias, ISP's marketing director for performance chemicals, says the technology is now being tested in a number of leading household cleaning brands.

Alco Chemical didn't make a delivery or encapsulation acquisition in 2004, but it did step up cooperation with its parent company, National Starch, according to Dallas Hetherington, business manager for Alco's encapsulation and delivery systems unit. He says National's delivery systems development group added resources last year that will allow it to spend more time serving the household and fabric care market while also investigating new delivery technologies.

David Del Guercio, director of Degussa's textile care business in North America, says encapsulation and controlled-release technology resides throughout his company and that the firm uses its Linking Knowledge internal collaboration initiative to apply the technology where it's needed.

Indigenous to Degussa's care specialties business unit is the organosilicone-based microencapsulation technology pioneered by Goldschmidt Chemical, which Degussa acquired in 2000. The technology is used extensively to deliver sun-protection ingredients, and Dougherty says his business line is looking to apply it to hard-surface cleaners.

Of course, the heavy-duty laundry detergents business is about more than just delivery technology. A classic detergent ingredient is the soil-release agent--an additive that deposits on fabrics, mainly polyester or polyester blends, during one washing and aids the removal of soil in subsequent washings. Rhodia is the standard bearer in this market with the polyester-chemistry-based Repel-O-Tex line, but it continues to face challengers.

In 2004, ISP launched Sorez 100, a polyethylene glycol-polyester soil-release copolymer that the firm has aimed squarely at Repel-O-Tex with literature claiming superior performance. Papoulias attributes its performance to a strong affinity to synthetic fibers, a small particle size, and unique complexing properties that prevent soil redeposition.

Uniqema, a unit of ICI, launched its own soil-release agent last year called Cirrasol PE 113. Applications Manager Harry Motson says PE 113 is attracting interest because of its compatibility with all typical detergent ingredients, including surfactants, builders, and thickeners. In addition, because the new compound is hydrophilic, he says it helps moisture pass through polyester garments, permitting detergent companies to make a "breathability" claim. Motson says PE 113 is being evaluated by detergent makers in large-scale trials.

Uniqema is known in the home and fabric care market mostly as a marketer of specialty surfactants and ester-based solvents with a good environmental profile. According to Motson, the PE 113 launch is part of a push into specialty additives by leveraging company expertise in related markets such as textiles. For instance, Motson sees the potential to capitalize on surface-modification technology that Uniqema has developed for markets including metalworking, paints, and fibers.

Cognis launched two new detergent ingredients in 2004, according to Rita Kster, head of global marketing for the firm's home care and industrial and institutional business. One is Plantatex LLE, a "lipid layer enhancer" that can be added to liquid laundry detergents for sensitive skin. The other is Plantatex HHC, a fabric care additive based on wax crystals that is heat activated via tumble drying or ironing. Kster says it provides a "new and different sensorial profile to consumers."

At the media event in Tarrytown, Ciba's business head for fabric appearance, Nicolas Spillmann, offered a look at a number of laundry-related ingredients that his company has introduced to support customers' fabric appearance, protection, and enhancement claims.

Spillmann said Ciba is finally making headway with the Tinosorb additive it launched three years ago for adding UV protection to clothing through the washing process. Recent successes include Lavatrice laundry detergent in Italy, UV brand fabric softener in Japan, and Radiant detergent in Australia.

A newer product is the Tinolux photocatalytic system, which uses the sun's rays to bleach stains and improve the appearance of white. Spillmann explained that the phthalocyanine-based chemistry--used for years with textiles and high-whiteness paper--works two ways: by catalyzing solar bleaching during line drying and by introducing a slight tint that enhances the appearance of white.

Spillmann said Tinolux is in use in the South Korean detergent brand Solar System; in Mexico's Ace; and in the South American brand Ala, where the label claims "whiteness recovery."

Ciba is also broadening the effects offered by existing product lines. The company has long marketed Tinotex, based on silicone emulsion technology, to companies looking to make easy ironing and antiwrinkle claims. At the briefing, Spillmann demonstrated a new member of the Tinotex family that improves water absorption in textiles, particularly those that have been treated with fabric softeners.

This product is already in use in the Indonesian detergent So Klin and in the Snuggle fabric-softener brand in Taiwan, where the Ciba technology supports a clothing "breathability" claim.

AS EVIDENCED by the countries of the brands Spillmann displayed, many of Ciba's textile care successes are coming from developing markets. However, consumers in developing countries often can't afford brands that contain premium ingredients. Consequently, detergent makers are working to modify their Western formulas for sale in the developing world.

One example is P&G's Tide Clean White, a Chinese brand that, according to Grime, went through a unique development regime. The process started with market research, which revealed that some of the ingredients used in conventional P&G products were not adding value in China. "We learned this consumer wants basic cleaning, which they supplement with elbow grease and additives where necessary," he says.

As a result, P&G removed the less valued materials and invested in a hardness-tolerant balance of surfactants and polymers. It raised the nonionic-to-cationic surfactant ratio, boosted soil suspension polymer and brightener levels, and added a perfume system designed for Chinese preferences.

At the same time, the supply chain was reworked with a decentralized contract-manufacturing network. The result, Grime says, was an overall detergent cost reduction in China of about 25% versus four years ago, Grime says. Volume, meanwhile, has increased by a factor of eight over the same period.

At Henkel, Mller-Kirschbaum says, researchers are studying the partial substitution of polycarboxylate-containing builder systems for phosphates--which took a big jump in price last year--in products sold in developing regions. For developing countries that have banned phosphates, the same researchers are also working to adapt the highly soluble soda ash/silicate builder that Henkel introduced in Western Europe last year. "By using the right ingredients, we can get innovation without cost increases," he says.

Bolstering Henkel's chances for success in cost-conscious markets, Mller-Kirschbaum notes, is last year's acquisition of Dial Corp., a U.S. maker of value-priced brands. Now, as Henkel expands beyond its core Western European market, it is able to call on Dial's U.S. experience with lower cost brands such as Purex laundry detergent. He says Dial know-how has already made its way, via Henkel, into the Chinese home care market.

Specialty chemical companies are scouring their portfolios for products that can help detergent makers like Henkel and P&G succeed in developing countries. BASF's Latella, for example, says the recent phosphate price increases have boosted the cost-competitiveness of standard polyacrylate sequestrants, even in phosphate-rich regions like China.

Mihalich says Rhodia has successfully moved its Nabion builder--a silicate/carbonate cogranule not unlike Henkel's new builder--from Europe and into developing regions such as North Africa and the Middle East that are feeling the phosphate pinch. Now the company is introducing Nabion in Asia.

According to Mihalich, that job has become easier in China, thanks to the country's recent relaxation in national specifications for detergents. "It opens the door to new approaches," he says. "We are talking to formulators in China who can start with a blank sheet of paper."

Alco's Beairsto maintains that close contact between supplier and customer--and even with other suppliers--is necessary to compete successfully in emerging home care markets. "Alco's view of partnership today extends beyond the supplier-formulator relationship," he says. "We are actively working with cosuppliers to create new raw materials that provide customers with better performance than is possible by using two products separately."

He draws an analogy to the auto industry. On one end are inexpensive, low-performance cars and on the other, high-performance, high-priced ones. In the middle, though, are the Toyotas and Hondas--efficient, well-made cars that are affordable because of innovative technology and modern production processes, not cheap parts and labor.

Beairsto says high-quality but affordable home and fabric care products are possible if chemical and consumer product companies collaborate. "We need to form effective working partnerships--not just sales-spiel rhetoric alliances, but true, 'roll up your sleeves and sit down at the lab bench' ones," he says. "Through effective use of these partnerships, detergent companies can reduce costs and compete aggressively in markets around the world."