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January 15, 2001
Volume 79, Number 3
CENEAR 79 3 pp.26-31
ISSN 0009-2347
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Detergent additive makers take their cues from industry leader Procter & Gamble

MICHAEL MCCOY, C&EN Northeast News Bureau

CONTINUES to be the pace-setter when it comes to fabric care innovation, and the bevy of new products it launched last year reinforces that role. New P&G products are a boon to the lucky companies it chooses as additive suppliers, but they can also benefit suppliers serving the cleaning product firms that imitate in P&G's wake.

 The P&G product that made the biggest splash last year was Tide Rapid Action Tablets, the first laundry tablets to hit retail shelves in the U.S. following their surprising success in Europe over the past two years. In addition, advanced versions of several existing P&G products also made their debut, most with technological improvements developed by P&G and its chemical company partners.

 Keith Grime, P&G's global R&D manager for fabric and home care, says the company's product introductions are based on the matching of new technology with consumer insights. "Our strategy is to match 'what's needed'—what the consumer wants—with 'what's possible'—what state-of-the-art technology can deliver," Grime says.

 According to Grime, P&G new product development balances internal R&D innovation with close collaboration with raw material suppliers that are expert in certain fields of chemistry. "While product design and formulation remains the exclusive domain of P&G," Grime says, "our partners act as true innovation collaborators on the chemistry side, as well as the ultimate supplier of the new material."

CHEMICAL COMPANIES are scrambling to partner with soapers for this latest industry innovation following the U.S. debut of the Tide laundry tablets—and the subsequent launch of a Wisk tablet from Unilever. If they can't supply ingredients for pioneers like P&G, they are happy to supply makers of me-too or second-generation products.

 The key differences between detergent tablets and conventional laundry powders are the binders that hold the tablets together and the disintegrants that force them apart in the wash. Grime won't disclose the disintegration technology of the Tide tablets, but industry observers say it's likely carboxymethyl cellulose combined with a sodium bicarbonate-citric acid mixture that provides an effervescent breakup when the tablet hits the wash water.

 The adoption of this fairly low-cost approach is a disappointment to chemical companies offering disintegration systems based on more expensive ingredients, but managers at these firms are confident that their systems will be considered for next-generation tablet products.

 For example, International Specialty Products (ISP) is offering a tablet disintegrant it calls Disintex 75 that's based on polyvinylpolypyrrolidone (PVPP) technology similar to what has been used for years by pharmaceutical tablet formulators. The company says PVPP swells on contact with water, causing rapid tablet breakup and helping soapers claim quick dissolution in the wash.

 Although it's used in European laundry tablets, Disintex isn't in the first round of U.S. products. However, Sotiri A. Papoulias, global marketing director for ISP's performance chemicals group, says the game is young for U.S. tablets. "The first pass was very basic tablets with not much emphasis on speed of disintegration," he says. "Now that the category is created, detergent makers are asking, 'How can I make my tablet better?' "

 Papoulias adds that ISP is also planning a series of blends of PVPP with other disintegrant materials in order to offer customers a range of cost and performance options.

INNOVATION: Novozymes' researchers worked with P&G to come up with a new detergent enzyme in record time.
is also pursuing the detergent-tablet market with Acusol 771, a swellable cross-linked acrylate polymer that's part of a broad line of rheology modifiers, dispersants, opacifiers, processing aids, and preservatives that the company sells to detergent and cleaning product manufacturers.

 Michael Robertson, global marketing manager with Rohm and Haas's consumer and industrial specialties unit, says the firm is pleased with the success of Acusol 771 so far. It's already being used in automatic dishwasher tablets, which were the first cleaning tablets to hit the U.S. market and helped pave the way for the laundry tablets.

 Robertson says Rohm and Haas is now working on a more complete cleaning tablet "solution" that combines an Acusol 771-type disintegrant with an acrylic tablet binder. Tablet binders allow detergent makers to reduce reliance on physical compression, a binding technique that tends to impede tablet disintegration. "Detergent makers want their tablets to disintegrate in the wash but also maintain their integrity in solid form," Robertson says. "Our solutions will help them accomplish both."  The higher price per pound of acrylates compared with some other disintegrants and binders is offset by greater effectiveness, Rohm and Haas points out. Kim Ann Mink, Americas marketing manager for the consumer and industrial specialties unit, claims that traditional cellulosics must be added at a level of 4 to 5% to effectively dissolve tablets, whereas 1.5% or less of an acrylic-based binder/disintegrant system is needed to provide a faster disintegrating and more robust tablet. "This frees up room for more actives in the tablets," she says.

 Although the new tablet was P&G's boldest marketing move in laundry products in 2000, the established cleaning product brands that it relaunched last summer with new performance claims are just as innovative technologically.

 At the top of this list is a new version of P&G's flagship liquid laundry detergent called Tide Deep Clean Formula. It features a proprietary mannanase enzyme known as Mannaway that was designed to remove carbohydrates in the mannan family. P&G developed the new enzyme in cooperation with the Danish enzymes producer Novozymes, a new public company that was formed late last year out of the enzymes division of Novo Nordisk.

A TEAM APPROACH, combining P&G expertise and consumer insights into the problem of carbohydrate residues on fabrics with the enzyme expertise of Novozymes, was used to develop the enzyme, says P&G's Grime. Peder Holk Nielsen, Novozymes' vice president of sales and marketing, adds that the resulting close collaboration led to the introduction of the technology in record time—"26 months from idea to ton quantities on the ramps of P&G factories," he says.

 The new Tide product addresses a cleaning issue that P&G and Novozymes are highlighting as part of their respective marketing efforts to consumers and detergent makers: the reappearance of stains on fabric after they have seemingly been washed away.

Nielsen notes that certain stains, such as those based on starch or protein, act like a glue that isn't removed by surfactants alone. Even though pure starch, for example, is colorless, it can latch onto cotton fabrics and provide a surface on which stain-causing soils can later bind.

According to P&G, guar gum—a polysaccharide in the mannan family that is found in many household products—is particularly culpable in this problem. Guar gum-containing stains that appear to have been washed out are actually still in hiding in the garment, the company says, waiting to stick to dirt that arises during wear or in the wash water and causing the stain to "reappear."

MANNANASE ENZYMES were developed specifically to address this problem, and their introduction in P&G products last year helped fuel a 10% rise in third-quarter detergent enzyme sales compared with 1999, Nielsen says. In fact, Novozymes predicts that mannanases may one day be as important to P&G as amylases, cellulases, and lipases—all basic cleaning enzymes—are today.

 But Nielsen emphasizes that Novozymes offers customers several different ways of attacking stain problems. "Mannanase isn't the only solution," he says, noting that what Novozymes calls total cleaning can be achieved through "cocktails" of other enzymes as well.

 Keith Gibson, a researcher in enzyme development and applications at the firm's Danish R&D center, says the total cleaning concept represents a new way of thinking for Novozymes in which enzymes are seen as reducing soil-binding on fabrics—sold, in effect, as antiredeposition agents in competition with traditional additives such as acrylate polymers.

 Indeed, Nielsen is confident that enzymes and other premium additives can compete successfully with older, harsher detergent chemicals in a variety of advanced cleaning applications. However, achieving this goal requires close cooperation between detergent makers and enzyme suppliers—something Novozymes is trying to foster as a stand-alone company.

 "There have been missed opportunities," Nielsen says, due to insufficient cooperation on refining new technology and making it competitive with older but well-optimized approaches. "We invite our customers to cooperate with us to bridge some of these competitive gaps," he adds.

 Alongside the mannanase-containing liquid Tide detergent, P&G launched a new laundry powder last summer called Tide WearCare that is in keeping with an industry trend to impart detergents with advanced fabric-care qualities—particularly in the realm of color protection. As Grime says, "Consumers look for their detergent to provide them with true fabric care, not just cleaning, and they want it with less effort."


cheer_clipped_eps12TWO TECHNOLOGIES combine to give WearCare its fabric-care qualities. One, Grime says, is a hydrophobically modified cellulosic material that binds to the fabric and helps prevent cotton fibrils from breaking loose during abrasion. It is this abrasion process, he notes, that makes a cotton garment look worn. This technology is also found in P&G's Cheer with Liquifiber.

 The second technology is a custom-designed imidazole derivative that acts as a dye fixative, helping to prevent the loss of fugitive dyes from cotton fabrics. Grime says this additive was designed to overcome some of the negative interactions that traditional dye fixatives have with anionic surfactants.

 Together, Grime claims, the additive combination "significantly extends the useful lifetime of cotton fabrics." Both technologies are proprietary to P&G, he says; the abrasion control technology was developed internally, whereas the dye-locking imidazole derivative was developed in collaboration with a specialty chemical partner.  Fixing dyes in place and keeping fugitive dyes from redepositing on other garments—a process known as dye-transfer inhibition or DTI—are major focuses of a number of detergent additive makers, notes Arno Cahn, a former Unilever executive who runs a consulting firm in Pearl River, N.Y., that bears his name. Cahn says most DTI agents are aromatic molecules that work by complexing fugitive dyes.

 ISP, for one, is assembling a stable of such DTI agents through internal product development and a new alliance with Reilly Industries.

 Papoulias notes that ISP has long been a player in DTI through its workhorse product, polyvinylpyrrolidone (PVP), which was commercialized in the early 1990s. In 1999, following briefings from several European customers, the company developed a next-generation inhibitor called ChromaBond S-100, a patented poly(4-vinylpyridinium betaine) based on pyridine chemistry. The new polymer is already in extensive use in Europe, Papoulias says; however, its expected debut by a U.S. laundry detergent maker has been delayed due to restructuring at the company.

IN OCTOBER 2000, ISP added yet another DTI compound, Reilly's poly-4-vinylpyridine-N-oxide (PVNO), to its lineup. Papoulias explains that the DTI application for PVNO was patented by P&G in the early 1990s and commercialized in several products around the globe. It was later licensed to Reilly, a leader in pyridine chemistry, as part of a P&G plan to generate additional revenue from royalties.

 Reilly, in turn, approached ISP, partly because of ISP's strong position in DTI and partly because Reilly was already contract manufacturing some of ISP's ChromaBond S-100 needs. "Reilly has a very strong technical and manufacturing organization," Papoulias says, "but they don't have the presence as detergent producers like we do."

 Papoulias notes that each of ISP's three dye-transfer products has its own detergent formula niche: PVP is a lower cost product for basic brands, whereas the two pyridine compounds are targeted at different premium applications. S-100, for example, isn't compatible with bleach-containing products, whereas PVNO, now called ChromaBond S-400, is.

 ISP claims leadership in dye-transfer inhibition—a market it says is worth $50 million per year—but other specialty chemical makers are pursuing DTI and the related dye-fixation segment with equal enthusiasm.

 One such company is Alco Chemical, a division of National Starch & Chemical. Kevin Beairsto, who heads Alco's detergent industry marketing efforts, notes that Alco will launch a new DTI agent this year that he says has been shown to be several times more effective than PVP.

"Consumers look for their detergent to provide them with true fabric care, not just cleaning, and they want it with less effort."
product, which departs from traditional aromatic DTI chemistry, works through a combination of hydrogen bonding and electrostatic interaction with the fugitive dye molecule, according to Allen Carrier, the firm's senior manager of R&D. It's light in color, unlike some competing products, and is effective in both liquid and powdered detergents, he adds.

 The product also represents another departure from Alco's traditional acrylate chemistry core. Carrier says the new chemistry continues Alco's evolution from a maker of largely commodity acrylate homopolymers just five years ago to a supplier weighted toward specialty, patented copolymers, and now nonacrylic compounds as well. This trend started under National Starch, he notes, but has accelerated under the broader corporate umbrella of ICI, which acquired National Starch in 1997.

 According to Beairsto, Alco is approaching color protection in several ways. As a complement to the DTI compound, the company is testing a dye fixative based on a patent-pending condensation polymer developed in its Chattanooga research facility. Also nonacrylate, the fixative is on schedule for launch late this year.

 Carrier says Alco has applied for a patent on a new antipilling technology that can lessen the worn or grey look associated with pilling or broken fibers in cotton garments. The technology is an alternative to the proprietary cellulosic abrasion-control approach that P&G uses in Tide WearCare and Cheer with Liquifiber. P&G and others also employ cellulases to enzymatically sheer off cotton pills.

 "As is often the case," Carrier says, "no one seems to care about certain detergent attributes until one of the majors launches a product containing it." Then, competitors clamor for additives that offer similar performance without copying the pioneer's technology. "If they want that performance, it must come from other means," Carrier says.

 He expects the Alco antipilling product will be able to provide that performance with an added benefit—it can be used in both liquids and powders. The cellulosic material, in contrast, is found only in powdered products.tide_clipped_eps8


CIBA SPECIALTY chemicals is another firm active in color protection, in its case largely through dye fixative technology. Mike Cheek, Ciba's marketing manager for home and fabric care in North America, notes that the company's work in this area is the result of efforts to transfer leading textile chemistry technology to the home care realm.

 Cheek explains: "In the past two years we've said, 'We're providing these effects in the production of fabrics; let's see how we can apply them in consumer products.' " This transfer, he notes, is in keeping with Ciba's corporate goal of providing high-value effects to its customers. In detergents, they tend to be effects above and beyond the traditional cleaning and freshening qualities that consumers have come to expect.

 One result of Ciba's home care effort is its Tinofix dye fixative, which Cheek says is found in cleaning products around the world and is under consideration for use in North American brands. And just as Alco is trying to move from DTI compounds into fixatives, Cheek says Ciba is expanding beyond fixatives into the DTI arena. Now in development in Ciba research labs, he reports, is a unique oxidative additive that selectively destroys fugitive dyes, rather than merely complexing them as current products do.  Cheek acknowledges that incorporating dye-fixative chemistry into laundry detergents can be difficult. "You are trying to apply the fixative to the fabric at the same time that you are trying to remove soil and stains," he says. For that reason, some Ciba customers are considering fixative chemistry as a component of a stand-alone pre- or postrinse laundry auxiliary product.

"Our strategy is to match 'what's needed'—what the consumer wants—with 'what's possible'—what state-of-the-art technology can deliver."
 Ciba is already finding success in the auxiliaries market with its Tinosorb UV absorbers, developed to be added to the wash to increase the sun protection of lightweight garments during the summer months. The company has marketed this product to the detergent industry for several years, and in 1999 it launched a version targeted at fabric softeners. But its first U.S. application will come this spring with the debut of a new Rit brand laundry auxiliary from Bestfoods Specialty Products called Sun Guard.

 Cheek says Sun Guard comes in a packet the consumer adds to the wash along with laundry detergent. Just one treatment, he says, increases the UV protection of clothing to the UV protection factor (UPF) of 30 recommended by the Skin Cancer Foundation.

 In contrast, detergents with Tinosorb built in are meant to work over the course of several washes, achieving a UPF of 15 after five washes and a UPF of 30 after 10 washes. Tinosorb-based detergents have been launched overseas, he says, and they recently debuted in Canada in a store brand marketed by Loblows, a national supermarket chain.


STAND-ALONE laundry products also are seen as a growth market for P&G. As the consultant Cahn notes: "P&G has 55% of the detergent market already. It's almost a commercial imperative to go into these areas when you have the market share that they do."

 P&G is extending the color protection concept to dryer-added fabric softener sheets with Bounce ColorSmart, which it calls the first sheet with specific color-protection technology. Grime says the new sheets are based primarily on a water-soluble diamine chelant that prevents or repairs damage caused by heavy metals to colored fabrics.

 According to Grime, metals such as copper, iron, and manganese from water and dirt can accumulate on fabrics during washing. The chelant in Bounce ColorSmart—which patent literature indicates may be tetrakis(2-hydroxypropyl) ethylenediamine—removes the metals and restores the dyes to their original color, he says.

 One of P&G's biggest recent successes has been its Febreze odor-removal product line, which is based on cyclodextrins—ring-shaped molecules based on six, seven, or eight glucose monomers that can either deliver or entrap odorous compounds.

 Grime notes that the company pioneered cyclodextrin technology in the late 1980s for delivering perfumes to fabrics and releasing them when the fabrics got wet—as when people dry their hands on a towel. "Later on," he says, "consumer insight work told us that the removal of odors around the home was an important market need. We reversed the cyclodextrin technology and used it as a vehicle to pick up or entrap odors."

febreze_clipped_eps11 P&G extended the cyclodextrin concept last summer with two new products: Bounce Fabric Refresher, a product similar to Febreze but sold under the Bounce name; and Febreze Clean Wash, a liquid laundry auxiliary intended to be added to the wash to aid in odor removal. Separately, under the Downy name, the company introduced a new wrinkle-reducing spray thought to be based on silicone chemistry.

 Industry watchers expect extension of existing product lines such as Bounce, Febreze, and Downy to be the soapers' primary means of expansion in the future as they try to pare down the number of brands in their portfolios. "We won't see a lot of new brands, but existing brands will be tagged with different effects," Ciba's Cheek predicts.

 This kind of brand cautiousness might seem to spell a slowing of innovation in cleaning products, but Cheek sees an upside for chemical producers that back up their additives with solid chemistry: Detergent manufacturers that do extend existing product lines are likely to draw on quality ingredients because, he says, "they have to do it right; they can't afford to jeopardize their brand integrity."

 To predict where fabric care innovation is going, Alco's Carrier likes to look back at how the soapers have expanded beyond detergents to satisfy other garment care needs such as fabric softening, stain pretreatment, wrinkle reduction, and odor removal. His conclusion: "We see major soapers trying to get involved in every phase of the garment wearing and cleaning cycle."

 Carrier expects them to develop new cleaning and deodorizing products that work, say, in the hamper. Also, he anticipates a move toward integrated cleaning systems where, for instance, a company's detergent contains a care ingredient that is later activated by using the same company's fabric softener.


THE CHALLENGE for specialty chemical makers will be to supply additives that achieve such goals without significantly raising consumer product prices. For example, Beairsto says one of the detergent industry's most elusive goals through the 1980s and 1990s was a polymeric cobuilder that would work as well as traditional polyacrylates but readily degrade in the environment. Such products are now available, but they are expensive. "For that reason, their acceptance has been very limited," he says.

 Papoulias says ISP is focusing on efficient use of expensive ingredients with what he calls delivery polymers—polymers that either direct an additive at the right target or delay its activation until the right moment in the wash cycle. Likewise, Carrier says Alco is drawing on National Starch's controlled release technology to "keep more expensive components in play during cleaning."

 With each successive generation, cleaning products get more and more complex, but most in the industry are confident that innovation will continue. "Are detergents more complex?" asks P&G's Grime. "Yes, but that's just the nature of modern detergent science. It's the price of entry, and a comprehensive, state-of-the-art product development process manages this complexity." n

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