• CORRECTION: This story was updated on July 13, 2012, to correct the derivation of Croda’s Keramimic 2.0 hair treatment protein. The statement that previously read, “Croda has also developed a lanolin-derived keratin protein, Keramimic 2.0 ...,” has been updated to read, “Croda has also developed a wool-derived keratin protein, Keramimic 2.0 ....”

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Volume 90 Issue 20 | pp. 13-18
Issue Date: May 14, 2012

Cover Story

Enhancing Cosmetics

Ingredient makers ramp up research in encapsulation and delivery systems
Department: Business
Keywords: personal care, cosmetics, delivery systems, acquisitions, hair, skin
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HAIR TRIGGER
Mass spectrometry image of peptides in Croda’s Keramimic 2.0 (green) matched to human hair proteins to condition and repair hair.
Credit: Croda
A mass spectroscopy image of peptides in Croda’s Keramimic 2.0 (in green) matched to human hair proteins so they condition and repair human hair.
 
HAIR TRIGGER
Mass spectrometry image of peptides in Croda’s Keramimic 2.0 (green) matched to human hair proteins to condition and repair hair.
Credit: Croda
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DELIVERY VEHICLE
A surfactant concentrated in the lamellar phase and engineered to form an onionlike vehicle has voids that can encapsulate and deliver active ingredients to skin and hair.
Credit: Rhodia
This drawing of a surfactant concentrated in the lamellar phase has voids which can encapsulate and deliver active ingredients to skin and hair.
 
DELIVERY VEHICLE
A surfactant concentrated in the lamellar phase and engineered to form an onionlike vehicle has voids that can encapsulate and deliver active ingredients to skin and hair.
Credit: Rhodia
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DRY WATER
Hydrophobic fumed-silica particles surround water droplets, creating a flowable powder slurry when compressed.
Credit: Evonik
Hydrophobic fumed silica particles surround water droplets creating a flowable powder that wets out when compressed.
 
DRY WATER
Hydrophobic fumed-silica particles surround water droplets, creating a flowable powder slurry when compressed.
Credit: Evonik
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CAPTIVATING CONCEPT
Before being applied to skin, alginate-based pearls containing antiaging ingredients are mixed.
Credit: Capsum
Capsum’s alginate-based DuoPearls containing anti-aging ingredients are mixed into an activating cream where they melt before application to the skin.
 
CAPTIVATING CONCEPT
Before being applied to skin, alginate-based pearls containing antiaging ingredients are mixed.
Credit: Capsum
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FLOATERS
Cellulose-based beads suspended in gel contain glitter pigments. They can also be used to preserve and encapsulate plant extracts, vegetable oils, and other cosmetic ingredients.
Credit: Pelletech
Cellulose-based beads suspended in gel contain glitter pigments but can also be used to preserve and encapsulate plant extracts, vegetable oils, and other cosmetic ingredients.
 
FLOATERS
Cellulose-based beads suspended in gel contain glitter pigments. They can also be used to preserve and encapsulate plant extracts, vegetable oils, and other cosmetic ingredients.
Credit: Pelletech

In February, Air Products & Chemicals acquired Rovi Cosmetics, a German maker of cosmetic active ingredients and encapsulation systems. The purchase was small—only 18 people were involved—but it marked Air Products’ first significant acquisition in the personal care space and put the firm in the middle of a technically challenging segment of the cosmetics business: ingredient encapsulation and delivery.

Like Air Products, many big chemical firms—including Clariant, Solvay’s Rhodia unit, BASF, and Lonza—have enlarged their participation in the growing and profitable cosmetic ingredient business through acquisition. They are attracted to a global beauty and personal care market that the consulting firm Euromonitor International set at $425 billion last year.

As participants in the personal care sector, many of the chemical giants are also competing for position in the increasingly sophisticated delivery systems arena. And smaller players, often adapting pharmaceutical-actives encapsulation and release techniques, are bringing delivery innovations to cosmetics makers as well.

Ingredients such as anti-inflammatory, dandruff prevention, and wrinkle reduction actives are often expensive. And they can degrade in the bottle if they aren’t protected. Some delivery systems protect against degradation. Others are intended to suspend ingredients, such as sunscreens, on the skin’s surface. Or they can be designed to deliver a cell-reparative payload just below the surface of the skin.

Ameann DeJohn, a product development consultant to small and midsized cosmetics makers, estimates that only 10 to 20% of cosmetics on the market today contain active-ingredient delivery systems. But in five years, she predicts, 35 to 45% of newly launched products will incorporate such systems.

Interest in delivery systems among luxury cosmetics makers is also on the rise. In the March edition of the newsletterBioencapsulation Innovations, Eric Perrier, executive vice president of research at the luxury goods firm LVMH, noted in an editorial that better encapsulation systems are needed to target specific cells, protect unstable ingredients, reduce side effects, and enliven product appearance.

Confirming interest at cosmetic formulation houses are data from Chemical Abstracts Services’ Search Service, Science IP. A recent search shows 2,194 patents were filed on hair and skin ingredient delivery systems in 2011, up nearly 25% from five years earlier.

Nikola Matic, a project manager at market research firm Kline & Co., reports that ingredient suppliers sell about $4 billion annually of specialty actives, specialty ingredients, and actives delivery systems in Europe. Although the delivery systems sector is small, with sales of about $106 million in 2010, it is growing faster than the other ingredient categories he covers. He predicts the sector will grow 7% annually over the next five years.

Already popular in Europe are liposomes and other phospholipid-based delivery systems, Matic says. After initially penetrating the high-end prestige products market, novel delivery systems are now entering mass-market categories including sun care, hair care, lip gloss, and color cosmetics.

Cosmetics makers are adopting novel delivery systems for skin using a variety of micelles, vesicles, surfactants, and polymers, but they don’t often reveal those details to the public, Matic notes. One company that makes an attempt to provide some information is Switzerland-based Laboratoires La Prairie. It ambiguously describes its antiwrinkle Skin Caviar Liquid Lift as containing “pearls” that hold a dose of “pure Caviar Extract” in a liquid gel serum “brimming with anti-wrinkle peptide.” Capsum, a small French delivery systems supplier, says it worked with La Prairie to develop the pearl technology.

Big chemical companies are also attracted to this kind of supply opportunity. “We were interested in Rovi because of the combination of actives and delivery systems it offered to customers,” says Solomon Lemma, Air Products’ global personal care business manager. The firm is already a maker of polymers for personal care products.

With Rovi, Air Products’ sales to cosmetics customers approach $50 million annually, moving it closer to its goal of being a full-service provider to the industry, Lemma says. But also important was the science-based approach Rovi takes in researching products for customers.

Since the acquisition, scientists from Air Products and Rovi have worked together to develop Dermoprotectyl, a skin care ingredient that combines two systems for delivering actives. One system, based on inulin sugar nanoscale vesicles, places sunscreen ingredients on the surface of the skin. A second system, using lipid protective spheres, deposits vitamins E and C just below the surface of the skin for a second line of defense against sun-induced damage.

Michael Sacher, Rovi’s delivery technologies R&D director, says his company brings deep academic roots to Air Products. Rovi works in close cooperation with universities in Germany to develop and document the effectiveness of its formulations. For instance, using confocal laser scanning microscopy, the firm is able to show customers that Dermoprotectyl deposits two sunscreens, octocrylene and avobenzone, on the skin’s surface. The technique also provides evidence that the vitamins penetrate 30 μm under the skin’s surface.

Like Air Products, Clariant is trying to build up its personal care business. “We decided that personal care is a core business for us,” says Ralf Zerrer, who is in charge of strategic marketing for Clariant’s industrial and consumer care business.

Clariant’s strengths are in traditional synthetic organic chemistry. So last August, Zerrer says, the firm bucked up its personal care credentials through a partnership with Belgium’s KitoZyme that gives Clariant access to fungi-derived personal care biopolymers. The company introduced three biopolymers at the In-Cosmetics show in Barcelona last month from its KitoZyme partnership.

Then in October 2011, Clariant bought Germany-based Ober­hausen Technology Center to bring formulation expertise in-house. OTC employs 10 chemists who are specialists in delivery technologies for personal care and household ingredients. Zerrer says Clariant is looking for other acquisitions and cooperation agreements.

When Clariant bought OTC, the smaller firm was developing ingredient encapsulation equipment it intended to license to customers. Later this year, Zerrer says, Clariant intends to go ahead with OTC’s plan to place the equipment in customers’ manufacturing facilities.

A Web link will allow Clariant to monitor the equipment. Customers will be able to use their own or Clariant-supplied raw materials to encapsulate active ingredients, such as retinol, in microsized particles. Retinol is a form of vitamin A known to repair skin, but it can irritate skin in large doses.

And for those who don’t want to encapsulate the ingredients themselves, Clariant says OTC will do it for them. At this point Zerrer is not prepared to reveal the mechanism behind the encapsulation technology, only saying it is “like enrobing a nut in chocolate.”

German chemical maker BASF has built up an impressive collection of cosmetic ingredients and technologies in recent years that includes actives delivery systems. In December 2010, it bought surfactants maker Cognis, which brought with it the active-ingredients supplier Laboratoires Sérobiologiques.

Earlier acquisitions such as sunscreen actives maker Ciba and pigment producer Engelhard—which owned delivery systems experts Collaborative Laboratories and Coletica—also enlarged BASF’s stable of products. “We have the broadest offerings and capabilities among ingredient suppliers in the personal care industry,” claims Simon Medley, senior vice president of personal care.

When creating products that deliver active ingredients to skin and hair, formulators must consider things such as polarity, solubility, and molecular weight, notes Ulrich Issberner, a former Cognis executive who now heads hair care marketing at BASF. Among BASF’s delivery systems is the Tinoderm line of phospholipid encapsulants, which the firm sells loaded with active ingredients such as vitamin A or E.

Surfactants are the basis of a delivery system offered by French specialty chemicals maker Rhodia. The firm, which has grown with the acquisition of U.S. surfactants company McIntyre in 2009 and Chinese surfactants maker Feixiang in 2010, has developed a fragrance and actives delivery system for body washes known as Miracare SLB.

The system is based on a coconut-derived surfactant in the lamellar phase, engineered to form an onionlike vehicle that captures fragrances and actives for dandruff, acne, and sun protection products, says Sandra Catarino, business development manager. Customers that want to keep fragrance on the skin can use a Rhodia formula that combines Miracare SLB with a cationic guar polymer, Catarino notes.

Dow Chemical too has enlarged its footprint in the personal care ingredient business, most recently through the 2009 acquisition of Rohm and Haas. Dow’s enhanced acrylic polymer expertise has led to a new polyacrylate, Epitex 66, designed to deposit sunscreens on skin and resist wash-off, notes Lionel Genix, global personal care marketing director. Formulations made with Epitex 66 won’t feel sticky as some waterproof formulations can, he adds.

In designing Epitex 66, Genix says, Dow considered other areas in which it has expertise, including cellulosic and polyurethane chemistry. But the polyacrylate gave the emulsion the right skin-feel. Sunscreens formulated with it maintain their sun-protective abilities better than those with pyrrolidinone eicosene copolymers, he says.

Sunscreen delivery systems have also been on the minds of product designers at Croda. The firm acquired ICI’s Uniqema business in 2006, enlarging its presence in personal care and also providing it with titanium dioxide-based sunscreens.

At the In-Cosmetics show, Croda exhibited a film-forming polymer designed to deposit sunscreen evenly on skin. According to Helene Hine, a marketing manager for the firm, SolPerForm 100 is a cross-polymer derived from poly­vinyl pyrrolidone and wheat protein. Often cosmetics makers find that it is difficult to evenly coat the uneven surface of the skin, Hine says, leading to low sun-protection-factor (SPF) values for their lotions. SolPerForm covers skin more evenly, thus uniformly dispersing ingredients and boosting SPF values, she says.

Croda has also developed a wool-derived keratin protein, Keramimic 2.0, to repair the outer layer of hair damaged from exposure to bleach, colorants, and other styling treatments. The firm puts the keratin through a proprietary process to ensure that it replicates the amino acid sequences naturally found in the cuticle and cortical regions of human hair. Then, Croda quaternizes the protein to make it cationic.

Using time-of-flight mass spectrometry, the company was able to verify its claim that Keramimic 2.0 repairs hair. The imaging technique shows that Croda’s cationic keratin repair protein was attracted to and filled in the most damaged sections of hair, which are anionic.

The analytical technique illustrates the lengths to which cosmetics ingredient suppliers are willing to go to provide science-based proof of their products’ usefulness. “Customers are asking for more data because consumers are demanding more performance,” Hine says.

A concept introduced by Evonik Industries shows that ingredient suppliers will even go down entirely new paths to create an effective cosmetics delivery system. Introduced last year, the system transforms powders into creams through the use of hydro­phobic and hydrophilic silica particles.

According to Matthew Romaine, an Evonik marketing manager, the powder-to-cream system is based on two types of silica. Particles of the firm’s hydrophobic Aerosil fumed silica are first used to surround tiny 2- to 4-µm droplets of water that may also contain a small amount of pigment. Evonik calls these captured droplets “dry water.”

The firm’s hydrophilic Sipernat precipitated silica is then used to encapsulate a blend of oleophilic emollients and other ingredients that may include fragrances and vitamins. When a blend of the two powders is rubbed on the skin, the dry water flushes out the emollient blend and creates an emulsion.

The powder-to-cream system can be used for hair-styling formulations, sunscreens, antiaging skin treatments, blushes, and other cosmetics. Romaine says Evonik is working exclusively with private-label cosmetics maker Dermaceutical Laboratories, of Teterboro, N.J., to bring the concept to market.

Evonik is approaching customers with ingredients and technologies assembled through mergers and acquisitions from years past. For other firms, the deals are much more recent. For example, Lonza, long a supplier of preservatives to the personal care industry, acquired the microbial control specialist Arch Chemicals just last year.

Vince Gruber, who came from Arch and is now global personal care R&D director at Lonza, is particularly enthusiastic about Lonza’s expertise in fermentation technology and hopes to harness it in the personal care business. Some of Arch’s active ingredients are the products of fermentation.

And Gruber says he is interested in developing active-ingredient delivery systems for cosmetics using Lonza’s pharmaceutical expertise. He cautions, however, that translating such knowledge to personal care is not a trivial matter and is likely to take some study.

Ashland, which enlarged its personal care presence last August through the purchase of International Specialty Products, is also considering new delivery systems for its portfolio of peptides, extracts, antioxidants, and other ingredients. The acquisition included ISP’s Hallcrest unit, which uses a phase-separation technology to encapsulate hydrophobic materials in capsules made of gelatin and gum arabic.

According to James Misch, formerly with ISP and now care specialties group vice president at Ashland, the firm is one to two years away from introducing new encapsulation technology. “We see vast opportunities in delivery systems. We’re looking to invest in our own technology and in the technology of others,” he says.

Executives at smaller companies would argue that it doesn’t take acquisitions to create effective cosmetics delivery technology. For example, the privately owned preservative maker Troy Corp. has developed an encapsulant for iodopropynyl butylcarbamate (IPBC), which protects aqueous formulations from yeast and mold. Although IPBC is typically used in personal care products at a concentration of 0.02% or less, it has the potential to irritate the skin of sensitive individuals, notes Klaus Nussbaum, Troy’s global head of home and personal care.

Pharmaceutical companies have developed coatings that slowly dissolve to release their contents, Nussbaum points out. Taking a lesson from the drugmakers, Troy developed a sugar encapsulant that gradually meters out IPBC into a formulation. The technology ensures that low and effective rates of IPBC will protect users and extend the shelf life of products.

Smaller companies are also offering encapsulation techniques that can work with any number of active ingredients. Capsum, the French company that worked with Laboratoires La Prairie, has developed three different-size encapsulation systems, according to Thomas Delmas, a senior researcher at the firm.

The first is called the DuoPearl and DuoPearl Inverse system. The pearls, about 4 mm wide, are either crushed or dissolved in a cream before being spread on the skin’s surface. They consist of three layers: an alginate hydrogel envelope inside of which is an oil- or water-based active-ingredient droplet surrounded either by an aqueous or lipophilic solution, respectively. In a second encapsulation system, called NeoShell, 20- to 200-μm polymeric capsules surround hydrophilic active ingredients. And a third system, called Neo­Gouttes Target, uses 20- to 200-nm nanoemulsions to encapsulate lipophilic actives.

Formed by two scientists and a technology manager in 2008, Capsum employs 25 people and has a portfolio of 25 patents. It has grown with the support of angel investors and the French government, explains Thomas Bibette, business development manager for the firm. He is the son of one of the scientist founders, Jérôme Bibette, director of the Colloids & Divided Materials Laboratory at the École Supérieure de Physique et de Chimie Industrielles in Paris. The other scientist founder is David A. Weitz, director of Harvard University’s Materials Research Science & Engineering Center in Cambridge, Mass.

The NeoShell capsules, developed in Weitz’s lab, are copolymers of polylactic acid and polyethylene glycol. Several NeoShell capsules, each with a different antiaging and antioxidant load, can be combined in one larger polylactic acid envelope, Delmas says. The technology isolates several compounds that could otherwise not be mixed together until applied to the skin, he notes.

The NeoGouttes Target technology was originally developed to encapsulate difficult-to-stabilize chemotherapy agents, Delmas says. Jérôme Bibette’s lab developed the nanoemulsion particles, which are mixtures of lipids and surfactants formulated to keep lipid-based active ingredients from crystallizing.

For use in personal care products, sugars or peptides can be attached to the outside of the particles, allowing them to target keratinocytes, fibroblasts, or melanocytes just under the surface of the skin. Once there, they can deliver a payload of antiaging or skin-lightening ingredients, he says.

Other firms also use encapsulation technology adapted from the drug industry. For example, Spirig, a Swiss pharmaceutical maker, set up Pelletech several years ago to cater to the personal care industry, says Reto Brügger, Pelletech managing director. Pelletech benefits from Spirig’s expertise in formulating pellets containing active ingredients for oral-dosage capsules.

The firm uses an entrapment technology based on cellulose, lactose, or mannitol, Brügger says, to encapsulate actives such as vitamins, fragrances, and pigments. Delivered as dry beads, they swell and soften in a water-based formula and then dissolve under pressure.

Formulators are captivated by the potential advances that delivery systems promise. LVMH’s Perrier, for instance, is intrigued by research trials that suggest delivery systems can enhance the performance of cosmetics. And like the delivery systems developers, he has great expectations for them. ◾

 
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