Surfactants have long been considered the foundation of many household and personal care formulations. In fact, according to a recent study by Kline & Company, Fairfield, NJ, surfactants accounted for 31% of volume sales of personal care products. And where would laundry detergents be without this ubiquitous ingredient? In recent years, the move toward green, gentle formulations both in household and personal care products, continues to impact the surfactant market. At the same time, growing demand in emerging markets is rejiggering how formulators and their suppliers deploy their assets.

Although some marketers are rethinking their reliance on emerging markets for growth, there’s no doubting that a shift in consumption is underway, according to a recent broad surfactant report by Markets and Markets, which predicted the overall surfactant market will grow more than 6% a year to 2017 to reach $36.5 billion. While synthetics will continue to dominate the category, consumption of bio-based surfactants is predicted to show significant growth. And while Europe is expected to remain the largest consumer of surfactants in 2017, Asia-Pacific will overtake North America as the No. 2 surfactant market during that time.

More specifically, anionic, amphoteric/betaine and amino acid surfactants are making gains in both emerging and mature markets, and use of alkanolamides is also growing in mature markets, according to David Kreckman, global product manager, surfactants, Lubrizol Advanced Materials.

A World Without Shampoo?
At the same time,  some predict radical changes are in the works when it comes to personal cleansing formulations.

“I honestly think in five years people are going to go, ‘Oh God, remember when we used to wash our hair with shampoo?’” Michael Gordon, Bumble and bumble’s founder told Wired last month. To meet the needs of these new consumers, Gordon has introduced the Purely Perfect collection of hair care products that includes a $40 cleansing cream that’s free of silicones, detergents and sodium laureth sulfate. What the formula does contain is aloe vera, rose flower, peppermint and evening primrose, stuff that Gordon insists nourish and hydrate the hair. According to the Purely Perfect website, it works on all hair types, including color-treated hair, and users will see dramatic results within one to three uses. 

The introduction of Purely Perfect dovetails with the publication of  “Happy Hair: The Definitive Guide to Giving Up Shampoo.” Author Lucy Aitken Read insists she hasn’t used shampoo in two years and maintains that left to its own devices or washed with natural substitutes, the scalp eventually returns to its natural balance, producing enough oil to keep hair soft and smooth without feeling greasy.

While consumers wait for their hair to return to its natural, non-greasy state, suppliers are reacting to issues that are currently impacting established markets. Robert Griffiths, vice president, sales, Americas at Innospec Performance Chemicals noted that the market for personal care products has been robust in 2014 and that Innospec has benefited as consumers continue to seek out mild, gentle cleansing solutions for both hair and skin care products.

“Our wide range of sulfate free surfactants deliver the performance and functional benefits sought after, including foaming, hair color retention and cost effectiveness,” explained Griffiths.

Meeting Market Trends
Let’s assume that Gordon’s dire prediction for shampoo doesn’t come true. That doesn’t mean there aren’t plenty of issues surrounding personal care formulations—and they’re not all devoted to being sulfate-free. According to David Kreckman, global product manager, surfactants, Lubrizol Advanced Materials, formulators also seek:

• Higher active, preservative-free surfactants that provide formulating flexibility and improve supply chain efficiency;
• Low 1,4 dioxane and amide-free formulations to address new Prop 65 standards and consumer expectations; as well as
• Food-grade preservative-based formulations to align with emerging regulatory and/or consumer expectations.

According to Crystal Clare Rampaul, technical marketing support specialist, Stepan, international safety and environmental concerns associated with certain preservative and preservative systems have led to more customer requests for surfactants that do not require a preservative (e.g., high active ether sulfates), have alternative preservatives, or are self-preserving. Stepan Company has been advertising a few surfactant offerings that are preserved by excess alkalinity, giving formulators more flexibility when developing their finished product. These products include Amphosol HCA-HP (cocamidopropyl betaine), Bio-Terege AS-40 HA (sodium C14-16 olefin sulfonate), and Stepanol WA-Extra HP (sodium lauryl sulfate). Stepan also offers a variety of surfactants with alternative preservatives and preservative systems.

Green is top of mind at AkzoNobel. The company has expanded its agreement with Solazyme and will co-develop up to 10,000 metric tons of algal oil for surfactant production. Company executives expect the Tailored algal oil under development would be able to replace both petroleum and palm-oil derived chemicals in a variety of products including household and personal care formulas. According to Dale Steichen, vice president and director of business development for specialty chemicals, Akzo Nobel, the research project should be completed in the next couple of years. The end result, he explained, will be to offer formulators customized materials that are tailored to meet specific requirements. At the same time, Steichen predicted the Tailored algal oil will offer significant cost advantages.

“It’s good, solid technology,” he told Happi. “It’s part of the journey toward sustainable surfactant production.”

Sustainability and the issues surrounding it, are here to stay, but for now, sulfate-free remains the most visible issue in the industry (for more on sulfate-free technology, read Happi’s new Formulator Forum column on p. 49 in this issue).

“The sulfate-free trend remains strong in North America as the surfactant chassis moves from premium salon brands to a wider mass market product base,” said Griffiths.

What’s more, according to Griffiths, interest in this technology throughout South America is also strong and brings the added challenge of salt-free formulations to the surfactant supplier.

According to Paul Washlock, vice president, personal care, North America, Evonik Corporation, the personal care industry is responding to consumer perceptions by formulating more sulfate-free formulations and making more sulfate-free claims. One challenge in sulfate-free formulations is achieving the desired viscosity. Overcoming the inherent low viscosity and thickening a sulfate-free formulation becomes a major task.

He explained that carbomer-type, polymeric rheology modifiers are well known for building viscosity, and would be a desirable choice for thickening a sulfate-free formulation except for one major drawback: their sensitivity to the presence of salt.
The Personal Care Business Line of Evonik Industries responded to this growing trend by developing a Carbomer-type thickener with salt-tolerant properties. The new Tego Carbomer 841 SER is designed to control the rheology of such surfactant systems. It proved not only to tolerate salt presence but to work synergistically with salt. Efficacy was examined by compatibility testing with different challenging ingredients/systems. Test results showed Tego Carbomer 841 SER works effectively in challenging surfactant systems; e.g. with NaCl alone and/or with other thickening agents that do not function effectively, and finally in sulfate-free and PEG-free formulations.

At the same time, there continues to be a push toward “green” chemistry. That push toward environmentally-friendly products, however, is now going beyond the chemistry.

“For example, our customers are requesting products that reduce the shipping of water, or improve energy efficiency during production or end use by the consumer,” Washlock explained. 

Evonik developed Tego Care PBS 6, a robust O/W emulsifier that provides a solution for low viscosity and/or sprayable emulsions. As emulsion stability is a key criteria, efficacy testing focused on this parameter. Efficacy was evaluated by compatibility testing with different known challenging ingredients and/or conditions. Efficacy was also compared to commercial benchmarks. Various systems were assessed, such as SPF 50 system in conjunction with an insect repellent (IR 3535), phenylbenzimidazole sulfonic acid (2%), natural preservative (benzyl alcohol, benzoic acid, sorbic acids) at low formulation pH (pH <= 5) and high electrolyte concentration such as 1% sodium chloride. These systems were all developed as fluid emulsions to test the effectiveness of the emulsifiers as they are the most difficult to stabilize. All test systems were stable with Tego Care PBS 6, while all benchmark emulsifiers failed in at least (and often more than) one system, according to Evonik.

Stepan executives see growing demand for products with improved aquatic toxicity and biodegradation profiles. According to Anne Gariepy, technical service and sales development manager, Stepan is consistently working to reduce its environmental footprint and continues to focus on delivering environmentally friendly products, including continued listing of surfactants on www.cleangredients.org for customers eager to comply with the US EPA’s Design for Environment (DfE) program.

Similarly, corporate sustainability and social responsibility continue to be a focus for Stepan. As a member of the Roundtable for Sustainable Palm Oil (RSPO), Stepan has publicly committed to begin certification of select facilities for the handling of sustainable palm oil/palm kernel oil by 2015.

“In response to increased interest in sustainable palm derivatives from our customers, Stepan Europe facilities have accelerated the supply chain certification process. Stepan’s Stalybridge and Wesseling facilities are expected to complete certification for handling mass-balance certified palm oil and palm kernel oil by the third quarter of 2014, ahead of our original 2015 commitment,” explained Gariepy.

In California, Stepan continues to respond to customer inquiries and requests for alternative product recommendations for both personal care and home care associated with chemicals being added to the state’s Proposition 65 list. One example is cocamide DEA and DEA replacement. Stepan has been able to recommend and has seen customers successfully use MIPA amides as well as non-amide chemistries in their re-formulation efforts. Stepan plans to launch a new DEA-free amide targeted for personal care in 2015.

According to Penny Antonopoulos, marketing manager, hair and body care, North America at BASF, as consumers become savvier about product claims and performance, they seek surfactant systems that deliver on those promises. In shampoo, that means formulas that fit their own hair type needs along with products that meet the needs of those in their household.

“They want more than just cleansing from their shampoos, they demand formulas that provide moisturization, volume, strengthening and scalp care,” explained Antonopoulos, who told Happi that manufacturers work with BASF Care Creations because of the breadth of technologies and the knowledge of surfactant chemistries.

“With this expertise, we have developed a number of systems that work in synergy with shampoo systems while delivering the performance benefits expected by consumers,” she said.

One such example is Lamesoft Care, a high performance multifunctional wax dispersion suited for surfactant-based applications. Its micronized lipid system offers skin and hair conditioning properties, especially in combination with cationic polymers. It also provides protection against hair breakage and enhances hair gloss and is a patented alternative technology to silicone-based systems. Another shampoo-targeted technology is Plantasil Micro, a transparent microemulsion based on natural, renewable raw materials that can be used to develop transparent formulations. This 100% naturally derived conditioning agent is an optimized blended surfactant-oil system that synergistically improves conditioning performance in rinse-off formulations when combined with cationics.

For body care formulas that do more than just clean, manufacturers look to blend various surfactant chemistries to deliver healthy skin care, according to Antonopoulos. BASF Care Creations Plantaren and Plantacare APG surfactants deliver a wide range of benefits to satisfy the expectations of consumers, including excellent foaming behavior and cleansing properties, yet provide outstanding mildness. BASF’s APGs also help support the emotional benefits that drive consumer purchase behavior, such as formulas that are made-for-me, provide healthy skin and are sensitive skin friendly, allow for an indulging/relaxing experience.

Finally, for formulators seeking cleansing systems for babies and children, BASF offers Plantapon TF, which is billed as a natural surfactant blend based on APG. It delivers effective cleansing properties with excellent foaming and sensory attributes.
“Tear-free certification of the final formulation is also possible when using Plantapon TF,” added Antonopoulos.

Household Innovations
Stepan Company introduced Steposol MET-10U, a novel low HLB nonionic surfactant derived from natural oils on March 24, 2014. Steposol MET-10U provides the strength of a solvent but has the efficacy of a surfactant. This readily biodegradable, environmentally friendly surfactant, which is designed to replace up to 95% by weight VOC solvents, achieves sustainability goals while improving cleaning performance, according to the company. Steposol MET-10U has shown up to 200% increase in cleaning efficiency compared to d-limonene, NMP and glycol ethers in various applications at equal weight, according to Nathan Shook, US distribution sales manager, Stepan.

In the past year, BASF acquired Henkel’s enzyme technology as well as Verenium, a biotechnology company which provided an excellent starting point to enter the profitable, fast-growing detergent enzymes market, according to Shafeek Razak, marketing manager, home care, North America, at BASF.

“Enzymes are one of many options like polymers, chelants and surfactants when formulating a detergent can help support performance and address market needs,” he said.

Razak also pointed out that compaction and increased concentration have provided the opportunity for new innovation within the home care and industrial and institutional cleaning market space.

“This driver is predominantly in the fabric care market, but with some interests for other segments also such as liquid dish and hard surface formulations,” he explained.  “These trends have allowed BASF to examine different product forms but also research different interactions of surfactants, polymers and chelating agents in order to deliver additional formulation benefits for our customers.”

Global Expansion
In their drive to reach underserved consumers around the world, multinational marketers are launching products in all corners of the globe and they expect their suppliers to provide a steady stream of product and innovation wherever their business takes them. Surfactant makers are up to the challenge and many have opened new facilities in new regions during the past year.

For example, Evonik’s Household Care Business Line is expanding into emerging regions, including Asia and South America.

“Our Shanghai plant started up in the fourth quarter and our plant in Brazil is slated to start up later this year,” noted Steven P. Snead-Smith, business director-NAFTA, Household Care, Evonik Corporation. “Some of these regions are expecting double-digit growth in the markets we focus on (home and fabric care). The European and North American market have remained somewhat flat, although there are still opportunities in new product development.”

Innospec opened a lab in Singapore earlier this year to provide local support for customers in the Asia-Pacific market. That move came on the heels of Innospec’s 2013 acquisition of Chemsil Silicones, which expanded Innospec’s specialty silicone business and offered a wider range of solutions to its customers, explained Griffiths.

Lubrizol has expanded its Sulfochem high active, low 1,4 dioxane anionic surfactant manufacturing capabilities and product line and will establish a surfactant manufacturing footprint at its Rio de Janeiro plant to support its customers’ needs in this dynamic region, according to Kreckman.

Stepan is also expanding in Brazil. The company has agreed to acquire a 30 KT/yr sulfonation plant in Bahia, Brazil. According to Crystal Clare Rampaul, technical marketing support specialist, this acquisition is complementary to the Stepan Vespasiano, Brazil plant and provides an opportunity to service customers in the growing northeast region of Brazil. Rampaul noted Brazil continues to be a strategic priority for Stepan. Closing this acquisition is subject to approval by the Brazilian antitrust authorities and by the Industrial Development Superintendence of Bahia State, as well as other customary closing conditions.

In a key personnel move, Scott Behrens, currently vice president of business management with more than two decades of experience at Stepan, has been promoted to the position of vice president and general manager, surfactants. He succeeds John Venegoni, who is retiring as of Sept. 5, 2014.

Whether it involves new personnel, or new products or new production facilities, suppliers continue to invest in order to find solutions for their customers, wherever their business takes them.

New Surfactants

Here is list of new surfactants introduced by industry suppliers during the past 12 months. To learn more, contact the company directly.

BASF Corporation
Florham Park, NJ
Tel: 800-880-5768   
Email: [email protected]; [email protected]
Website: www.carecreations.com; www.care-chemicals.com

DEHYOUND HDL 90
Description: Alcohol ethoxylated and sodium laureth sulfate
Applications: Concentrated detergents laundry, unit dose, liquid hand dish
Use levels: 10% to 65% or as required
Comments: Dehypound HDL 90 is a surfactant system designed for high active detergents. As the home care market continues to evolve towards higher active products–the demand for raw materials that combine performance with low water content become paramount for formulators. In response, BASF introduces Dehypound HDL 90, which incorporates benchmark science in a form that is high active, low in water content, easy to handle, and flexible in use.

DEHYTON PK 35
Description: Cocoamidopropyl betaine
Applications: Personal care—body wash, face wash, liquid hand soap, shampoo; Home care—manual dishwash, liquid laundry
Use levels:  2-5% or as required
Comments: Dehyton PK 35 is an amphoteric surfactant with a dry residue of about 35%. Ideal for use in a variety rinse-off personal care applications such as body wash. It can also be used in household formulations including manual dishwashing and liquid laundry detergents.  It is an effective foam booster and viscosity builder. When combined with anionic surfactants it also achieves a synergistic effect creating a milder formulation.

PLANTAPON TF
Description: Decyl glucoside (and) polyglyceryl-10 caprylate/caprate (and) coco glucoside (and) glyceryl oleate
Applications: Baby care, body wash, face wash, shampoo, sensitive skin formulas
Use levels: ~20%
Comments: Plantapon TF in a natural surfactant blend based on APG technologies for use in gentle cleansing formulas, such as baby care products or other applications requiring mildness. It delivers effective cleansing properties with excellent foaming and sensory attributes. Tear-free certification of the final formulation is also possible when using Plantapon TF.

Innospec Performance Chemicals
Salisbury, NC
Tel: 704-633-8028 
Email: [email protected]
Website: www.innospecinc.com

PUREACT GLUCO RANGE (Pureact Gluco D, Pureact Gluco C and Pureact Gluco L)
Description: Pureact Gluco D—Decyl glucoside, Pureact Gluco C—Coco-glucoside, Pureact Gluco L—Lauyl glucoside
Applications: Shampoos, body washes, facial cleansers, bath oils
Use levels: 1-15%
Comments: Very mild, sulfate free surfactant that has good synergistic effects with other surfactants by reducing irritation of harsh surfactants and improving foam quality to give a rich creamy lather.

ISELUX ULTRA MILD
Description: Water (and) sodium lauroyl methyl isethionate (and) cocamidopropyl betaine (and) sodium methyl oleoyl taurate (and) lauryl glucoside (and) coco-glucoside
Applications: Ultra mild hair and skin cleanser formulations
Use levels: 25-30%
Comments: This concentrated surfactant blend is derived from readily renewable plant sources, is free from sulfates, EO, 1,4-dioxane, nitrosamines, parabens, alkanolamides and formaldehyde. It can be cold processed and provides a dense creamy lather.

Lubrizol
Cleveland, OH
Tel: 800-379-5389
Website: www.lubrizol.com/personalcare/

SULFOCHEM ES-70DXS (2)
Description: Sodium laureth sulfate
Applications: Personal care and home care cleansing applications
Use levels: 10 to 40%
Comments: Versatile primary, plant based high solids surfactant that is easy to process, with lower color, lower residual odor, extremely low residual 1,4 dioxane, with no alcohol, preservatives or antioxidants.

SULFOCHEM TD365DXS
Description: Trideceth sulfate
Applications: Personal care and home care cleansing applications
Use levels: 10 to 40%
Comments: Versatile primary, high solids surfactant that is easy to process, with lower color, lower residual odor, extremely low residual 1,4 dioxane, with no alcohol, no preservatives and no antioxidants

SULFOCHEM ALS-70
Description: Ammonium lauryl sulfate
Applications: Personal care and home care cleansing applications
Use levels: 10 to 40%
Comments: Versatile, non-ethoxylated, plant based high solids primary surfactant that is easy to process, with lower color, lower residual odor, extremely low residual 1,4 dioxane, with no alcohol, preservatives or antioxidants.

Stepan Company
Northfield, IL
Tel: 847-446-7500
Email: [email protected]
Website: www.stepan.com/Steposolmet

STEPOSOL MET-10U
Description: N,N-dimethyl 9-decenamide
Applications: Cleaning agent/solvent replacement in all-purpose cleaner (APC), kitchen degreaser, driveway/concrete cleaner, oven cleaner, car wash/vehicle care, engine degreaser, adhesive remover, paint & ink remover, metal cleaning
Use levels: 0.5-5%
Comments: This naturally-derived, readily biodegradable nonionic surfactant, designed to replace solvents, has a Kauri-Butanol value greater than 1000, boiling point of 297°C, Biorenewable Carbon Index of 75%, and a formulating pH range of 3-12. Visit www.stepan.com/Steposolmet  to obtain more information on promotional literature, starter formulations, application demonstration videos, guidance documents on formulating and material compatibility, safety information and more.