CARE

ALEXANDER THIEMANN, JESSICA SCHOLZE, SILVANA ESTARITA, KURT DIEKER Dr. Straetmans GmbH, Merkurring 90, 22143 Hamburg, Germany

Alexander Thiemann

Conditioning, naturally going back to earth!

KEYWORDS: conditioner, dermofeel® quadegra, natural, potato starch, ready biodegradability, performance

Hair care cosmetic formulators permanently strive for new conditioners which allow them to satisfy the Abstractdiverse demands of the growing natural cosmetic market. In response to these demands dermofeel® quadegra, a liquid, preservative-free conditioner, which combines performance and easy handling with environmental friendliness has been developed. dermofeel® quadegra conditioning agent is natural-derived from chemically modified potato-starch and is easily and also cost-effectively applicable in a variety of formulations, like , shower gels and sprays. dermofeel® quadegra stands for low moisture pick up and a substantive but at the same time removable conditioning film. These characteristics offer formulators a unique balance between instant conditioning performance and hair style manageability. In this study we report dermofeel® quadegra´s biodegradability, aquatic toxicity and performance and make extensive comparisons to benchmark conditioners of petrochemical, as well as natural origin.

INTRODUCTION Conventional conditioners of petrochemical feedstock (e.g. Polyquaternium-7) provide acceptable In the last couple of years consumers and producers of solutions with respect to handling and cosmetic cosmetic products increasingly targeted their focus on performance. However, most of these exhibit questions regarding the environment. This trend is the disadvantage of poor biodegradability with the result reflected in growing market numbers worldwide and in an of accumulation in the environment. increasing range of natural and sustainable cosmetic raw materials implemented in personal care products. In As a consequence, polymers based on natural Germany, the largest natural cosmetic market in Europe, backbones have been developed in order to provide raw total sales of natural cosmetic products increased in 2012 materials with an improved inherent biodegradability. by 5.5 percent, claiming a total share of 6.8 percent of These natural backbones were initially found in the cosmetic market (1). Worldwide in 2011, according to polysaccharides such as cellulose (e.g. the Kline Group, natural and natural personal Polyquaternium-10) or guar (e.g. Guar care products were estimated to account for 25 billion Hydroxypropyltrimonium Chloride). Nowadays in hair care USD of the market (2) with a double digit growth between the most widely used conditioners comprise primarily the 2005 to 2010 (3). Polyquaternium-10, but also Polyquaternium-7, This global market growth is expected to continue and and cationic guars like Guar Hydroxypropyltrimonium thereby emphasizes the need for cosmetics producers to Chloride. While some of these polymers lack the position their product lines adequately in this innovative requested biodegradability and/or low eco-toxicity others and promising market segment. lack the desired performance. This illustrates the continuous challenge to the hair of In addition to the performance and the natural origin of a developing a natural-based conditioning agent with the cosmetic raw material, producers also begin to consider right balance of environmental friendliness and its ecological footprint. For hair care products, which are performance. released to the aquatic environment after varying stages of sewage treatments, the ecological footprint depends As a response for the needs of the market a potato on the biodegradability and aquatic toxicity of each starch-derived, readily biodegradable hair conditioner individual ingredient. with an excellent performance, comparable to

24 H&PC Today - Household and Personal Care Today, Vol. 9 nr. 5 September/October 2014 benchmark products has been developed. Liquid DOC (Dissolved organic carbon), CO2 production or O2 dermofeel® quadegra (INCI: Aqua, Starch uptake. Different test methods (OECD 301 A and D) were Hydroxypropyltrimonium Chloride, , Sodium Lactate, applied due to differences in method-requirements of the Lactic , Sodium Chloride, Glycerin, Levulinic Acid, tested substances depending on their specific physical p-Anisic Acid) allows easy handling in the laboratory or characteristics (e.g. solubility, vapor pressure, adsorption). during high-scale product manufacturing (Figure 1). Nevertheless, both test methods are comparably eligible dermofeel® quadegra´s substantive but easily removable and are internationally approved for diagnosis of ready film gives a good balance between adequate biodegradability. In Germany the OECD tests are part of conditioning and dry hair manageability. Moreover is it the administrative regulations for water endangering readily biodegradable and possesses a low aquatic chemicals (VwVwS) (5). toxicity. The results show that dermofeel® quadegra components after 28 days were reduced to an extent of 64 percent, BIODEGRADABILITY indicating dermofeel® quadegra´s ready biodegradability. In contrast the benchmark conditioner, The biodegradation Polyquaternium-10, after 28 days was degraded to an of a substance can extent of solely 17 percent. Consequently the benchmark be described as its conditioner did not fulfill the requirements and therefore, decomposition by according to our results, cannot be regarded as readily micro-organisms biodegradable, a result further supported by the (mainly aerobic manufacturer’s product information (6). bacteria) into simpler substances such as carbon dioxide, water and ammonia (4). Figure 1. Liquid dermofeel® quadegra.

The biodegradability of dermofeel® quadegra and a benchmark conditioner Table 1. Results of the ready biodegradability and aquatic toxicity (Polyquaternium-10) was tested by external studies of dermofeel® quadegra. institutes (Centre de Transfert de Technologie ODESSOL, France; AnoxKaldnes, Sweden) via OECD 301 D (“Closed bottle method”) and OECD 301 A (“DOC die-away”) type tests, respectively (detailed test AQUATIC TOXICITY results available upon request, summary in Table 1). A potential aquatic toxicity of dermofeel® quadegra was The biodegradability test methods of the OECD 301 series analyzed via an acute immobilization test of daphnids screen for ready (fast) biodegradability of chemicals in (Daphnia magna). The test was performed by an external an aerobic aqueous solution. Test substances were test institute (Centre de Transfert de Technologie inoculated and incubated for 28 days in a mineral ODESSOL, France) according to the OECD guideline 202. medium containing an inoculum of microorganisms. In this test, in an aqueous solution, the concentration Degradation of the test substance over time was (EC50(48h)) of dermofeel® quadegra´s components was measured with either one of the degradation parameters determined at which 50 percent of the daphnids were

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The easy-to-use blends for economic and 9 various products safe preservation can be used in nature-inspired or certified natural shampoos or shower gels. The conditioning agents were incorporated for the test in a quite simple, economically orientated Ether Sulfate/Betaine anionic base (see Table 2). The conditioners were included into the base according to the concentrations recommended by the suppliers. For the effective prior elimination of potential contaminants on the European human hair (strongly bleached, remis; Table 2. Formulation of the Ether Sulfate/Betaine surfactant shampoo base Kerling) from previous treatments (e.g. bleaching, implemented in performance evaluation tests with various conditioners. transport), and prior to combing force measurements, each individual hair tress was washed three times with 10 percent Ether Sulphate. immobilized after 48h due to toxic effects. In our test the Then determination of the basic combing force of each EC50(48h) of dermofeel® quadegra´s components individual hair tress was conducted. A potential change in accounted for 53 mg/L (Table 1). the combing force of each individual hair tress was This relatively low aquatic toxicity together with the ready measured after three washes with the shampoo base biodegradability indicate a very low overall eco- including the different test conditioners. In addition to toxicological impact of dermofeel® quadegra on combing force measurements a comparative, synchronic, aqueous environments. The Polyquaternium-10 sensory assessment of the hair and an assessment of the benchmark showed in similar tests, according to the foam quality during the shampoo procedure was manufacturer, a slightly higher toxicity with an EC50(48h) conducted by in-house experts. value between 34-48 mg/L (6). Another benchmark raw material, Guar Hydroxypropyltrimonium Chloride, has The combing force reduction of shampoo including the been widely accepted as an alternative conditioner for market benchmark Polyquaternium-10 turned out as good natural shampoo formulations. It does in fact perform as expected (-71 percent combing force reduction) better in terms of biodegradability and aquatic toxicity (Figure 2). The combing force reduction of dermofeel® (7), but does not deliver the same performance when it quadegra (-64 percent combing force reduction) showed comes to the reduction of combing forces (see Figure 2) that it has a conditioning effect, superior to or hair style lasting (see Figure 3). Polyquaternium-7 and Guar Hydroxypropyltrimonium Chloride and close to the Polyquaternium-10 benchmark conditioner. Guar Hydroxypropyltrimonium Chloride, the COMPARING PERFORMANCE benchmark conditioner when it comes to foam quality, revealed a very fine and creamy foam, but at the same New natural or naturally-derived conditioning agents time was largely rinsed-off and therefore the caring have to fulfill certain performance expectations in order sensation on the hair was quite poor. This in parts to compete with benchmark conditioners in the market. contributed to its low reduction of the combing force (-7 As an immediate effect a conditioner has to exhibit percent combing force reduction). dermofeel® sufficient adhesion to the hair in order to allow for a quadrega´s foam quality alone was comparable to the satisfactory combing performance and for a regulation of foam quality gained from both Polyquaternium polymers, the humidity uptake by the hygroscopic hair. In the long run and as a consequence of repeated applications, a conditioner should not build up multiple layers by irreversible adherence to the hair in order to avoid bad hair manageability and limited hair style lasting. In this study the performance evaluation of dermofeel® quadegra included comparisons to market benchmark conditioners on the wet hair combing force and on the hair style lasting in terms of curl retention.

Combing force and foam quality Wet hair combability was tested in Dr. Straetmans application laboratories to learn more about the instant performance on combing force reduction of dermofeel® quadrega compared to the benchmark products Polyquaternium-10, Polyquaternium-7 and Guar Hydroxypropyltrimonium Chloride. Furthermore ® the synergistic effect of dermofeel quadegra on Figure 2. Wet hair combing force reduction after 3 washes with a Sulfate/Betaine Guar Hydroxypropyltrimonium Chloride and Dr. anionic surfactant shampoo base containing the different conditioners. ® Percentages represent the amount of active conditioning substances Straetmans dermofeel P-30 (INCI: PCA Glyceryl implemented into the base. P-values (unpaired, two-sided t-test) indicate Oleate) was analyzed. Similar to Guar significant differences between the combing force before and after the washes. Hydroxypropyltrimonium Chloride, dermofeel® P-30

26 H&PC Today - Household and Personal Care Today, Vol. 9 nr. 5 September/October 2014 with an average quantity of creamy foam. The Hydroxypropyltrimonium Chloride. The lasting of the combination of dermofeel® quadegra with Guar differently treated hair curls was evaluated simultaneously Hydroxypropyltrimonium Chloride resulted in a synergetic in a chamber with high humidity (aprox. 80 percent) and effect of a better combing force reduction due to was documented after 4 hours. dermofeel® quadegra and the typically creamy foam of Guar Hydrypropyltrimonium Chloride. An even better The results show that the hair tress washed with dermofeel® synergy of fantastic foam quality and compatible quadegra (Figure3, No.4) in a humid environment combing force reduction was only achieved by the revealed less of a curl drop than its competitors. This results combination of dermofeel® quadegra and dermofeel® indicate, that dermofeel® quadrega alone and in P-30. Due to the improved adherence of dermofeel® P-30 combination with dermofeel® P-30, similar to other liquid compared to Guar Hydroxypropyltrimonium Chloride, a starch raw materials, stands for low moisture pick up. compatible combing force reduction was combined with Furthermore the conditioner, in contrast to an excellent foam quality and quantity. Polyquaternium-7 (No.3), Polyquaternium-10 (No.8) and even Guar Hydroxypropyltrimonium Chloride (No.6), after repeated washing doesn`t seem to overload the hair tress with heavy multilayer films, which weight would contribute to a loss in curl retention. These two characteristics offer a unique balance between a decent conditioning film on the cuticle and dry hair manageability – nearly independent from the number of applications.

CONCLUSION

Dr. Straetmans dermofeel® quadegra, as a naturally- derived conditioner, combines eco-friendliness with Figure 3. Comparison of curl retention of dermofeel® quadegra, excellent performance. This study shows that dermofeel® benchmark hair conditioners and combinations in a ~80 percent humidity chamber. 3: Polyquaternium-7; 4: dermofeel® quadegra; quadegra, due to its low aquatic toxicity and its fast 5: dermofeel® quadegra & Guar Hydroxypropyltrimonium biodegradation, exhibits no severe danger for aquatic ® Chloride; 6: Guar Hydroxypropyltrimonium Chloride; 7: dermofeel ecosystems. Performance evaluation showed that quadegra & dermofeel® P-30; 8: Polyquaternium-10 dermofeel® quadegra successfully reduced combing forces of wet hair, without extensive build-up effects. Furthermore dermofeel® quadegra combines easy handling in low and high-scale preparations of Curl retention formulations, due to its liquid consistency with a lower The efficacy of a conditioner depends on its ability to form moisture uptake on the hair compared to benchmark a complex with the hair due to electrostatic interactions. conditioners. A lower moisture uptake provides the hair The resulting complex between the anionic and the with a robust volume and prolonged hair style lasting, cationic conditioner can actually be more stable than any features not solely interesting for tropical countries with complex that might be formed by attraction between a high temperatures and humidity. conditioner polymer and an anionic surfactant such as sodium lauryl sulfate. This means that some of these polymers can be resistant to removal, even with clarifying REFERENCES AND NOTES shampoos. A consequence might be, after repeated shampooing, a build-up effect of heavy multiple layers of 1. Dambacher E.: Der Markt in Deutschland, in Naturkosmetik conditioner, causing deficiencies in the hair style Jahrbuch 2013, Edited by Dambacher E., Ed. manageability and lasting (8). So on one hand conditioners Naturkosmetikverlag e.dambacher, Dortmund, Germany have to exhibit a sufficient adhesion to the hair in order to (2013). 2. Dambacher E.: Der internationale Kosmetikmarkt, in prevent removal during the rinsing process, on the other Naturkosmetik Jahrbuch 2013, Edited by Dambacher E., Ed. hand they should not form multilayer films during repeated Naturkosmetikverlag e.dambacher, Dortmund, Germany shampooing with subsequent overload. Furthermore, they (2013). have to be compatible to aqueous systems in order to 3. St Paul, M.N., “Natural personal care - an overview of the US enable the production of suitable cosmetic formulations market”. Kline & Company, March 15 (2011). but at the same time they should have an intrinsic 4. Glossary of Environment Statistics, Studies in Methods, Series F, resistance towards the uptake of moisture. No. 67, United Nations, New York (1997). 5. Bundesministerium der Justiz, Verwaltungsvorschrift To test for these complex demands the curl retention of wassergefährdender Stoffe (VwVwS) - Administrative hair tresses was tested after repeated washing. Therefore Regulations for water endangering chemicals, (1999). 6. Safety Data Sheet UCARE™ Polymer JR-400, Amerchol hair tresses were washed in total 20 times with the Corporation: http://www.dow.com/webapps/msds/ShowPDF. Ethersulfate/Betaine surfactant shampoo base (Table 2), aspx?id=090003e88007e86e (last checked on Apr. 28 2014). ® th containing either Polyquaternium-7, dermofeel 7. Mabille, C., Catarino, S. “Designing environmentally-friendly & quadegra, Guar Hydroxypropyltrimonium Chloride or cost-efficient shampoos”, Body Care: grooming, protection & ® Polyquaternium-10 alone, or dermofeel quadegra in hygiene – H&PCToday 8 (2), 20-23 (2013). combination with dermofeel® P-30 or Guar 8. US 4,725,433. Matravers, P. Issued Feb. 16 (1988).

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