From BB to CC Creams Innovative Formulation of Multitasking Care T. Baldecchi J. zur Lage, R. Bai, S. Wu J. Zhuang, G. Witte, F.

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1 English Edition International Journal for Applied Science Personal Care Detergents Specialties T. Baldecchi J. zur Lage, R. Bai, S. Wu J. Zhuang, G. Witte, F. Pflücker From BB to CC Creams Innovative Formulation of Multitasking Care

2 T. Baldecchi R, J. zur Lage*, R. Bai**, S. Wu***, J. Zhuang****, G. Witte*, F. Pflücker* From BB to CC Creams Innovative Formulation of Multitasking Care The Origins The German dermatologist Dr. C. Schrammek is said to be the inventor of the original»blemish Balm«product that was reported to be created in the 1960 s (1). The main goal of the original multi-tasking product was to protect and soothe the skin after surgery and at the same time, to provide light coverage to hide marks or redness that could have been induced by this operation. The product was taken to South Korea by nurses in the 1970 s and, by word of mouth, it gained a lot of popularity in that country during the 1980 s and 1990 s. Its success is due to the natural nude look that the product confers while smoothing out any visible imperfection on the skin. Compared to foundation, its added value is that it is less drying and heavy. It also has added benefits such as antiaging, sun-protection and skin whitening properties. One proof that these products have become a compelling reference in Asia is that the creams have successfully broadened their market segments, as BB creams for men s care exist in Korea and Japan. Because of the fact that the wording Blemish Balm is protected by copyright, the name»bb cream«is the phrase that is widely used nowadays. Nevertheless, to get rid of this barrier, some creative brands make the initial BB stand for Blemish Base, Beauty Balm or Beblesh Balm. The World is a Global Village As it was said to be the beauty secret of popular Korean actresses and singers, the use of the BB cream rapidly spread to other Asian countries such as Japan, Taiwan, China or Singapore in the following decade. In the last two years, BB creams also raised interest in Western countries. The possibility to replace a foundation (2), a moisturizer, an antiaging cream, a UV-protection (and even more) with a single product was certainly the main reason for their fast-growing popularity among urban and active women who have less and less time to spend in caring for their look. Nevertheless, even though the concept of the hybrid cream was seductive, formulators had to adapt the product to meet the specific needs of their targeted customers before such a product could be successful in Europe and in the USA. Changes in the Abstract Last year, European and North American customers saw the novelty come from East with the first massive launches of BB creams. This multitasking product immediately became a huge trend because the cream delivers immediate results by correcting visible skin imperfections --like a foundation-- and also adds long term benefits, by treating the skin -- like a traditional skin care product. sensorial profile had to be taken into account, same as the colors and shades to match a Caucasian or Ethnic skin tone (3). CC Cream The BB Cream Version 2.0? While the BB cream is the trendy, musthave product at the moment in Europe, a new generation of products has just been launched to compete with it in the Asian market. CC creams, usually claimed that this stands for Colour Control, are the new hot topic in Today s Asian market (4). It is remarkable to see that a French company like Chanel decided to launch its CC cream Complete Correction only in the Asian market. CC creams can be seen as an improved version of the BB cream concept with a better coverage, an enhanced skin feel and also active compounds with higher efficacy and better long-term results on the skin. On their way to Europe, BB creams already had to adjust these parameters so it may be the case that, if a formulator paid major attention to the previously exposed properties while creating his BB cream, this formula already meets all the criteria of a CC cream. Let us take a closer look at the formulation aspects and the challenges formulators face. Challenge I An Optimized BB/CC Creams Base»How can I introduce the color pigments without negative interfering with my current skin care emulsion system?«or 2 SOFW-Journal

3 »How can I achieve a stable, weightless and light covering foundation with the addition of the desired active ingredients?«before starting formulating a BB/ CC cream, the formulator needs to take into account the aspects of both the skin care emulsion (sensorial feel, texture, stability etc) and the make-up product (skin coverage, skin adhesion, long lasting effect etc.). Of course, the choice of the emulsion system is of paramount importance. BB creams were originally inspired by the color cosmetic formulations so it was not unusual to find W/Si or W/O systems which are very popular due to their ability to ensure an optimal dispersion of a higher amount of pigments, a great sensorial feel and/or a long lasting effect. But O/W systems are getting more popular because of its light weight and less oily skin feel. In many cases, O/W system also enables an easy process to incorporate the heat sensitive active ingredients. This is all the more true for European customers for which O/W systems are somehow a standard for facial care, BB creams included, as they display better moisturizing properties. We can underline that the trend for O/W emulsions totally fits in the CC cream concept where a less oily texture is displayed and more active ingredients are incorporated. Starting working with pigments when you are used to formulating only white creams does often generate a lot of anxiety. Some are even wondering whether they will get their lab coat, lab bench and mixing equipment clean again, other are afraid of handling those insoluble particles. To achieve a homogeneous product with an even skin coverage during the application, it is critical to make the right choice of the pigments and their use levels. A pre-dispersion step or the use of a dispersing aid, e.g. a wetting agent, could be very helpful. For W/Si structure, hydrophobically treated pigments are usually preferred as they can be easily dispersed in the external oil phase. For O/W emulsion type, non-treated or hydrophilically treated pigments (such as glycerin coated pigments) can be recommended. For process reasons, it may happen that you have to disperse your pigments in the internal phase. You will then have to reconsider the selection of the pigments. Nevertheless, depending on the use-level, you really have to ensure that the emulsion structure can cope with the pigment load in terms of stability but also aesthetics (5). Formulating an O/W BB cream is a challenge that is very similar to formulating an O/W sunscreen with inorganic UV-filters. Thus, it is interesting to have a closer look to what is in a»mineral«sunscreen. As the emulsifiers and emollients have the tendency to be absorbed onto the large surface area of the pigments used, the pigment and oil phase ratio, as well as the process would be critical to the texture and long term stability of the finished prototypes. It is recommended to disperse the pigments in the emollients before adding the emulsifiers. Extra emulsifiers could improve the stability in long run. Since higher levels of emollients are needed in the prototypes with high level of pigment, light emollients with high spreading properties are highly recommended. The following emollients, which are widely used in sunscreen formulation, are likely to ensure an optimal balance between good pigment dispersion and pleasant skin feel: propylheptyl caprylate, dicaprylyl carbonate, C12-15 alkyl benzoate, isodecyl neopentanoate, isononyl isononanoate, ethylhexyl stearate or caprylic/capric triglycerides. Rheology modifiers and stabilizers, such as synthetic polymer or natural hydrocolloids or clay, could also play an important role in the texture and skin feel of the O/W type of BB/CC Creams. With different use levels, or the combination use of different rheology modifiers, interesting textures can be generated with desired skin feel. Challenge II The Right Choice of the Color & Functional Additives Due to the difference of the skin tone between Asian and Caucasian women, the preference of the BB cream colors and shades are quite different too. In Western countries, customers will look for colors ranging from peach to beige whereas in Asia, the requests will focus on ivory/porcelain skin tone with pink shades. As the BB cream is supposed to give a natural look to the face, the consumers should select a color which is closest to their skin tone. At the moment, one big limitation is that the range of colors available for BB or CC creams is not as wide as the one for foundations but be sure that if they keep on gaining popularity, this will be quickly solved. An alternative to the traditional iron oxides (CI77491, CI77492 and CI77499) and pigmentary grade titanium dioxide (CI77891) could be the use of mass-tone colored interferential pigments. Due to their specific structure composed of a Mica substrate and a Titanium dioxide and iron oxide coating, they display a subtle colored interference that is more transparent than pure iron oxide and gives a more natural look without any»mask effect«. As they are plateletshaped, the bigger the particle size, the shinier is the effect. Thus to achieve a matte appearance, smaller particle pigments (<50µm) are preferable in the BB cream applications. In addition to them, pure interferential pigments, i.e. particles with a white mass-tone and a colored interference, could be helpful for the skin tone adjustment: for Caucasian skin, the use of pink or red interference pigments will warm up the face and confer to it a radiant look; for Asian skin, immediate optical whitening properties could be achieved with a blue interference that counterbalances yellow hues. Functional fillers such as silica beads (alone or combined with mica platelets), bismuth oxychloride or boron nitride, could also be of interest. These inorganic particles can contribute to improve the skin feel and the spreading properties. Other fillers like particles displaying a soft focus effect are often used in BB creams. They smooth out skin imperfection to achieve an immediate optical wrinkle reduction and a smoother skin tone. As the consumers are more educated in regards to the aging process by the sun damaging to the skin, a UV protection claims are almost essential to the BB Cream products. CC creams tend to claim a higher SPF, which is consistent with the fact that they are meant to provide an enhanced protection and efficacy than the BB creams. When it comes to select SOFW-Journal

4 the suitable sun protection systems, there are several parameters to be checked. Photostability, broad spectrum protection and the compatibility with other ingredients (iron oxides above all) have to be taken into account especially when formulating with organic UV-filters. The right balance between protection and skin feel is not easy to reach as some organic UV-filters may impart tackiness to the formulation. Here encapsulated UV filters could be an elegant way to optimize the skin feeling without loss of UV protection. Furthermore, we already mentioned some tips for incorporating mineral UV-filters in the emulsion as it is similar to dispersing pigments. Inorganic UV-filters are well appreciated by Asian formulators because they contribute to the hiding property of the formulation while giving a slight whitening effect. Ingredients INCI (%) Phase A UV-TITAN M765 1) TITANIUM DIOXIDE, TRIETHOXYCAPRYLYLSILANE, ALUMINA 3.00 Eusolex OCR 1) OCTOCRYLENE 9.00 Eusolex ) BUTYL METHOXYDIBENZOYLMETHANE 2.50 RonaCare AP 1) BIS-ETHYLHEXYL HYDROXYDIMETHOXY BENZYLMALONATE 2.00 RonaCare Bisabolol 1) BISABOLOL 0.20 RonaFlair Soft Sphere 1) SYNTHETIC FLUORPHLOGOPITE, SILICA 2.00 RonaFlair LDP White 1) SODIUM POTASSIUM ALUMINUM SILICATE, CI (TITANIUM DIOXIDE), SILICA 2.00 Colorona Imperial Topaz 1) MICA, CI (BISMUTH OXYCHLORIDE), CI (IRON OXIDES), CI (IRON OXIDES), CI (IRON OXIDES) 0.60 MiBrid Color Powder CI (TITANIUM DIOXIDE), DIMETHICONE, DISODIUM CAPRYLOYL SA/NAI-TR-10 2) GLUTAMATE 5.00 MiBrid Color Powder CI (IRON OXIDES), DIMETHICONE, DISODIUM CAPRYLOYL SA/NAI-Y-10 2) GLUTAMATE 0.20 Cithrol DPHS 3) PEG-30 DIPOLYHYDROXYSTEARATE 2.00 KSG-15 4) CYCLOPENTASILOXANE, DIMETHICONE/VINYL DIMETHICONE CROSSPOLYMER 2.00 KSG-210 4) DIMETHICONE, DIMETHICONE PEG-10/15 CROSSPOLYMER 2.00 KF ) PEG-10 DIMETHICONE 0.30 KF ) PEG-9 POLYDIMETHYLSILOXYETHYL DIMETHICONE 1.00 Tegosoft TPP 5) PPG-15 STEARYL ETHER BENZOATE, C12-15 ALKYL BENZOATE, DIPROPYLENE GLYCOL DIBENZOATE 4.00 Crodamol OSU 3) ETHYLHEXYL STEARATE 4.00 Dow Corning 200 (5cs) 6) DIMETHICONE 6.00 Xiameter PMX ) CYCLOPENTASILOXANE, CYCLOHEXASILOXANE 4.00 Phase B Keltrol CG-RD 7) XANTHAN GUM 0.20 Aristoflex AVC 8) AMMONIUM ACRYLOYLDIMETYLTAURATE / VP COPOLYMER Butanediol 1) BUTYLENE GLYCOL 3.00 Complexing agent Water, demineralized AQUA (WATER) Phase C UV-TITAN M040 1) TITANIUM DIOXIDE, SILICA, GLYCERIN 5.00 RonaCare Ectoin 1) ECTOIN Butanediol 1) BUTYLENE GLYCOL 6.00 RonaCare Sodium Chloride 1) SODIUM CHLORIDE 1.00 RonaCare Sodium Citrate 1) SODIUM CITRATE 0.30 Preservatives Procedure: Add all ingredients of phase A and mix until uniform. Heat to 60 C. Add all ingredients of phase B and mix until uniform. Heat to 60 C. Mix Phase B into phase A step by step. Homogenize. At 40 C, stir for 10 minutes then add phase C. Homogenize. Formulation 1 Multi-functional BB cream (W/Si). In vitro SPF = 58 4 SOFW-Journal

5 BB Cream Formulations Merck Global Application Technology (GAT) network consists of nine different cosmetic laboratories located in Darmstadt, Paris, Philadelphia, Sao Paulo, Taipei & Shanghai. Three BB Cream formulations developed by the Merck GAT laboratories have been chosen to demonstrate the possible BB Cream prototype options as shown below: The Multi-functional BB cream (Formulation 1) has been developed for the Chinese market. This dark pinkish BB cream is a typical W/Si emulsion with hydrophobically coated pigments. With the use of both organic and inorganic UV-filters, this prototype has provided a high SPF value and an effective UVA protection. PEG-30 Dipolyhydroxystearate is used as a dispersing aid to improve the pigment dispersion and the emulsion stability. Soft focus effect is provided by a light diffusing pigment based on a silica structure. The active compounds Bisabolol and Ectoin confer soothing properties as well as an intense moisturization. Bis-ethylhexyl hydroxydimethoxy benzylmalonate generates superb antioxidant power while providing sebum control. The sandy colour of the O/W emulsion (Formulation 2) is adapted to fair skin type within the Caucasian population and has been developed for the European Market. It contains 10% of untreated pigments to get the appropriate color and hiding power. A high SPF is achieved by a combination of organic UV-filters and surely the inorganic particles in the formula con- Ingredients INCI (%) Phase A RonaFlair Soft Sphere 1) SYNTHETIC FLUORPHLOGOPITE, SILICA 1.50 RonaFlair LDP White 1) SODIUM POTASSIUM ALUMINUM SILICATE, CI (TITANIUM DIOXIDE), SILICA 1.50 RonaCare Ectoin 1) ECTOIN 1.00 Glycerol 85% 1) GLYCERIN, AQUA (WATER) 6.00 Triethanolamine 1) TRIETHANOLAMINE 0.10 Keltrol CG-SFT 7) XANTHAN GUM 0.15 Complexing agent Water, demineralized AQUA (WATER) Phase B Titanium -(IV)- oxid 1) CI (TITANIUM DIOXIDE) 9.00 Unipure Yellow LC 182 9) CI (IRON OXIDES) 0.74 Unipure Red LC 381 9) CI (IRON OXIDES) 0.15 Unipure Brown LC 889 9) CI (IRON OXIDES), CI (IRON OXIDES) 0.07 Unipure Blue LC 686 9) CI (ULTRAMARINE BLUE) 0.04 Phase C Eusolex OCR 1) OCTOCRYLENE 8.00 Eusolex ) BUTYL METHOXYDIBENZOYLMETHANE 1.50 RonaCare AP 1) BIS-ETHYLHEXYL HYDROXYDIMETHOXY BENZYLMALONATE 1.00 Oxynex K liquid 1) PEG-8, TOCOPHEROL, ASCORBYL PALMITATE, ASCORBIC ACID, CITRIC ACID 0.03 Hydrolite-5 10) PENTYLENE GLYCOL 5.00 Miglyol 812 N 11) CAPRYLIC/CAPRIC TRIGLYCERIDE 5.00 Montanov ) ARACHIDYL ALCOHOL, BEHENYL ALCOHOL, ARACHIDYLGLUCOSIDE 4.00 Eutanol G 13) OCTYLDODECANOL 2.80 Avocado Oil 14) PERSEA GRATISSIMA (AVOCADO OIL) 2.00 Bentone Gel GTCC V 15) STEARALKONIUM HECTORITE, PROPYLENE CARBONATE, CAPRYLIC/CAPRIC TRIGLYCERIDE 1.00 Phase D Simulgel EG 12) SODIUM ACRYLATE/SODIUM ACRYLOYLDIMETHYLTAURATE COPOLYMER, ISOHEXADECANE, POLYSORBATE Phase E Preservatives Fragrance Energy 16) PARFUM 0.20 Procedure: Add all ingredients of phase A and mix until uniform. Heat to 60 C. Add all ingredients of phase B and mix until uniform. Heat to 60 C. Mix Phase B into phase A step by step. Homogenize. At 40 C, stir for 10 minutes then add phase C. Homogenize. Formulation 2 BB cream sand. In vitro SPF = 36 SOFW-Journal

6 Ingredients INCI (%) Phase A Water, demineralized AQUA (WATER) Butanediol 1) BUTYLENE GLYCOL 4.00 Pluracare E ) PEG Phase B Eusolex T-PRO 1) TITANIUM DIOXIDE, ALUMINA, MANGANESE DIOXIDE 7.00 Colorona Oriental Beige 1) MICA, CI (TITANIUM DIOXIDE), CI (IRON OXIDES) 3.00 Parteck LUB Talc 1) TALC 2.00 Phase C Water, demineralized AQUA (WATER) Complexing agent RonaCare Ectoin 1) ECTOIN 2.00 Phase D Crodamol GTCC 3) CAPRYLIC/CAPRIC TRIGLYCERIDE 7.00 Vegetable Squalane 17) SQUALANE 4.00 RonaCare AP 1) BIS-ETHYLHEXYL HYDROXYDIMETHOXY BENZYLMALONATE 1.00 Sensolene 18) ETHYLHEXYL OLIVATE 2.00 Montanov 202 6) ARACHIDYL ALCOHOL, BEHENYL ALCOHOL, ARACHIDYLGLUCOSIDE 5.00 Phase E Simulgel NS 12) HYDROXYETHYL ACRYLATE/SODIUM ACRYLOYLDIMETHYLTAURATE COPOLYMER, SQUALANE, POLYSORBATE Phase F Water, demineralized AQUA (WATER) 5.00 RonaCare Luremin 1) SORBITOL, DIHYDROXYMETHYLCHROMONE 2.00 RonaFlair Soft Sphere 1) SYNTHETIC FLUORPHLOGOPITE, SILICA 2.00 Preservatives Procedure: Prepare separetely phases A,B and C. Add phase B to A, then phase C to A/B. Heat A/B/C and D to 80 C. Then add D to phase A/B/C. Homogenize. Add phase E. Prepare phase F and maintain under agitation. At 40 C, add phase F. Adjust ph to Formulation 3 BB cream»5 in 1 care«. SPF: between 15 and 25 (estimated) tribute to the good overall sun protection. Here, the UVA filter Butyl Methoxydibenzoylmethane is photostabilized by Octocrylene. Xanthan gum, hectorite derivate and acrylate polymers are needed for the stability of the emulsion and the suspension of color pigments. An optical wrinkle reduction and a zero imperfection skin aspect can be obtained thanks to a novel soft focus filler based on ceramic microspheres (INCI: Sodium Potassium Aluminium Silicate, Titanium Dioxide, Silica). The last formulation is a beige O/W cream (Formulation 3). Also designed for the European customers, the formulation is expected to display a medium SPF. The mass tone of this BB cream is only generated by the mixture of a beige interferential pigment with a manganese-coated mineral UV-filter. No additional iron oxide or titanium dioxide particles have been used. The latter displays a broad-spectrum protection against harmful UVrays but also a proven anti-radical activity. The formulation provides a slight skin coverage, leading to a very»nude«result. Soft skin feeling can be achieved thanks to a functional filler composed of synthetic mica platelets and silica beads. The following benefits are provided by a powerful cocktail of the List of suppliers 1) Merck KGaA/Rona 2) Miyoshi 3) Croda GmbH 4) Shin Etsu SIlicones Europe B.V 5) Evonik 6) Dow Corning 7) C. P. Kelco 8) Clariant GmbH 9) Sensient Cosmetic Technologies three active compounds Ectoin, Bisethylhexyl hydroxydimethoxy benzylmalonate and Dihydroxymethylchromone: cell protection and long term moisturization, efficient prevention of oily and impure skin and retinol-like anti-aging properties. The emulsion system, the light texture and the multiple activities are very likely to support a CC cream claim here. 10) Symrise 11) Sasol Germany GmbH 12) Seppic 13) BASF AG 14) Gustav Heess GmbH 15) Elementis Specialties 16) Cosnaderm GmbH 17) Laserson 18) B&T S.r.l. 6 SOFW-Journal

7 Conclusion When skin care meets make-up, BB cream definitively brings you the benefits of the two worlds. BB creams and their latest improved version, CC creams, are expected to continue to gain popularity not only in Asia but also in Europe as well as the north and south American markets. These multitasking (or multifunctional) cosmetic products provide a nude look and a treated, protected skin in one single application which is ideal for customers who do not have the luxury of the time for the beauty routine. Throughout the technical challenges pointed out and the formulation examples, it has been highlighted that the main task for a formulator is to guarantee a pleasant skin feel and texture while perfectly incorporating color pigments. We also noticed that there are still slight differences between European and Asian markets. Blemish Balms and Color Control creams are certainly products of bright perspective and new developments are to be expected. Next steps could be to offer a wider range of colors to adjust to every skin types (6), just like foundations. Anyway, it is just a matter of time to discover what the initials of a»dd cream«or»ee cream«will stand for! References (1) Schoeneck A., Eine Creme und ihre Geschichte. Brigitte, June 2012, P83 (2) Bénézet A., Complexion: when make-up turns into care. Expression cosmétique N 9, May 2011, P54-55 (3) Goldfarb S., Une belle peau sinon rien. Cosmétiquemag N 130, June 2012, P49 (4) Scott R, Smith C., Colour control creams: the new blemish balms. Personal Care, June 2012, P16-17 (5) Baek Y.Y., Choi S., Blemish balm creams offer flawless results. Personal Care, December 2011; P60 (6) Martin-Phipps C., Foundations: the feminine paradox, Expression cosmétique N 16, July 2012, P22-26 R Corresponding author: Thierry Baldecchi Merck Chimie S.A.S. 201 rue Carnot Fontenay-sous-Bois France thierry.baldecchi@merckgroup.com Authors address: * Jutta zur Lage, Gabriele Witte, Frank Pfluecker Merck KGaA Business Field - Cosmetics Frankfurter Str Darmstadt Germany ** Robert Bai Merck Chemicals (Shanghai) Co., Ltd. N 428, Sanbang Road, Chedun Town, Songjiang Shanghai P.R. China *** Sherry Wu Merck Ltd., 6 F, N 89, Section 2, Ti-Ding Boulevard Taipei, 114 Taiwan **** Judy Zhuang, EMD Chemicals, One International Plaza, Suite 300 Philadelphia, PA United States of America n SOFW-Journal