In the first article of this short series1, I questioned the reasons that push cosmetic brands to phase out useful ingredients and then exemplified by the family of Parabens. Likewise, Phthalates and Silicones were (and are still) badly treated by the media – sometimes for good but usually for bad reasons. The entire families were punished when only one or a few representatives were actually guilty.
Anyhow, the market is always right and it is now time to think about alternatives to these useful ingredients. However, and as a general principle, I believe that cosmetic brands would be better advised to communicative positively rather than using free-from claims based on fears and negative feelings. In other words, highlight the presence of good ingredients rather than claiming the absence of stigmatized ingredients.
Phthalates are a family of esters based on phthalic acid. Many members of this family have interesting and varied properties. In the cosmetics industry, Phthalates have been used as a solvent, plasticizer, film former, denaturant, odor masker and hair conditioner.
Until quite recently, it was possible to find Dibutyl Phthalate in nail polish (to prevent nails from becoming brittle) or Dimethyl Phthalate (DMP) in hair spray (to help avoid stiffness). The presence of other phthalates in cosmetic products were also possible as the result of a migration from the plastic container to the product.
These last few years, the European Union voted many pieces of legislation prohibiting or restricting the use of phthalates because of valid safety concerns. As of today, only DMP and Diethyl Phthalate (DEP) can still be used in cosmetic products.2,3 All other members of the family are deemed unsafe and strictly prohibited. Interestingly enough, Dimethyl Phthalate has virtually no use in the cosmetic industry and the last phthalate to stay in use is Diethyl Phthalate.
Practically odorless, Diethyl Phthalate (CAS 84-66-2) is mainly used as a solvent and a fixative in fragrances.4 Romain Pantoustier, a reputed Perfume Craftsman and Scent Designer5, shared his knowledge and experience about the choice of alternatives to Diethyl Phthalate in perfumery. Dipropylene Glycol is an excellent, inexpensive and odorless alternative. It is considered as a much better solvent than Propylene Glycol. Isopropyl Myristate also represents a well-known option.
Furthermore, and when it makes sense in the context of a specific fragrance development, odorous alternatives include:
- Benzyl Benzoate
- Musks (Galaxolide, Tonalide, Ethylene Brassylate (so-called Musk T))
- Resins (Opoponax, Benzoin, Peru Balsam)
DEP is also used as a denaturing agent and it can be found in SDA Alcohol 39 C endorsed by the US Government. Although DEP remains a theoretical possibility for the denaturation of alcohol in the EU, other systems are preferred.
As recommended by the EU Commission, either Isopropyl Alcohol (IPA) and/or tert-Butyl Alcohol (TBA) should be added to alcohol as a minimum denaturant in the manufacture of certain products in cosmetic and perfume production. These denaturants should be used in products with an alcohol level above 20%, or 5% for mouthwash.
Unlike the Parabens or the Phthalates, the Silicones are a vast family of chemicals only related by a common structural pattern made of silicon and oxygen. As a consequence, Silicones can have all kinds of properties and be used for all kinds of purposes.
There are entire books focusing on the cosmetic applications of Silicones6 and this article does not intend to provide an exhaustive list of the commercially available silicones and their alternatives. The focus will be on two particularly infamous silicones, regularly criticized by cosmetic products reviewers: Dimethicone (CAS 63148-62-9 / 9006-65-9 / 9016-00-6) and Cyclopentasiloxane (so-called D5, CAS 541-02-6).
Dimethicone is a simple polymer of the structure outlined above, with R = Methyl. Its use started in the fifties, the first Silicone formulated in personal care products. Today, this is the most common and the least expensive Silicone available on the market.
Amongst its numerous qualities, Dimethicone is colorless, inert and exists in a great range of viscosity, which allows its use in skincare, hair care and color cosmetics. Typically, Dimethicones with low to medium viscosity (5 to 1,000 cst) are widely used in skincare products while high-viscosity Dimethicones (60,000 to 100,000 cst) are more commonly used in hair care products.
In skincare products, Dimethicone is particularly appreciated for its ability to fill in uneven texture and fine lines. It helps create a smooth look in products like foundations. As a consequence of its hydrophobicity, it also provides a protective cover on skin, which helps retain moisture. In hair care products, Dimethicone is used to smooth hair, provide better comb-through and add some sheen.
So, what is wrong with Dimethicone?
Dimethicone is a safe ingredient that can be used without any legal restriction in the EU. The main problem of Dimethicone is its very low solubility in water and its resulting coating action: it is accused of building up on hair and making it heavy, flat and greasy. Removing Dimethicone from the hair would then require aggressive sulfate-based shampoos, which are known to dehydrate and weaken the hair.
In skincare products, Dimethicone has been reported to create an artificial coating that traps everything under it, causing breakouts and blackheads. Furthermore, it would prevent the other cosmetics applied from accessing the skin. On top of that, and this claim is at least partly true, Dimethicone does not biodegrade easily and represents a threat for the environment.
Cyclopentasiloxane (D5) is a Dimethicone chain of five units, with units 1 and 5 linked together to form a cycle. The greatest advantage of D5 is to impart a dry and pleasant skin feel, which consumers appreciate. It is a fast-spreading emollient that helps spread the emulsion homogeneously on the skin to evenly distribute active ingredients.
Unfortunately D5 raised both safety7 and environmental concerns8 in the EU9 (as well as other countries such as Canada). The initial restriction of D5 at less than 0.1% in wash-off products should be extended to leave-on products, causing the end of this remarkable ingredient at relatively short notice10.
Two big options exist when it comes to replacing Dimethicone and Cyclopentasiloxane, namely with or without Silicones.
Some Silicone derivatives have good to excellent solubility in water and, therefore, do not show the same disadvantages as Dimethicone. However, they have similar qualities, with especially excellent hair conditioning properties and the ability to impart a silky soft feel to the skin.
This is notably the case for Dimethicone Copolyols, which are classified by their ratio of ethylene oxide and propylene oxide molecules. For instance, Bis-PEG/PPG-14/14 Dimethicone is Dimethicone end-blocked with an average of 14 moles of ethylene oxide and 14 moles of propylene oxide. The biggest drawback of these water-soluble Silicones is probably their price.
Regarding D5, the unique dry skin feel characteristic of this ingredient is not due to its volatility, which is very low at skin temperatures, but to its low surface tension. This effect can be mimicked by mixing small amounts of alkyl Silicones with natural oils (e.g. behenyl dimethicone is soluble in soybean oil and reaches a critical micelle concentration at about 4%, at which point it gels the oil).11
Many Silicone-free options are available on the market although it is rather difficult to find a one-to-one replacement. Dimethicone may be replaced by mixtures such as:
- Coco-Caprylate/Caprate (e.g. Cetiol LC, BASF), considered as a medium spreading emollient “for modern cosmetic applications”
- Butylene glycol Dicaprylate/Dicaprate (e.g. Dermofeel BGC, Evonik Dr. Straetmans GmbH)
Another category of substances reported to have very similar properties to Silicones are the Alkanes. For instance, Coconut Alkanes seem to offer an acceptable alternative to some forms of Dimethicone (e.g. the interesting mixture Coconut Alkanes and Coco-Caprylate/Caprate, Vegelight 1214 LC, Biosynthis). Of course, this approach is not compatible with the use of the marketing claim “free from mineral oils”.
In hair products, Dimethicone may be replaced by other film-forming ingredients such as C12-15 Alkyl Benzoate Isopropyl Myristate or PPG-3 Benzyl Ether Myristate (e.g. Crodamol STS, Croda). Although they are considerably more expensive, natural alternatives such as Broccoli Seed Oil (so-called natural Dimethicone) have been identified as remarkable surrogates.
Finally, amongst the hundreds of proposed alternatives, it is worthwhile to say a word about Inolex and their LexFeel “N” range of raw materials. Each raw material is made of the same cosmetic ingredients (Diheptyl Succinate, Capryloyl Glycerin and Sebacic Acid Copolymer). The ratio between these ingredients can be varied to imitate Dimethicones of different viscosities. The number after “N” indicates the equivalent Dimethicone (e.g. LexFeel® N200 is a suitable alternative to 200 cSt Dimethicone).
Cyclopentasiloxane may be replaced by light emollients such as:
- Dicaprylyl Ether, which combines a very high spreadability with good stability
- Dicaprylyl Carbonate, which significantly improves the sensory performance of the final formulation.
- A mixture of Isododecane, Disteardimonium Hectorite and Propylene Carbonate (e.g. Bentone Gel ISD V, Elementis Specialties), reported to be a volatile emollient, leaving a dry, non-greasy skin feel
- A combination of Dicaprylyl Carbonate, Stearalkonium Hectorite and Propylene Carbonate (e.g. Cosmedia Gel CC, BASF) seems to improve the velvety skin feeling of a leave-on product
Alkanes also are a possible alternative. The mixture C13-16 Isoparaffin, C12-C14 Isoparaffin and C13-C15 alkane (e.g. Presperse, SiClone SR-5) is described as indistinguishable from Cyclopentasiloxane and usable in skincare, hair care, and color cosmetics.
The Parabens1, the Phthalates, the Silicones. These three cosmetic ingredients families are not chemically related and serve completely different purposes. Nevertheless, they all share the common point to be… great ingredients!
Reformulating a cosmetic product is not an easy task. It is expensive and time-consuming as one-to-one replacements are rare. Beyond the performance aspects, many other parameters need to be taken into consideration like the stability and the price of the new formula or the conditions of availability of the new raw materials, to name just a few.
Beyond the significant workload a reformulation requires, the question of its relevance should also play a role in the decision-making process. Does it make sense to phase out an ingredient that effectively fulfills its duties, is safe, inexpensive, compliant with the legislation and readily available?
It is obvious that marketing plays a critical role in this world and maybe it is not reasonable to expect the cosmetic manufacturers and cosmetic brands to withstand market pressure. Companies have to adapt to the market; this is a vital necessity. But, then, who is supposed to do the hard work and counter misinformation? Maybe this should be the role of the Authorities to support its industries when necessary and, in full objectivity, say the truth to its citizens.
- Preservative Deep Dive: Parabens and their Alternatives
- SCCNFP Opinion on Diethyl Phthalate (June 2002 – PDF)
- SCCP Opinion on phthalates in cosmetic products (March 2007 - PDF)
- Fixative are used to equalize the volatilities between the fragrance ingredients.
- NeZ ZeN - Parfumerie Artisanale, Rue du Président 11, 5000 Namur, Belgium.
- For instance, the excellent “Silicones for Personal Care”, A.J. O’Lenick Jr., 2008, Allured Publishing Corporation.
- SCCS Opinion on D5 (July 2016 - PDF)
- Regulatory proposal of ECHA on D4 and D5 [Download PDF] and its annex [Download PDF]
- Regulatory update on D4 and D5
- ECHA Registry of Intentions – Restriction of D4 and D5 in leave-on products
- Silicones and Silicone alternatives [PDF], John Woodruff, “Soap, Perfumery and Cosmetics magazine”, 2015.
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