Deciphering Frizz Control Hair Care Formulas

Frizz control hair care has been around for almost 20 years. Frizzy hair is a major issue for women with curly hair that has especially been chemically or mechanically treated. These consumers spend time each day adjusting and controlling the style of their hair, specifically to control the onset of frizz in high humidity environments. This market continues to exhibit innovation as new technologies and products are consistently being launched.

Moisture has a significant impact on hair frizz because water vapor in the air can be transported inside the cortex of the hair shaft, modifying the temporary hydrogen bonds created by hair proteins during styling. These proteins are based on four, twisted long chain amino acids running lengthwise down the shaft. The chemical bonds between the protein chains provide the cohesion that establishes the natural form of the hair. Water/humidity/dampness can disrupt this cohesion but drying allows for the reformation of the keratin chains, which can be temporarily altered as part of the styling process and during hair drying.

Another primary contributing factor to frizzy hair is damage to hair strands due to rough brushing, i.e. the lack of a good conditioning agent for wet and dry combing; chemical treatments such as perming, bleaching and coloring; UV exposure; and heat styling. All of these factors lead to a damaged cuticle and split ends, potentially increasing porosity and swelling of the hair cuticle, creating another entry point for style-disrupting moisture.

A secondary contributor to frizz is dry hair that becomes statically charged due to hair’s negative charge. This charge results in the repulsion of hair’s protein keratin strands—hard, fibrous proteins comprised of polypeptide chains—when shampooed with negatively charged depositing ingredients.1 As hair becomes coarse and dull from cuticle damage, it loses its tensile strength in the cortex.

Key Components for Frizz Repair

Hair care products that control or repair frizz must eliminate lifting of the cuticle, minimize loss of internal lipids, and improve hair tensile strength. Conventional methods utilize a physical coating to smooth the cuticle, modulate moisture content in the cortex, and improve both wet and dry combing. The most widely used smoothing ingredients are silicone fluids, i.e. high molecular weight dimethylsiloxanes or polydimethylsiloxane gums such as dimethicone or dimethiconol.

The search continues for raw materials that effectively coat and smooth the cuticle and that minimize the effect of humidity while not creating buildup on hair, which can be perceived as greasy and dirty. Recent hair smoothing technologies have been based on crosslinking the dimethylsiloxane backbone (e.g. dimethicone crosspolymer) and combinations with complex esters, such as diethoxy ethyl succinate and dicaprylyl ether.

Frizzy hair can temporarily be controlled with the daily use of a good conditioner. It does not matter whether the conditioner is deposited from a 2-in-1 shampoo, a rinse-off conditioner, or a leave-on conditioning product, so long as a sufficient quantity is deposited to reduce the degree of friction on hair during wet and dry combing. Controlling the amount of deposited conditioner is difficult, as it can be hindered by consumer application techniques, degree of damage to hair, etc., thus it is important for consumers to adjust the amount or type of conditioner they apply to their hair to meet their individual conditioning needs. The most popular conditioners that provide good frizz control contain varying molecular weights of dimethicone, an amine-functional siloxane such as amodimethicone, or a suitable polyquaternium complex (polyquaterium-8). Supplementing these conditioning additives with a cationic surfactant such as behentrimonium chloride or cetrimonium chloride enhances the conditioning additive’s substantivity for longer lasting performance.

Another popular frizz control approach is to apply to the hair an anhydrous serum or a w/s emulsion that deposits a high molecular weight polydimethylsiloxane, e.g. silicone gum. This approach fills the gaps where humidity can enter the cuticle to smooth it. Although this approach is effective, excessive deposition can result, leaving a greasy, heavy feel on hair that could be perceived as “dirty.” Since siloxanes are water-insoluble, they are also difficult to remove and can build up after continued applications.

Taking some of the described approaches, following is a sampling of anti-frizz hair care patents issued in recent years. Ranging from leave-in hair conditioning and treatment of hair during the relaxing process, to dibasic acid ester penetration and controlling hair shape, they provide product developers with recent insights into this market.

Recent Anti-frizz Patents

Leave-in hair conditioning: This invention relates to a non-aqueous leave-in conditioning composition especially for frizzy hair and/or hair strongly damaged from chemical processes such as permanent shaping, oxidative coloration and bleaching.2 According to the patent, in order to improve the surface properties of hair fibers, a number of ingredients have been suggested such as cationic charge ingredients and oily substances. Among the oil substances, silicone oils have increasingly been used. Described by this patent is the discovery that a water-free composition comprising one or more cyclomethicones at 50% w/w or greater, and at least one dialkyl carbonate, improves the combability, elasticity and shine of hair, resulting in a more natural hair feel.

Treating damaged hair during chemical relaxing: According to this patent, the hair cuticle is an important factor in torsional mechanical properties although its contribution to bulk longitudinal mechanical strength is minor. Therefore, tensile strength can be used to evaluate not only hair damage, but also to indicate if damage has penetrated to the cortex. One way to restore the natural quality of damaged hair is to recover its reduced tensile strength. The present disclosure describes a method of treating one or more hair shafts including the cuticle layer and cortex. The treatment is comprised of one or more polymers with a pore size of about 5–5,000 angstroms that can penetrate the hair shaft. Specifically, an effective amount of a composition containing an anionic polymer or copolymers is used to treat the hair shaft.3

In general, the polymers used should be of a size that is able to penetrate into the cortex of the hair shaft but not easily migrate out of the cortex. Therefore, polymers that are linear, branched, hyperbranched or dendritic may meet this criteria. The polymers may be homopolymers, copolymers, terpolymers or a combination thereof; or they may be cationic polymers (CIP2), anionic polymers (CIP1), nonionic polymers, amphoteric polymers, zwitterionic polymers or a combination thereof.

In its principal aspect, the disclosed invention includes ~1–10% w/w of a cosmetically acceptable hair repair polymer based on solids of an anionic polymer, wherein the anionic polymer is: a homopolymer of polyacrylic acid, a copolymer from ~10–90 mole % of polyacrylic acid, or a base addition salt; and from about 90–20 mole % of one or more anionic or nonionic monomers.

Dibasic acid ester penetration enhancement: The present invention describes an oil-based hair treatment that improves the surface and internal conditions of damaged hair, adds strength and shine, provides a non-sticky light finish, and prevents static electricity.4 The invention also discloses a method for preparing the treatment by combining a dibasic acid ester compound with a specific oil agent. The inventors found that a dibasic acid ester compound, bis-diethylene glycol ethyl ether succinate or bis-ethoxydiglycol succinate, acts as a penetration-enhancing agent, exhibiting high permeability to hair, excellent safety and almost no odor. The dibasic acid ester compound disclosed is a combination of a poly- (or mono-)ethylene glycol monoether or a derivative thereof selected from a wide range of materials (see Poly- (or mono-)ethylene Glycol Monoether or Derivative Selections) and a dibasic acid.

Controlling hair shape: Natural wavy hair is thought to be formed by factors such as the distribution of ortho- and para-cortex cells, quality and quantity of keratin-related protein, amount of disulfide bond of protein, transglutaminase and other differentiation-related enzymes present in the hair root, and the shape of the hair bulb itself. A study by Schlake also showed that insulinlike growth factor binding protein-5 (IGFBP-5), expressed in the medulla of mice, plays an important role in determining hair morphology.5, 6 In the human hair follicle, IGFBP-5 is expressed in the hair papilla and root sheath and plays an important role in reconstructing the extracellular matrix.7, 8 However, the relationship between IGFBP-5 and human hair morphology has not been reported, and hair structures and cycles considerably differ between mice and humans.

The present invention describes a method for determining or modulating hair morphology and properties such as naturally wavy and frizzy hair, and for evaluating or selecting a hair morphology modulator by employing an index of the expression level of the IGFBP-5 gene or IGFBP-5 protein in a human hair follicle.9 The inventors evaluated human hair morphology using molecular biological techniques and found that the IGFBP-5 gene and IGFBP-5 protein are expressed at high levels in the hair follicles of subjects with frizzy hair. They also found that hair morphology can be modulated without damaging hair; for example, natural wavy or frizzy hair can be straightened, or straight hair can be waved. In addition, the patent discloses how a material such as a drug or a cosmetic composition for modulating hair morphology can be evaluated or selected.

Recent Frizz Control Product Launches

In the early 1990s, John Frieda launched Frizz-Ease Serum, a product to control frizzy hair through the application of a cyclomethicone/dimethiconol gum blend. Since then, the basic technology behind frizz control has not changed much, as evidenced by the following commercial examples. The changes largely have been to modify the delivery system of high molecular weight siloxanes and to incorporate frizz control in other conventional hair grooming systems, e.g., shampoos.

The examples presented here are featured to demonstrate claim positioning as well as how specific ingredients are incorporated to support these claims. The information is taken from publicly available sources and is included for illustrative purposes only. The estimated ingredient ranges are provided as a starting point from which formulators are encouraged to build their own unique formulas.

John Frieda Frizz-Ease Hair Sérum: This serum, shown in Figure 1 and Table 1, is promoted as helping to correct and transform dry and medium frizz instantly. The serum is designed to work with hair straighteners by protecting hair from heat protection, keeping hair glossy, smoothing hair and adding body. The product features a dimethiconol/cyclopentasiloxane blend of polymers with keratin protein (hydrolyzed silk) and its anti-frizz action is said to last up to three days.

Avon Advance Techniques Frizz Control Lotus Shield Anti-Frizz Treatment: This product, shown in Figure 2 and Table 2, was designed to repel water like a lotus leaf to resist up to 97% humidity. It utilizes functional siloxanes such as silsesquioxane crosspolymer and vinyl dimethicone/methicone to form stronger bonds with hair and is claimed to keep hair smooth and “well-behaved” for three days. According to the manufacturer, 80% of panelists agreed that it instantly eliminates frizz. This leave-in treatment is said to form a lightweight barrier that helps block out humidity to fight against bad weather and to fight frizz without weighing hair down.

Sassy Treatment Cream: This cream, shown in Figure 3 and Table 3, features an advanced liposome system, possibly a combination of polyacrylamide and fatty acids, to deliver avocado oil, ceramide and bio-lipids deep into the cortex of the hair for nourishment. The cream is said to improve the hair texture, reduce frizz and leave hair smooth and manageable.

FX Special Effects Curls Up Crema para Restablecer los Rizos (Curl Reviving Mousse): This mousse, shown in Figure 4 and Table 4, is formulated with dimethicone copolyol and VP/DMAPA acrylates to add volume, texture and control to frizzy and uncontrollable curls. According to the manufacturer, it tightens curls, eliminates frizz and provides long-lasting hold without weighing hair down or leaving it sticky. The water-resistant film-formers lay the cuticle down to control frizz caused by humidity.

Frosini Trilogia Hair Treatment T + A (Smooth Effect Anti-Frizz Salt-Free Shampoo): This shampoo, shown in Figure 5 and Table 5, is said to hydrate hair, providing a smooth effect, preventing unmanageable hair, fighting frizz and protecting against damage caused by hot styling tools. The shampoo is formulated with polyquaternium-28, polyquaternium-55, keratin, a silicone complex and d-panthenol to restore vitality, provide thermal protection, reduce volume and improve resistance to humidity.

Corpus Cosméticos Indústria e Comércio Finesse Creme para Pentear Condicionador Sem Enxágue (Anti-frizz Leave-in Combing Cream): This combing cream, shown in Figure 6 and Table 6, features a self-adjusting technology based on pH modulation of the proteins with acetamide MEA and citric acid to restore strands, hydrate, nourish, protect, infuse shine and fight frizz, to help deliver smooth, soft hair that detangles easily. Its light formula reportedly leaves no residue and provides a gentle application. The product is based on a classical quaternium complex of conditioners such as behentrimonium chloride, cetronium chloride and cetyl alcohol in addition to water-resisting film-formers such as dimethiconol and VP/dimethylaminoethyl methacrylate copolymer to control frizz, especially during higher humidity situations.

Living Proof No Frizz Humidity Blocking Conditioner: This conditioner, shown in Figure 7 and Table 7, is said to block humidity, hydrate and restore shine to all hair types. Where other silicone-based anti-frizz products weigh hair to keep it straight, this conditioner reportedly deeply hydrates hair, leaving it soft, smooth and able to withstand conditions that cause frizzy, unmanageable hair. It contains polyfluoroester to lock in moisture, smooth hair, and repel dirt and oil, allowing users to go longer between washes.

Formulator Beware

Defining the elements to make a product control hair frizz is difficult. For the most part, hair damage is not repaired because hair is dead when it leaves the scalp. Therefore, consumers can only control frizz by styling it and making it more manageable. The trend in frizz control products has been to create softer, less depositing products so the hair feels as natural as possible, as well as to incorporate anti-frizz control into product forms other than the traditional serum such as shampoos, conditioners and styling gels.

When creating a frizz control product, it is best to avoid ingredients that will leave the hair sticky or impart a “dirty” feeling coating that result in unnatural shine/gloss, or that incorporate hydroscopic components, e.g. glycerin. If hair feels dirty or greasy, consumers will wash it more frequently, which consumers associate with increased frizz. Thus, the formulator should consider the demand for hair that is as natural looking as possible.

Looking long-term at this product category, key ingredients to consider are siloxane elastomers that provide a hydrophobic film-forming cuticle smoothing coating. Also, there is a possibility to envision a growing segment developed around more flexible polyurethanes, as long as the film is light and not greasy feeling. Reproduction of the article without expressed consent is strictly prohibited.

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1. Morphological and Macromolecular Structure, ch 1 in Chemical and Physical Behavior of Human Hair, CR Robbins, Springer-Verlag, New York, 4th ed (2002) pp 1–4
2. US Pat Application 20070110694, Leave-in hair conditioning composition, M Hoffmann and M Lateulere, assigned to Kao Professional Salon Services GmbH (May 17, 2007)
3. US Patent Application 20100166692, Method for treating damaged hair in conjunction with the relaxing process, YZ Hessefort,  BT Holland, JM Atkins,  S Weiz, XH Li and V Kompalitch, assigned to Nalco Company (Jul 1, 2010)
4. US Pat Application 20100203003, Oily hair cosmetics, Y Kokeguchi, K Takeda and K Kiyotaka, assigned to Kokyu Alcohol Kogyo Co, Ltd (Aug 12, 2010)
5. T Schlake, FGF signals specifically regulate the structure of hair shaft medulla via IGF-binding protein 5, Development 132 2981–2990 (2005)
6. T Schlake, Segmental Igfbp5 expression is specifically associated with the bent structure of zigzag hairs, Mech Dev 122 9 988–997 (2005)
7. SM Firth and RC Baxter, Cellular actions of the insulin-like growth factor binding proteins, Endocr Rev Dec 23 6 824–854 (2002)
8. JA Batch, FA Mercuri and GA Werther, Identification and localization of insulin-like growth factor binding protein (IGFBP) messenger RNAs in human hair follicle dermal papilla, J Invest Dermatol 106 3 471–475 (1996)
9. US Patent Application 20090280088, Method for controlling hair shape, A Hachiya and P Sriwiriyanont, assigned to Kao Corp. (Nov 12, 2009)

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