Creative Developments (Cosmetics) Limited

Colour 1997

Colour cosmetics are the visible products of our industry and the most fashion driven. While skin care is mostly prophylactic and any improvements to its condition are slow and gradual the use of colour can be dramatic. Unfortunately the colours available to the formulator are strictly limited and with today's international markets are further restricted by the need to be acceptable in them all. The FDA certified colours continue to be the international standard but not all colours permitted in the EU have FDA certified equivalents and in some cases the FDA specification is less demanding than the EU, especially for nickel and zinc content. The nickel content of pigments has become a significant issue because of sensitisation problems caused by the wearing of cheap white metal jewellery. [REF 1]

Because of such restrictions developments are more in the way that colour is used and improvements to the products in which it is incorporated. Such improvements include the use of boron nitride and of polyethylene spheres to add slip and lubricity to loose and pressed powders and the treatment of pigments with fluorinated polymers to enhance skin feel and reduce processing problems [REF 2].

Despite the commercial importance of colour cosmetics there were few papers on the subject at the recent IFSCC Congress in Sydney but two describing recent developments in makeup proved outstanding. [See Manufacturing Chemist January 1997]. Optical Properties of Stratum Corneum and Development of Natural-Looking Makeup, Nishikata K et al., Pola Co., [REF 3] described the importance of the goniometric optical properties of the skin in determining its appearance and how the semitransparent nature of stratum corneum was found important in contributing to the “natural look” of bare skin. To develop natural-look makeup, Nishikata et al prepared several novel complex pigments consisting of plate-like, high refractive-index pigments covered with a low refractive index substance. Using these optically-modified complex pigments, they formulated Optically Simulated Dermal (OSD) Makeup. Panel tests confirmed that OSD makeup allowed the users to look far more natural and less artificial than conventional makeup. The second paper described the Development of Novel Thin-layered Material Based on a New Photo-complementary Colour Theory and its Application in Cosmetic Foundation by T. Katsuyama and a team from Shiseido Laboratories. [REF 4] The authors studied the optical properties of the foundation layer formed on the surface of the face and applied their findings to develop a new type of foundation by utilising the light-splitting ability of titanium dioxide-coated mica, achieving transparency and a natural finish. To overcome the problem of white glitter due to light scattering, a new coloured TiO₂-mica with ultra-fine ferric oxide particles was made.

Initially lip colours were applied as liquid rouge; lipsticks were introduced to the public with the invention of the first pushup case in 1915. In 1934 Francis Chilson wrote “The requirements of a good lipstick are that it must not be injurious, it must spread easily without being excessively greasy; its colour must be reasonably permanent; it must not sweat, crumble nor crack. In addition to these requirements its colour must be absolutely uniform, unchanging and free from mottling” [REF 5]. This definition is still valid today and a third paper given at the IFSCC Congress described the Observation of the sweating of lipstick by scanning electron microscopy [REF 6] and reported the discovery that the wax matrix underneath the lipstick surface changed from a fine, uniform structure to a coarse, non-uniform structure. It was also found that the structure of the wax matrix at the surface region of lipstick was affected by flaming, moulding temperature, the compatibility of the waxes and oils, by the addition of pigment, and the passage of time. In most cases, as the size of wax matrix was increased, sweating was reduced and delayed.

Looking through historical formulations for lipstick the base appears to have changed little between those described by Chilson in 1934 and many still offered today so it is little wonder that the same problems still beset the manufacturer. However there have been advances and there is a far greater range of emollient oils now available which can improve texture and feel and pigment dispersion and durability. Glyceryl diisostearate available as Dermofeel GDI from Dr. Straetmans is described as a non-oxidiseable oil component with good pigment dispersing qualities and a smooth skin feel while glyceryl triisostearate, Dermofeel GTI, is a viscous oil with high skin substantivity and is claimed to improve lipstick durability. Many other esters are recommended as pigment dispersing aids and for improving the application properties of the stick. These include dioctyl sebacate, tridecyl neopentanoate, cetyl octanoate, isodecyl oleate and octyldodecyl stearoyl stearate, all available from Trivent and diisostearoyl trimethylolpropane siloxy silicate from A&E Connock. While most improvements to the lipstick base have been in replacements for the oily components, di-C14-15 alkyl tartrate available as Cosmacol ETL from Enichem is a high melting point waxy multi-purpose lipid and an alternative to natural waxes.

A patent search for lipstick reveals that the majority of patents are for improvements in the case rather than the product. One granted to the Procter & Gamble Co. is for a product with a high level of hydrophilic moisturiser [REF 7] and describes formulations containing up to 20% of polyhydric alcohols and the like. A second patent granted to the same company [REF 8] describes lipsticks containing polar materials such as glycerine for their moisturising properties but states that such inclusions make the base more prone to sweating than is usual. This problem is overcome in the patent by the inclusion of a gelling agent such as propylene carbonate, ethyl cellulose, hydrophobic silica and clays and a surfactant which forms an association structure or liquid crystal with the polar solvent. The lipsticks described are substantially free from castor oil and the pigment is dispersed in the polar solvent/surfactant mix before being blended with the waxes and oils. The product is claimed to be more durable, have added moisturising benefits and be non-sweating than conventional products not containing polar materials.

The major difference between all decorative product formulations of fifty or more years ago and now is the introduction of silicone compounds. Silicones are now making regular appearances in lipsticks with the inclusion of cetyl dimethicone, cetyl dimethicone copolyol and stearoxy dimethicone recommended by Goldschmidt Chemical Corporation and cyclomethicone is the basis for the new slimsticks.

The use of silicones in other forms of makeup is well established and has done much to improve liquid foundations and similar products. The cyclomethicones are much used to disperse the pigments, improve application and impart a pleasant skin feel. They are also used to improve product durability and a patent granted to Revlon [REF 9] describes a product comprising volatile silicones, a silicone ester, a natural or synthetic wax, up to 30% of an oil component plus powders and pigments which is claimed to be transfer resistant and can be used for a variety of makeup applications. Enhanced durability is also claimed in a patent granted Dow Corning [REF 10] whereby an aqueous latex of a cross-linked polydiorganosiloxane is incorporated into the emulsion base which, on application in a product such as a cream eye shadow acts a film forming agent and improves application and resistance to rub-off of the product. Nor is the use of silicones restricted to liquid and stick products; a patent granted L’Oreal [REF 11] describes anhydrous powder compositions containing at least one silicone oil, at least one silicone wax, at least one silicone resin and optionally, at least one silicone gum and at least one phenyl dimethicone, this mixture being used as a binder for eyeshadows and other pressed powder products.

Multifunctional products continue to be of interest and a patent granted to Maybelline [REF 12] manages to include a sunscreen, a free radical scavenger, a moisturising agent, a skin firming agent plus pigments in a water-in-oil emulsion to smooth the skin, moisturise, firm and protect and improve the complexion. For those looking for multifunctionality the Cosmacol esters are useful for introducing the benefits of alpha hydroxy acids without the usual formulation problems. These esters are also claimed to be excellent dispersing aids and may be used in both o/w and w/o systems. For those wishing to add sun protection the Tioveil and Sunveil pre-dispersed pigments from Tioxide Specialties simplify the incorporation of micronised titanium dioxide and zinc oxide respectively in makeup products and they are now available dispersed in cyclomethicone and phenyl trimethicone as well as a range of esters. Advanced Polymer Systems supplies a number of different microsponges including one loaded with Vitamin A Palmitate which may be incorporated in free flowing or pressed powder products and also Polytrap beads containing cyclomethicone to add lubricity.

The US Cosmetics Corporation offers a mica substrate coated with aluminium hydroxide which eliminates strong specula reflectance and diffuses light in a similar manner to skin. This diffusion effect can be used to mask wrinkles and skin imperfections and the literature available through S. Black is well illustrated with colour photographs showing this application. Well illustrated literature is a feature of The US Cosmetics Co. and their brochure on talc has excellent scanning electron microscope pictures as well as X-ray diffraction data and particle size analysis histograms.

Although the pigments and dyestuffs allowed in cosmetics is strictly limited the suppliers are still able to offer a wide range of shades and colour effects. Kingfisher Colours claims to be the leading supplier in Europe of FDA certified colours and is able to undertake bespoke production to customers requirements of shade, strength and physical quality including the supply of barium-free grades. Anstead International also produce to customer requirements and are able to supply lipstick pastes prepared by triple roll milling with castor oil and oxide blends mixed with talc or titanium dioxide. Anstead’s have recently introduced a range of soap colours which mix readily with water and readily disperse throughout the soap.

The author can remember the first introduction of pearl pigments in the early sixties and the problems experienced with the bismuth oxychloride available at that time. Then came the mica based pearls and now there is an incomparable range of every shade and colour effect. Topy Industries in association with Nihon Koken Kogyo have produced a synthetic mica which because of its purity and freedom from iron and manganese contamination is a clear crystal which is used to produce iridescent colours with high colour saturation. The Sumitomo Chemical Co. produces a range of TiO₂ based materials including an ultrafine grade for UV screening and an anatase grade which darkens in sunlight and fades in the dark. This is available through Rahn UK who also supply the Permashade titanium dioxide and iron oxide coated silicas which resist colour and opacity changes when wetted by sebum or perspiration. Rona produces pearls in many forms including interference colours, titanium dioxide coated mica with and without additional pigments, transparent colours and dispersions of bismuth oxychloride and a wide range is also available through Engelhard, formerly The Mearl Corporation.

Pressed Powder Eyeshadows

The use of aluminium starch octenylsuccinate adds lubricity, water resistance and a silky feel to the following formulations; Dry Flo Elite LL is coated with lauroyl lysine which is hydrophobic with excellent skin adhesion and Dry Flo Elite BN is coated with boron nitride providing a high degree of slip; Dry Flo PC is the uncoated form; all three materials are supplied by National Starch.

INCI Name	% w/w	% w/w	% w/w	% w/w
Phase A
Zinc Stearate	3.00	3.00	3.00	3.00
Aluminum starch octenylsuccinate (&) lauroyl lysine	25.00		5.00
Aluminum starch octenylsuccinate (&) boron nitride		25.00		5.00
Aluminum starch octenylsuccinate			20.00	20.00
Imidazolidine urea	0.20	0.20	0.20	0.20
Pigments & Talc	64.80	64.80	64.80	64.80
Phase B
Isopropyl myristate	3.00	3.00	3.00	3.00
Caprylic/capric triglyceride	2.00	2.00	2.00	2.00
Isoeicosane	2.00	2.00	2.00	2.00

The pigments are blended with talc to the required shade and mixed well with the ingredients of Phase A. Separately the Phase B items are mixed together and the mix blended with Phase A. The finished product is pressed at 1500psi.

Lipstick

In this formulation the glyceryl diisostearate (Dermofeel GDI) and glyceryl triisostearate (Dermofeel GTI) improve pigment dispersion, stick stability and the texture and feel on application and the product has a high degree of skin substantivity and resistance to wear.

Ingredient	%w/w
Ceresin	4.00
Candelilla wax	8.00
Carnauba wax	2.00
Castor oil	30.00
Glyceryl diisostearate	30.00
Glyceryl triisostearate	10.00
POE (25) POP (20) 2-tetradecyl ether	1.00
Glycerin	2.00
Propylene glycol	1.00
Water	5.00
Antioxidant and fragrance	qs
Titanium Dioxide and pigments	7.00

W/O Liquid Foundation

In this formula supplied by Goldschmidt Chemical Corporation the cetyl dimethicone copolyol (Abil EM-90) polyglyceryl-3 oleate (Isolan GO-33) is the emulsifier system and the cetyl dimethicone (Abil Wax 9801) and cyclomethicone greatly add to the products texture, durability and pleasant skin feel.

Ingredient	%w/w
Phase A
Cetyl dimethicone copolyol	2.00
Polyglyceryl-3 oleate	1.00
Cetyl dimethicone	1.00
Octyl palmitate	1.00
Hydrogenated castor oil	0.40
Beeswax	0.80
Phase B
Cyclomethicone	18.00
Red/Yellow/Black iron oxides	3.00
Titanium dioxide	7.80
Talc	1.70
Phase D
Butylene glycol	2.80
Water	60.00
Sodium chloride	0.50
Phase E
Fragrance & preservatives	qs

Heat together the ingredients of Phase A to 85-90^oC and mix until uniform.

Cool to 70^oC and add cyclomethicone followed by the ingredients of Phase C; mixing thoroughly to disperse. Cool to 50^oC with mixing.

In a separate vessel combine the ingredients of Phase D at ambient temperature and add slowly to the main mix with slow agitation; when all added increase mixing speed and mix for 10 - 15 minutes. Homogenise and add fragrance and preservatives as required.

REF 1 Beale R, Kingfisher Colours Ltd. personal communication.

REF 2 Woodruff J, Woodruff's Ingredients & Formulary Handbook, Miller Freeman, 1997, pp151-155

REF 3 Optical properties of stratum corneum and development of natural-looking makeup, Nishikata K et al., Pola Co.

REF 4 Development of novel thin-layered material based on a new photo-complementary colour theory and its application in cosmetic foundation by T. Katsuyama et al Shiseido Laboratories.

REF 5 Chilson F, Modern Cosmetics, Formulation and Production published by The Drug and Cosmetic Industry, New York, 1934.

REF 6 Observation of the sweating of lipstick by scanning electron microscopy. Su-Youn Seo et al. Household & Personal Care Products R&D Institute, LG chemical Ltd. Korea

REF 7 Patent No US 5593662; The Procter & Gamble Co.; Moisturising lipstick compositions.

REF 8 Patent No. WO 95/11000; The Procter & Gamble Co.; Non-sweating lipsticks.

REF 9 Patent No. US 5505937; Revlon Consumer Products Co.; Cosmetic compositions with improved transfer resistance.

REF 10 Patent US 5512272; The Dow Corning Co.; Cosmetics with enhanced durability.

REF 11 Patent No US 5496544; L’Oreal; Powdered cosmetic composition containing a silicone fatty binder.

REF 12 Patent US 5560917; Maybelline Intermediate Co.; Cosmetic makeup