SPF from 8 to 14: maximum 40-min water resistance properties
SPF from 15 to 29: maximum 2-h water resistance properties
SPF > 30: maximum 4-h water resistance properties Cosmetics 2017, 4, 15 7 of 11 8. Formulation Solutions A precise formulation strategy has to be set in order to match with all the described (6) Use polar solvents to inhibit Norrish-Type-I cleavage of Avobenzone (Paraffin is bad, Ethanol requirements (SPF, UVA, Critical wavelength, water resistance). Moreover, one should consider is good); other variables, like the solubility and stability of some UV filters and, being cosmetic items, the sensorial This aspects. important phase requires also some considerations concerning: Particularly for the high SPF values, the best starting point is the selection of the right (a) The type combination ofof UVB finalandusers. UVA The useable filters, of Octocrylene, Ethlylhexyl to reach the right Methoxycinnamate broad spectrum protection and andthePABA best derivatives possible stability.isInnot suggested this phase, theforuse consumers with sensitive of a well-known, alreadyskin or forformula, tested, baby products [30]. the suggestions of the The (b) suppliers market: and/or Europe, the Japan,useUSA,ofetc.,a similarly sunscreen to whatsimulator happens freely available also for test methods, online the (https://www.sunscreensimulator.basf.com) number of available sunscreen ingredients areis some possible different starting according to theapproach. Usually, the different legislations. In blending USAof(where a highsunscreen number of UV filters products are at lowaspercentage sold OTC and not is better than a products) as cosmetic combination the of two or available threenumber of them of at UV highfilters percentage, both limited is extremely for safetyin concerns comparison andtoalso to achieve Europe. a synergic Also their maximum combination allowed of effects. The ideal percentages areaim is thecases in many highest possible different protection (Ethlylhexyl with the minimum Methoxycinnamate possible allowed amount at 10% of UV in Europe, filters. at Moreover, 20% in Japan); a high amount of sunscreen ingredients is often associated to a bad (greasy or waxy)If final (c) perception a water resistanton the skin. formula Some good is requested, combinations the could be: use of hydrosoluble UV filters (Phenylbenzimidazol Sulfonic Acid) could be a bad idea; (a) Diethylamino Hydroxybenzoyl Hexyl Benzoate and Ethylhexyl Triazone in 3:1 ratio [24]; (b) Among Octocrylene and filters, theButyl Methoxydibenzoylmethane selection of inorganic filters is aninincreasing a ratio of more trend orforless the3:1 [25]; of ‘natural’ request (c) Octocrylene + Butyl Methoxydibenzoylmethane + Bis-Ethylhexyloxyphenol claims. Titanium dioxide and zinc oxide are the most widely used metal oxides as UV Methoxyphenyl filters. They Triazine [26]; are efficient, almost photostable, absorb the UVB and UVA radiations and re-emit them mainly as (d) Bis-Ethylhexyloxyphenol visible fluorescence or heat. For their Methoxyphenyl Triazine chemical-physical (Bemotrizinol) characteristics, + Diethylhexyl the surface of the twoButamido pigments has toTriazone be coated+ Butyl with Methoxydibenzoylmethane “inert” substances like silica, (based on our alumina, experience, stearic acid or unpublished data). If silicone compounds. uncoated, TiO2 surface, Moreover, after UV the addition absorption, of small amountemits excited electrons, of inorganic UV filterswhich helpscan generate to boost thefree SPFradicals, values, resulting in oxidative damages into the dermal layers. On the other side, ZnO, if uncoated, because solids are able to scatter the UV rays and increase their probability to hit and interfere with can modify the pH of the product as it tends to turn partially into Zn hydroxides, partially releasing OH − the molecules of ‘chemical’ UV filters. ions in Thetheuse system [31].Methoxydibenzoylmethane of Butyl Moreover, the coating prevents the agglomeration (Avobenzone) is almostofessential particlesto and keephigh reach the pigments well dispersed in the system, while improving the stability and UV UVA protection, but it has to be adequately stabilized in order to avoid the undesired protection efficacy of the sunscreen product. reaction (Figure 2): photo-ketonisation
Figure 2. Irreversible photoreactions of Avobenzone [27].
Figure 2. Irreversible photoreactions of Avobenzone [27].
The stabilization of Avobenzone could be reached by using different strategies [28,29]:
Titanium dioxide and zinc oxide are especially used in their ‘nano-sized’ form for many reasons. (1) nanosize The The rightdimension stabilizers:enhances the protection capacity [32]. Moreover, the smaller the particles, the higher the homogeneity of the layer onto the skin, the better the coverage of the epidermis. Finally, for particle size of about 35 nm, nanoparticles are big enough to absorb, scatter and reflect short-wavelength UV radiation while they keep invisible to the longer-wavelength, visible light. In this way, the sunscreen formulation is transparent to the eyes. The optimum particle size for high UVB and UVA attenuation but good transparency is between 40 nm and 60 nm [33] (see Figure 3).
Photostabilization of Butyl Methoxydibenzoylmethane (Avobenzone) and Ethylhexyl Methoxycinnamate by Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S), A New UV Broadband Filter