THE RAW MINERAL SALTS USE IN COSMETICS FORMULATIONS: ASSORTMENT, MINERAL RAW MATERIALS CHARACTERISTICS AND COSMETICS FORMULATION TECHNOLOGY

全文:

The cosmetic products on the base of mineral salts from the natural ingredients: mineral water (thermal spring water), sea water, lake salt and brine, minerals (bischofite) are widely used nowadays. Such popularity is due to the wide spectrum of biological activity of natural minerals: anti-inflammatory, moisturizing, reparative, UV- protective, anti-oxidant, etc. Cosmetic products based on mineral raw materials are presented as formulations for the everyday treatment, and for correcting certain cosmetic problems such as skin aging, acne, dry and sensitive skin, cellulite and psoriasis, atopic dermatitis, rosacea [1-6]. Most mineral cosmetic formulations are so-called cosmeceuticals - intense action cosmetics. Their signified activity conduced the implementation peculiarities: primarily through beauty parlors and specialty shops (professional cosmetics brands «Algologie», «Biomaris»), pharmacy chains (brand medical cosmetics «Vichy», «La Roche-Posay», «Bioderma», «Avene» based on the thermal waters) [7-9]. The range of cosmetic products based on certain types of raw materials of mineral origin is shown in Table 1 [2, 10-16]. The data presented in Table 1 show the diverse range of cosmetics based on natural mineral salts, presented by means for primary care (creams and gels for face and body, lotions, tonics, micellar water, shampoos) and intense care (masks, serums, scrubs, peels). These products include different cosmetic forms: creams, lotions, tonics, lotions, serums for the face and body, and cosmetic for hair care (shampoos, masks, conditioners). It should be noted a small assortment of Russian products, presented by series of cosmetics “Rapan” (gels and facial lotion for the face), bischofite series, and more wildly represented series of “Formula vodyi” presented by face creams for different skin types, milks and lotions, face masks. Raw materials of mineral origin are characterized by very complex ion composition with of magnesium, calcium, sodium and chloride prevalence, and the presence of various minerals (Table 2) [9, 17-21]. As follows from the table, raw materials differ by mineralization: the minimum is observed in thermal waters, and the maximum - bischofite brine. The mineral raw materials used in cosmetics, contain cations of magnesium, calcium, potassium, sodium, high concentrations of chloride, sulfate, bromide, hydrocarbonate anions. The presence of various trace elements (selenium, copper, zinc, silicon, iron, strontium, manganese) is noted in minerals composition and the most often in the thermal waters content. The chemical composition of the natural mineral salts determinates their effect on the skin. Silicic acid exercises a drying effect on skin. Magnesium salts exhibit anti-inflammatory activity, showing antagonism to inflammatory mediators - serotonin, histamine, prostaglandins and the magnesium ability to reduce the cyclooxygenase activity. Magnesium salts action is associated with tissue and immunity increase. Calcium salts possess anti-inflammatory activity, restoring electrolyte balance in inflammation. Sodium chloride improves microcirculation and the inflammatory focus resorption. The studies established anti-inflammatory activity of thermal water «La Rosh-Posay» caused by the presence of selenium and strontium. Anti-inflammatory effect plays a role in formulations against acne, for the anti-age skin care, skin care for atopic dermatitis and psoriasis [3, 22-24]. Sodium, potassium, magnesium, calcium, phosphorous are the components of skin natural moisturizing factor which leads to their use for dry skin care and anti-age care [17, 25-27]. Natural thermal water (spring water) is a balneological mineral water with a temperature of at least 20 °C, often characterized by a high silicic acid content (more than 50.0 mg/dm3) and up to 250-300 mg/dm3 for external use. Thermal springs are used in balneotherapy in different countries (Russia, France, Belgium, the USA, and Hungary), for example there are up to 1,200 thermal springs in France. Thermal springs are common in the North Caucasus, the Altai, the Black Sea coast, the Baikal region and the Far East in territory of Russia. They chemical composition divided into five classes (classification is given in European data): bicarbonate, sulfate, sulfide, chloride, weakly mineralized trace metal [24, 28, 29]. Thermal waters used in cosmetics contains a wide range of trace elements such as iron, manganese, zinc, chromium, cobalt, copper, nickel, lithium, aluminum, fluorine, bromine, iodine, phosphorus and selenium [9, 20, 29]. Cosmetic series containing natural waters are «La Roche-Posay» (France), «Vichy» (France), «Uriage» (France), «Aven» (France), «Biotherm» (France), “Formula vodyi” (Russia). Sea water - water concentrated in seas and oceans characterized by the persistence of the salt composition, the main components of which are chloride and sulphate anions, sodium, calcium, magnesium, potassium cations, dissolved gases and a small amount of organic substances. Chlorides are dominated among the salts (sodium chloride, magnesium chloride); further sulfates (magnesium sulfate, calcium sulfate, potassium sulfate), carbonates (calcium carbonate), bromides (magnesium bromide) [2, 11, 21]. The known cosmetic brands on the basis of the seawater and seaweed presented by European producers are «Phytomer», («Jacques Dessange», France), «Talasso SPA» («Integra», Spain), «Algologie» (France). Brine water is saline lakes, bays and firth water, usually covering a layer of a mud. Mineralization of the brine can be very high, and often comes to 300-350 g/l. The composition includes various mineral ions, preferably sodium, calcium, magnesium, potassium cations and sulfate, hydrocarbonate, chloride anions, organic substances (humic acids, vitamins, amino acids, peptides, polysaccharides). Manufacturers, including Russian, produce cosmetic lines on the basis of the lakes brine: cosmetics based on Saki lake mud (series “Fitobiol”, “Gaia”), cosmetic series “Rapan”. The promising sources of brine are the lakes of the European part of Russia - Elton, Baskunchak, Tambukan, Siwash, Tinaki lakes complex [21, 23, 30, 31]. Amud water extracts (mud solution) are used as well as brine. Mud solution is a liquid phase of a mud, obtained by pressing, centrifugation or filtration, and consisting of the salts dissolved in water, organic compounds and gases. The chemical composition of mud solution basically corresponds to the brine, which formes this mud. The salts in mud water consist of sodium, magnesium and calcium cations, chlorine, sulfate and bicarbonate anions. It also contains organic material. For a cosmetic product use is offered, for example, cosmetic substances based on brine and mud solution “Tambuil-water extract” (LLC “Bivitex”, Nalchik) [29, 31, 32]. Cosmeceuticals products based on minerals from the Dead Sea are also widely represented. The Dead Sea is salt lake, which is fed by numerous mineral springs and the Jordan River. Salinity the Dead Sea at 8 times the Atlantic Ocean and 40 times the Baltic Sea. Sodium chloride content in the Dead Sea water is 25-30% of the total salt composition (vs. 77% for sea water), while the share of magnesium salts, up to 50%. The high (80 times higher than in the Atlantic Ocean) content of bromine is also a characteristic feature of the composition. Israeli and Jordanian firms (up to 40 types of cosmetic brands) produce cosmetics on the basis of Dead Sea highly concentrated saline solutions, brine, thermal springs and mud. The most active in this sector, companies operate in Israel (brands «Sea of SPA», «Ahava», «Talia», «Dr. Sea», «Premier», etc.) and Jordan (brand «Bloom», «La Cure» and «VIVAcity») [4, 17, 33, 34]. Bischofite - a magnesium chloride mineral (MgCl x6H O) (P.G. Feldman, 1984), named after its discoverer professor of chemistry at the University of Bonn Karl Bischoff, who lived in the xIx century. The main component of bischofite is MgCl x6H O (80-99%), the balance impurities including isomorphic bromine (0.5-0.9%), carnallite, halite, kieserite, anhydrite, as well as numerous trace elements, in number more than 70 titles. The extensive research of bischofit mineral of Volgograd origin On VolGMU base are carried out: chemical, technological and pharmacological. It was found that the bischofite ointment improves tissue regeneration by providing a stimulating action on the reparative processes in the infected and uninfected skin defect healing and advances the clearance of bacterial contamination of infected wounds in rats. Bischofite ointment shows a bacteriostatic effect against opportunistic microorganisms to (St. aureus, St. epidermalis, C. ablicans, E. coli). A rapid decrease in swelling of tissues and accelerating the formation of granulation tissue in the treatment with the bischofite ointment on the model cold injury was revealed. Overall, these findings suggest a promising use of bischofite in cosmeceuticals formulations [21, 35]. Cosmeceuticals are the products, which are used after various researches, and therefore the use of all product ingredients is scientifically proven. This approach characterizes the development and research of cosmetic products based on thermal water («Vichy», «Aven», France), cosmetics based on Dead Sea products («Ahava», Israel) and is similar to the approach used in research of bischofite mineral semisolid formulations for topical administration (Russia) [6, 9, 35-37]. The range of products containing Dead Sea mud and salts composition, has up to a thousand names submitted by various manufacturers and include creams, serums, gels, masks, foams, lotions, scrubs, shampoo, toilet soap, salt baths. Different mineral complex concentration depending on the purpose (basic or intensive care) the formulation might be used. The literature and patent data have showed that cosmetics based on mineral salts solutions, as well as therapeutic mud, can be divided into three main groups according to the concentration of mineral components and product dispersal specification [6, 34, 38-44]. The first group of cosmetic formulations contains high concentrations of natural mineral substances (more than 10%) and include face and body mask which can be characterized as highly viscous disperse products. The second group includes masks, creams, serums (oil/water or water/oil emulsions) containing mineral salts in a concentration of 1-10%. The third group is represented by cosmetic formulations with a low concentration of salts in the range of 0.01-1% (cleansing milk, face creams, gels for the skin around the eyes, lotions, tonics). Highly concentrated Dead Sea, bischofite and brine solutions cause a decrease in the stability of cosmetic forms, resulting on their complicated manufacturing process and storage. Technological complexity of manufacture and low emulsion stability during storage dues to the high ionic strength of the brine solution, which introduces a certain restrictions on the salt content in the cosmetic formulations [34, 42, 45-47]. The phenomena of the instability of emulsions containing mineral salts, is explained by the lyophobic systems stability theory, theory DLVO (Derjaguin-Landau-Verwey-Overbeek theory). According DLVO theory the stabilization of emulsions or suspensions can be presented as a combined result of the interaction of attraction and repulsion forces between the droplets or particles, respectively, dispersed in a dispersion medium. Thus, an oil/water emulsions are stabilized by the adsorption of an ionic surfactant on the surface of the oil droplets, which subsequently gains a positive or negative charge. The occurred zeta potential contributes repulsion of the approaching particles. If repulsive forces prevail over the forces of attraction, the emulsion is stable [34, 48]. It should be noted that the magnitude of the zeta potential depends on the electrolyte concentration and ions valence in solution, for example, cations in the case of negatively charged emulsion. In systems containing in general a high concentration of electrolytes, and in particular, divalent ions (typical for mineral natural products with high salt content) electrostatic repulsion is substantially reduced [21, 37]. The data of the study of the model oil/ water emulsions stability in the presence of supporting electrolyte - sodium chloride, used in cosmetic formulations as a viscosity regulator are presented. It was found that the zeta potential of the emulsion droplets produced by caprylic/capric triglyceride as the oil phase in the presence of emulsifi and nonionic and anionic nature falls from 5 mV to 45 mV after sodium chloride adding. This is associated with increasing ionic strength, and, as a consequence, contraction of the diffuse part of the double electrical layer, which leads to the rapid emulsion phase separation [49]. These physical and chemical processes occurring in emulsions (creams, lotions, masks) creates certain difficulties during the cosmetics emulsion formulations based on mineral salts development. It should take into account that the cosmetic products must meet all criteria of stability for 1.5-3 years. In addition to these electrostatic interactions, high salt concentrations can lead the salting-out and precipitation of other components of the emulsion cosmetic formulation, which also may affect the stability during storage, and make the consistency and appearance changes the of the product [34, 46]. For solving the problem of instability of cosmetic products in the presence of mineral salts several technological approaches can be used: - The use of nonionic surfactants (glyceryl stearate, cetyl alcohol, ceteareth-n, montanov, olivem-1000, polysorbat); - Careful experimental selection of compatibility of the salt composition with the other components; - The use of polymer colloid to thicken and stabilize the system in particular emulsions; - The use of microencapsulates, nanoparticles, nanoemulsions, liposomes [24, 46, 48, 50]. The polymer colloid use to thicken and stabilize is a common method for stabilizing cosmetic emulsions in general, and particular in compositions containing mineral salts. For example, in highly viscous dispersion - the cosmetics masks containing mud and high salt concentration (the first group of cosmetic products according to the proposed classification) polymers agents provide the desired consistency and stability [30, 51, 52]. Thicken agents used in creams brand «Ahava» are xanthan, polyvinylpyrrolidone, biosaccharid gum-1, hydroxyethyl cellulose, guar gum, etc. Polysaccharide containing algae extracts of Laminaria, Fucus, Ascophyllum are used with the similar function [10, 37]. Data research stability and efficient of cosmetic formulations with thermal water and mineral salts based on biosaccharid gum-1 gel showed the highest stability and more pronounced moisturizing properties compared with containing thermal water cream-gels on the basis of polyacrylate and creams emulsion [46]. At the same time, thicken polymers are the high molecular weight compounds, and are possible to intermolecular interactions and complex formation with ions that natural minerals contain. Mineral complexes are capable for forming coordination bonds (chelates) with a magnesium and calcium ions due to donor-acceptor interaction between the metal ion and polymer ligand. Substitution of protons by metal ions and formation of ionic bond is also possible [45, 53]. This interaction should also be taken into account when creating cosmetics formulations. As an example, studies under development of the bischofite mineral semisolid formulations for topical routes of administration can be mentioned. The compounds forming complexes by physical or chemical interactions with viscosity loss or complete destruction were selected and eliminated during research [21, 45]. It also should be noted very sensitive to fluctuations in pH and electrolytes presence carbopol gels, gelling agent, most often used in cosmetics. This should be taking into account when using the thermal waters, characterized by alkaline or acidic pH, as the aqueous phase for carbopol gel preparation [30, 51, 54]. The influence on cosmeceutic formulations stability the high electrolytes (magnesium and calcium) concentrations, it should be noted the presence of such components of natural mineral complex as iron II ions. Iron II ions are pro-oxidant compounds that trigger free radical chain reactions. The high concentrations prooxidant availability in cosmetics emulsions facilitates lipid peroxidation and vegetable oils rancidity. This product gets a sharp, unpleasant odor and has the skin irritating properties [26, 29]. To solve this problem the purification of natural raw materials is used. For example, it can be mentioned that the use bischofite mineral, containing a number of impurities, in pharmaceutical practice is limited. One of the main bischofite impurities is iron, which is contained in the mineral itself, and misses as a result of corrosion of the metal pipe during its production. Taking this into account a method of bischofite purification has been proposed. The results showed a low toxicity level of the purified bischofite solution (LD for females rats was 6.3 ml/kg, and in males - 7.2 ml/kg, in comparison with unpurified form below twice) [21]. Sulfides which are part of some of the thermal waters, silt sulfide mud and brine lakes can engage in redox reactions. Additionally, hydrogen sulfide is characterized by an unpleasant odor, which impairs the organoleptic properties of the cosmetic product. In view of the foregoing, it should be noted that in the development of cosmetics formulations with mineral salts, including the choice of optimal mineral salt concentration, must include extensive tests on stability: colloidal stability, rheology tests, thermal conductivity and their change during storage. The rheological behavior of the cosmetic product after mineral complex addition and its stability under different temperature storage conditions (e.g., 8 °C, 20-25 °C, 37 °C, 45 °C) are usually studied [42, 43, 46, 47, 55]. Another limiting factor for mineral salt use in cosmetic formulation is their effect on skin moisture sense after application, and the lack of tightness of the skin. This side effect mostly pronounced in highly mineralized mud. They often used in mask form, compositions in which therapeutic mud is distributed in foundation (clay, gels, polysaccharides, talc, magnesium aluminum silicate) in this consequence. At the same time, one of the benefits of thermal waters as cosmetics is their low salinity, providing a moisturizing effect without the existence of the skin dryness [26, 30]. On this basis, evaluation of moisturizing properties of cosmetic formulations based on mineral raw materials may be for optimal concentration selection. It is carried out practically using sensory tests on volunteers (volunteers questionnaires, subjective analyses), and objective analyses by instrument methods - measurements of aqueous con- tent of the corneum stratum (corneometry) [6, 37, 46]. Thus, theuseofnaturalmineralrawmaterials in cosmetic formulations, has an apparent efficacy in a variety of cosmetic problems, including acne, dry skin, aging, cellulite, atopic dermatitis, psoriasis. Natural raw material that contain mineral salts, has a fairly wide resource base, including different natural sources (brine lakes, thermal water, bischofite mineral, etc.). At the same time, the development of new cosmetic products on the base of mineral salts is associated with the specifics of this group of raw materials (ability to affect the stability of the formulation and the sensory properties of the finished product).

作者简介

S. Evseeva

«Bivitex»

Email: sbevseeva@yandex.ru
Nalchik, Russian Federation

B. Sysuev

The Volgograd State Medical University of Public Health Ministry of the Russian Federation

Email: bsb500@yandex.ru
Volgograd, Russian Federation

参考

补充文件