PL234148B1 - Carrier/active substances system, and cosmetic compositions that contain such a system - Google Patents

Description

Description of the invention

The subject of the invention is a carrier / active substance system containing silica airgel as a carrier for active substances. The invention also includes cosmetic compositions containing this system.

Silica in various forms is used in cosmetics due to its excellent thickening, thixotropic, anti-sedimentation and dispersing properties. Mixed with water (5% silica to 95% water) it creates "dry water" in the form of a powder, which when used in creams moisturizes the skin and prevents it from shining. Valuable properties of silica include the ability to absorb sebum and scatter light, which has the overall effect of improving the appearance of the skin. Silica used in w / o emulsions allows to obtain higher viscosity. In concentrations higher than 3%, it allows you to eliminate the feeling of greasy cosmetics, making the skin feel dry. Due to the absorption of fats, it is usually present in cosmetics intended for oily and combination skin. Silica can be found in cosmetics that conceal wrinkles and even out skin tone. It is also a component of peels and cleansing gels. Silica aerogels can be used as a dispersant (dispersing solid or liquid substances in solid or liquid media).

It is known from publications and patents to use hydrophobic silica aerogels as carriers of active substances contained in cosmetic compositions. To obtain a hydrophobic silica airgel, the process of hydrophobization of unmodified silica aerogels containing hydroxyl groups is carried out by subjecting them to a silylation process by using alkylchlorosilanes, siloxanes, silazanes, which reacts the hydroxyl group to form an alkylsilyl group.

WO 2013/087927 describes the use of a hydrophobic silica airgel in cosmetics in a composition with a hydrophilic homo-polymer or acrylic copolymer.

WO2012 / 084781, US2014 / 0302105, WO2013 / 117550 and KR2008-0040097 describe the use of hydrophobic silica aerogels as ingredients in cosmetics that cleanse the skin with a matting effect. In these cosmetics, hydrophobic silica aerogels act as an absorbent that absorbs excess sebum, causing the skin to become matte after application.

The patents US2015366783, US2015132350, US2014302105, US2013337026 describe the use of hydrophobic silica aerogels in cosmetics as carriers for active substances, e.g. vegetable and mineral oils. The obtained effect is the care and nourishment of the skin with unsaturated fatty acids without the effect of oiling it.

In the carrier / active systems according to the invention, unmodified hydrophilic silica aerogels were used. Hydrophilic silica aerogels have different chemical properties compared to hydrophobic silica aerogels. Due to the content of hydroxyl groups in the entire structure of the hydrophilic airgel, it has a highly developed surface. Depending on the synthesis method, the size and shape of the pores can be adjusted, which allows for selective sorption and the release of active substances introduced into cosmetics. In addition, the presence of hydroxyl groups facilitates the removal of impurities from the skin surface, contributing to the increase in the effectiveness of cleansing cosmetics.

Hydrophilic silica aerogels can be a carrier of hydrophilic active substances. Hydrophilic silica aerogels can be directly loaded with hydrophilic substances, just as hydrophobic silica aerogels can be loaded with hydrophobic substances exhibiting lipophilicity. The use of an appropriate silica airgel allows for the release of active substances loaded with the airgel at a rate resulting from the airgel structure.

The publications and patents describe the use of vitamins A, E and C in cosmetics, which are considered the most valuable for the skin. In the case of these vitamins, their antioxidant and anti-inflammatory importance is appreciated. Free radicals generated by the action of UV radiation as well as air pollution penetrating the skin are effectively neutralized by vitamins, which protects skin cells against the destructive effects of these harmful factors. These vitamins are able to suppress pigmentation and lighten discoloration, stimulate collagen synthesis, smooth the skin surface. Of these three vitamins, vitamin C is unstable in cosmetic compositions.

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There are reports in the literature on the synergistic action of three vitamins A, C and E, consisting in an effective breakdown of radical chain reactions in the skin.

From the point of view of cosmetic utility, the most valuable is the combination of vitamins C, E and A in one carrier, allowing the simultaneous release of three vitamins. The problem, however, is the simultaneous loading of the silica airgel carrier with various active substances, some of which are hydrophilic (e.g. vitamin C) and others lipophilic (vitamin A and vitamin E).

It is important from the point of view of a cosmetologist and a cosmetics technologist to introduce hydrophobic (lipophilic) active substances into liquid hydrophilic dispersion media by means of hydrophilic silica airgel. The invention solves this problem by producing a microemulsion with a hydrophobic substance and loading the hydrophilic silica airgel with this physicochemical form.

The carrier / active substances system containing silica airgel as a carrier for active substances, according to the invention is characterized in that the carrier of the active substances is a hydrophilic silica airgel, and active hydrophobic and / or hydrophilic substances are embedded in the carrier in the form of a microemulsion.

Preferably the carrier / actives system comprises a hydrophilic silica airgel with a bulk density of 0.02 g / cm ³ to 0.03 g / cm ³ .

Preferably, the carrier / active substances system comprises hydrophilic silica airgel in a weight ratio of the active substances of 0.2 to 20.

Preferably, in the system according to the invention, the active substances are vitamin C or vitamin E or vitamin A or mixtures thereof.

Preferably, the microemulsions of active substances contained in the hydrophilic silica aerogel carrier are made with natural emulsifiers and co-emulsifiers.

The cosmetic compositions according to the invention are characterized in that they contain a carrier / active substance system as defined above.

Preferably, cosmetic compositions contain an airgel carrier / active system system as defined above in an amount of from 0.5% to 10% by weight.

Due to the invention, it is possible to load a carrier, which is a hydrophilic silica airgel, with simultaneously active hydrophilic and hydrophobic substances converted into a microemulsion. In addition to the vitamins mentioned, the hydrophilic silica airgel carrier can be loaded with other active substances or their mixtures, for example:

- Queen Cactus extract for one night (Phytofleur Cactus) - photoprotective substance,

- white mulberry root extract (Morus Alba Root) - lightening agent,

- sea buckthorn extract (Seabuckthorn) - a rejuvenating substance,

- marigold extract (Marigold) - a soothing substance,

- sodium hyaluronate - moisturizing substance.

Important advantages of microemulsions are: optical isotropy, low viscosity, homogeneity and thermodynamic stability. Microemulsions are formed spontaneously without any mechanical energy. Microemulsions can be prepared by the following methods:

- by mixing the lipophilic active substance, emulsifier and co-emulsifier in appropriate amounts, and then slowly adding water (or other polar substance) until the system is clear,

- by mixing the oil phase, the emulsifier and the water (or other polar substance) and then slowly adding the co-emulsifier until the system is clear.

The invention, consisting in the use of hydrophilic silica aerogels as functional carriers of active substances with different lipo- and hydrophilicity, for example simultaneously vitamins C, E and A in order to achieve synergy of action, creates the possibility of obtaining compositions that meet the various requirements set for modern skin care and nourishment preparations .

Moreover, it was surprisingly found that the unstable vitamin C packed into the pores of the hydrophilic silica airgel carrier is not as unstable and does not lose its properties as quickly as if it is incorporated directly into the cosmetic (without the carrier).

In a detailed illustration of an embodiment of the invention, and in order to demonstrate the beneficial effect of the invention of the use of hydrophilic silica airgel, vitamins C, E and A were used as active substances loaded with hydrophilic silica airgel.

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Table 1. Cosmetic characteristics of vitamins C, E and A.

Vitamin Vitamin C Vitamin E Vitamin A Characteristic - hydrophilic substance chemically unstable, decomposes under I went to the light and oxygen it works in water environments and on the border of water and lipid areas stable lipophilic substance the highest activity of utocopherol • works in the lipid phase and at the interface it has an affinity for lipophilic and hydrotllic radicals free retinol is unstable and unstable, its esters are used in cosmetics. range of use of retinol and its esters in cosmetics in the amount of max. 0.1% Cosmetic action antiradical activity - regulation of collagen biosynthesis ability to reduce the left tocopheric radical (synergism with vitamin E) lightening of discoloration moderate exfoliation effect natural anti oxidant anti-irritation and anti-inflammatory effect protects the walls of the dishes the blood of the little ones vitamin Λ storage capacity anti-radical activity accelerating the renewal of the epidermis regulation of keratinization • regulation of melanogenesis • reduction of sebum production

In the examples of implementation of the invention, hydrophilic silica airgel produced at the Industrial Chemistry Research Institute in Warsaw was used, the properties of which are presented in Tables 2 and 3.

Table 2. Physicochemical properties of hydrophilic silica airgel.

Property Value Specific BET surface area 593 m ² / g Average particle size 10 nm Average pore size 16 nm Total pore volume 0.49 cm 7g Pore size distribution Heterogeneous SiO ₂ content calculated on a dry weight basis > 99.8% w / w Bulk density 0.0225 g / cm ³ PH value 4% water dispersion 3.7-4.51

Table 3. Water absorption of hydrophilic silica airgel.

Water absorption Character <240% Loose powder <280% Gel consistency <300% Liquid suspension

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The following raw materials have been used in the embodiments of the invention:

- emulsifier: Polyglyceryl-6 Caprylate, Polyglyceryl-4 Caprate, Polyglyceryl-4 Cocoate, Polyglyceryl-6 Ricinoleate, TEGO Solve 61, Evonic Ind.

- co-emulsifier: PEG-7 Glyceryl Cocoate, TEGO Soft GC, Evonic Ind.

- emollient: Caprylic / Capric Triglyceride, Labrafac CC

- argan oil: Argania Spinosa (Argan) Nut Oil

- vitamin E: dL-a-Tocopherol,

- vitamin A Retinyl Palmitate

- vitamin C L-Ascorbic Acid.

Example 1. System: carrier - hydrophilic silica airgel / hydrophilic ac-

active - vitamin C. Hydrophilic Emollient airgel Vitamin C 10% water solution 11 pcs. wt. 8 pcs. wt. 1 part wt.

Example 2. System: carrier - hydrophilic silica airgel / hydrophobic active substance - vitamin E.

The introduction of hydrophobic vitamin E into the structure of hydrophytic silica airgel was preceded by the preparation of a microemulsion with this vitamin using an emulsifier and a co-emulsifier.

Layout recipe:

Hydrophilic airgel Emulsifier Co-emulsifier Argan oil Vitamin E 1 part wt. 8 pcs. wt 1 part wt. 0.5 parts wt. 0.5 parts wt.

Example 3. System: carrier - hydrophilic silica airgel / hydrophobic active substance - vitamin A.

The introduction of hydrophobic vitamin A into the structure of hydrophilic silica airgel was preceded by the preparation of a microemulsion with this vitamin using an emulsifier and co-emulsifier.

Layout recipe:

Hydrophilic airgel Emulsifier Co-emulsifier Argan oil Vitamin A 1 part wt. 8 pcs. wt. 1 part wt. 0.5 parts wt. 0.5 parts wt.

Example 4. System: carrier - hydrophilic silica airgel / hydrophobic active substance - vitamin A and vitamin E + hydrophilic active substance - vitamin C.

The introduction of hydrophobic vitamins A and E into the structure of hydrophilic silica airgel was preceded by the preparation of microemulsions with the participation of these vitamins with the use of an emulsifier and a co-emulsifier.

Layout recipe:

Hydrophilic airgel Emulsifier Co-emulsifier Argan oil Vitamin 10% aq C Vitamin E and / or A 2 part wt. 8 pcs. wt. 1 part wt. 0.5 parts wt. 0.5 parts wt. 0.5 parts wt.

The airgel / active ingredient systems according to the invention can have an extended qualitative composition, since the pore structure of the hydrophilic silica airgel allows more bioactive and auxiliary components to be "packed" therein.

The research on the release of active substances from the carrier-hydrophilic airgel / active substance (vitamin or vitamin mixture) was carried out for mixtures constituting the basic composition of cosmetic compositions (cosmetic bases), in which the carrier / active substance system is in the water phase protected with a preservative, next to the chelating agent. Cosmetic bases in various physicochemical forms are presented below: example 5 and 6 for gel, example 7 for emulsion:

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P r z l a d 5. Hydrophilic airgel 2.5 parts wt. Emulsifier 10 pcs. wt. Co-emulsifier 1 part wt. Argan oil 0.5 parts wt. Propylene glycol 8 pcs. wt. Vitamin C 1 part wt. Chelating agent qs. * Preservative qs. Water up to 100 parts wt. * sufficient quantity Hydrophilic airgel 11 pcs. wt. Argan oil 0.5 parts wt. Emollient 4.4 parts wt. Vitamin C 2 part wt. Propylene glycol 8 pcs. wt. Chelating agent qs. Preservative qs. Water up to 100 parts wt. Example 7. Hydrophilic airgel 1.7 parts wt. Emulsifier 8 pcs. wt. Co-emulsifier 1 part wt. Vitamin C 0.85 part wt. Vitamin A 0.85 part wt. Vitamin E 0.85 part wt. Chelating agent qs. Preservative qs. Water up to 100 parts wt. The content of stable forms of hydrophilic and hydrophobic active substances was monitored

by high performance liquid chromatography HPLC. A standard curve was determined for the dependence of the concentration of vitamins A, E and C on the intensity of the UV absorption signal. Individual solutions were analyzed by determining the% content of vitamins in the vehicle in the cosmetic base. The concentration of vitamins C, E and A was determined immediately after placing the hydrophilic airgel carrier loaded with vitamins contained in the cosmetic base and after 7 and 14 days of their storage at room temperature (examples 5-7). The reference value was the measurements of vitamin stability, i.e. the determination of the concentration of vitamins directly in an aqueous solution - for vitamin C (example 8) and in the microemulsion system - for vitamins C, E and A (example 9), stored under the same conditions of time and temperature as the bases cosmetic products containing hydrophilic silica airgel (examples 5-7). The obtained chromatographic data are summarized in Table 4.

P r z k ł a d 8. Vitamin C 2 part wt. Propylene glycol 8 pcs. wt. Chelating agent qs. Preservative qs. Water up to 100 parts wt P r z k ł a d 9. Emulsifier 8 pcs. wt. Co-emulsifier 1 part wt. Vitamin C 0.85 part wt. Vitamin A 0.85 part wt. Vitamin E 0.85 part wt. Chelating agent qs. Preservative qs. Water up to 100 parts wt

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Table 4. Content of stable forms of vitamins from the airgel carrier (examples 5-7) and stability of vitamins in aqueous solution and in microemulsion (examples 8-9).

Example No. Vitamin Initial concentration. % Concentration after 7 days. % Concentration after 14 days. % Vit. C. 1.00 0.87 0.77 6 Vit. C. 2.00 1.66 1.23 7 Vit. C. 0.85 0.70 0.64 Vit. AND 0.85 0.72 0.52 Vit. E. 0.85 0.75 0.64 8 Vit. C. 1.00 0.30 0.05 _ _ 9 Vit. C. 1.00 0.35 0.10 Vit. AND 1.00 0.70 0.48 Vit. E. 1.00 0.62 0.46

Comparative studies of the release of vitamins A, C and E in cosmetic bases containing: hydrophilic silica airgel / active substances (according to the invention) and hydrophobic silica airgel / active substance system (example 10) were performed. Changes in the content of vitamins not embedded in the airgel carrier were also checked (Table 5).

Example 10. Hydrophilic airgel Emulsifier Co-emulsifier Vitamin C Vitamin A Vitamin E Chelating agent Preservative Water 1.7 parts wt. 8 pcs. wt. 1 part wt. 0.85 part wt. 0.85 part wt. 0.85 part wt. qs. qs. up to 100 parts wt.

Table 5. Comparison of the vitamin content in cosmetic bases containing: hydrophilic silica airgel and vitamins (according to the invention) or hydrophobic silica airgel and vitamins.

Sample Type: Vitamin A % AND and Vitamin E% 1 Vitamin C % emulsion cosmetic base Beginning; ^{1 1} 1 After 7 After 14; ,. 1,. , and the Beginning days; dmachi After 7 days After 14 days Start · After 7 'After 14' days with airgel hydrophilic m (Example 7) 0.85 0.72 '0.52 0.85 0.75 0.64 0.85 ' 0.70 0.64 with airgel hydrophobic m (Example 10) • 0.85 1 0.75 0.54 0.85: 0.69 0.56 0.85 and 0.53 ¹ 0.34 disrupting a silica airgel (Example 9) 0.85 ^j 0.60 0.41 0.85 0.53 0.39 0.85 0J0 ¹ 0.08 i

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As can be seen from the above list for vitamin A, the results for both types of carrier are comparable. The advantage in this case is that it can be introduced together with the active hydrophilic substance. For vitamin E, the results are more favorable with a hydrophilic airgel. For vitamin C, which is unstable in cosmetics, significantly more favorable results were obtained in the case of cosmetic base with hydrophilic silica airgel, compared to cosmetic base with hydrophobic silica airgel and cosmetic base without carrier.

Airgel systems according to the invention, containing a hydrophilic silica airgel carrier / hydro- and / or lipophilic active substances, in particular active substances of the vitamin C, A and E type and plant extracts (e.g. one night queen cactus extract, white mulberry extract, extract sea buckthorn, marigold extract) meet the criteria for cosmetic raw materials and are intended for use in various physicochemical and cosmetic forms, in particular in white cosmetics. They can be used in so-called cosmetics. in aqueous solutions, for example in micellar lotions or in shampoos, and in cosmetic emulsions, for example in creams or milks.

The airgel systems according to the invention combine the characteristics of e.g. vitamins and silica. Due to the content of active substances such as vitamins A, E, C and their synergistic interaction, these systems will provide cosmetic compositions with nutritional, anti-aging and revitalizing properties. The presence of hydrophilic silica airgel enriches the product with such features as: the ability to absorb sebum, the ability to scatter light. The airgel system, the hydrophilic silica carrier / active substances, protects the active substances against the adverse effects of the external environment.

The following is a specification of cosmetic bases containing hydrophilic silica airgel / active substances prepared according to the embodiments of the invention:

- appearance: homogeneous emulsion throughout, without lumps,

- color: white to cream,

- smell: characteristic of the ingredients used in the composition,

- pH 5.50-6.00,

- density at 20 ° C, g / cm ³ : 0.940-0.970,

- emulsion stability at 40 ° C, 7 x 24 h: complete,

- emulsion stability at 5 ° C, 7 x 24 h: complete,

- microbiological purity: complete.

Below are examples of cosmetic formulations containing a hydrophilic silica airgel / active system.

Example 11. Micellar gel for make-up removal

The gel removes makeup and impurities from the skin without affecting its hydro-lipid layer. It leaves a natural protective film on the skin. The gel contains vitamins A, E, C, panthenol and licorice extract enclosed in a hydrophilic silica airgel carrier, which soothe irritations.

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Table 6. Recipe of the micellar gel for removing make-up.

Ingredients according to INCl Function wt.% Aqua Solvent up to 100 Tetrasodium Giutamate Diacetate A wanting agent 0.40 Bis-Stearyl PEG / PPG-8/6 SMDI / PEG-400 Copolymer Rheology modifier i 1.60 Disodium Cocoyl Giutamate Biosurfactant 0.18 Phenoxyethanok Ethy! Hexylglycerin Preservative 0.80 Maltooligosyl Glucoside / Hydrogenated Starch I lydrolysate Emollient 4.00 Aqua. Polyglyceryl-6 Caprylate. PolygIyceryl-4 Caprate. Polyglyceryl-4 Cocoatc, Polyglyccry | -6 Ricinolcatc, Propylenc Glycol. Caprylic / Capric Triglyceride, Silica. PEG-7 Glyceryl Cocoate, Phenoxyethanol. Ethylhexylglycerin. Ascorbyl Glucoside. dl-aTocopherol. Retinyl Palmitate. Acrylic / Acry lale Ester Copolymer. Tetrasodium Giutamate Diacetate Hydrophilic carrier system acrogel ionic silicon / substance active according to the invention, example 5 5.00 Panthenol Active substance 0.20 Glycyrrhiza Glabra Root Extract Active substance 0.50 Citric Acid Pl-l regulating agent _ Qs and

Example 12. Hand cream.

An active cream designed for the care of dry, sensitive hand skin. The cream protects the skin from drying out, increases its resistance to external factors and detergents.

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Table 7. Recipe for hand cream.

Ingredients according to 1NC1 Function wt.% Glyceryl Stearate. Ceteareth-20.Ccteareth- Cetearyl Alcohol. Cetyl Palmitate 2. Emulsifier 5.00 ^; Cetearyl Alcohol Emulsifier l.OO [Cotton Seed Oil Emollient 5.00 and Simmondsia Chinensis (Jojoba) Seed Oil Emollient 3.00 Phenoxyethanol, Ethylhexylglycerin Preservative 1.00 Aqua Solvent up to 100

Glycerin Humektant and 5.00

Xanthan Gum Rheologite modifier : 0.30 Aqua. Polyglyceryl-6 Caprylate, Polyglyceryl-4 Capratc, Polyglyceryl-4 Cocoate. Polyglyceryl-6 Ricinoleate, Propylenc Glycol, Silica, PEG-7 Glyceryl Cocoate, Phenoxyethanol, Ethylhexylglycerin, Argania Spinosa (Argan) Nut Oil. Ascorbyl Glucoside, dl-aTocopherol. Retinyl Palmitate, Tetrasodium Glutamate Diacctate System: hydrophilic silica airgel / active substances according to the invention, example 7 5.00 Citric Acid Regulating agent pil _

Claims (7)

Patent claims A carrier / active substance system, containing silica airgel as a carrier for active substances, characterized in that the carrier of the active substances is a hydrophilic silica airgel and the active hydrophobic and / or hydrophilic substances are embedded in the carrier in the form of microemulsions. 2. The carrier / active substances system according to claim The process of claim 1, wherein the hydrophilic silica airgel has a bulk density from 0.02 to 0.03 g / cm ³ . 3. The carrier / active substances system according to claim 1, A method as claimed in claim 1, characterized in that it contains hydrophilic silica airgel in a weight ratio of active substances from 0.2 to 20. 4. The carrier / active substances system according to claim 1, The method of claim 1, characterized in that the active substances are vitamin C or vitamin E or vitamin A or mixtures thereof. 5. The vehicle / active substances system according to claim 1, The process of claim 1, characterized in that the microemulsions of active substances contained in the hydrophilic silica airgel carrier are prepared using natural emulsifiers and co-emulsifiers. 6. Cosmetic compositions, characterized in that they contain a carrier / active system as defined in claims 1 to 5. 7. Cosmetic compositions according to claim 1 6. A composition according to claim 6, characterized in that they contain the carrier / active substances system as defined in claims 1 to 5 in an amount of 0.5% to 10% by weight.