Water-in-oil emulsions based on cetyl diglyceryl tris (trimethylsiloxy)-silyl ethyldimethicone as an emulsifier, containing one or more particulate and / or non-water-swellable starches and / or starch derivatives

Description

[0001] The present invention relates to a cosmetic preparation in the form of water-in-oil emulsions based on cetyl diglyceryl tris-(trimethylsiloxy)silyl ethyldimethicone as an emulsifier, which contain one or more particulate and / or non-water-swellable starches and / or starch derivatives selected from the group consisting of tapioca starch.

[0002] Users place a number of demands on modern skincare products, especially facial creams. They should nourish the skin, particularly by providing long-lasting hydration. This is generally achieved through moisturizers that bind water in the stratum corneum (e.g., glycerin). Additionally, added lipids keep the upper skin layers supple and reduce transepidermal water loss.

[0003] Furthermore, users often expect an effect against the signs of skin aging, such as the formation of wrinkles, loss of skin elasticity, or the appearance of age spots. For this purpose, active ingredients are used that, for example, stimulate the activity of skin cells, but also increasingly UV filters that block UVA rays, which are particularly responsible for skin aging. All these ingredients pose a significant challenge for a pleasant sensory experience, as they remain on the skin as a film after the volatile components of the formulation evaporate, and are then perceived by the consumer. These perceptible residues are often described negatively and prevent the feeling that the product has been completely absorbed into the skin.

[0004] Conventional water-in-oil (W / O) emulsions are popular with consumers for caring for or treating dry skin. W / O emulsions also offer advantages when incorporating color pigments, for example, in tinted day creams and makeup. Unfortunately, many W / O emulsions are characterized by the negative aspect of leaving an oily residue on the skin that is slowly absorbed. Furthermore, their physical stability is often limited. This is particularly problematic when W / O emulsions are to be formulated with larger quantities of microparticulate powder raw materials or sensory additives. Typical examples of these microparticulate sensory additives are aluminum starch octenylsuccinate and nylon-12.

[0005] Silicone-based emulsifiers almost without exception contain PEG and PPG groups as their hydrophilic components. Typical examples include Cetyl PEG / PPG-10 / 1 Dimethicone (Abil EM 90, 180) from Evonik or PEG-10 Dimethicone (ES-5612 Formulation Aid) from Dow Corning. These examples are successful and long-established water-in-oil emulsifiers on the market. However, the selection of PEG-free silicone emulsifiers is limited. Examples include KF-6100, KF-6104, KF-6105, KSG-710, KSG-810, KSG-820, KSG-830, and KSG-840 from Shin Etsu, or Abil EM 120 from Evonik.

[0006] These W / Si silicone emulsifiers are typically used in high concentrations of several percent. The selection of oils for W / O emulsions, and especially for W / Si emulsions, is limited because a high proportion of nonpolar oils is required for good long-term stability. Therefore, silicone oils and / or liquid hydrocarbons are primarily used in W / Si emulsions.

[0007] The object of the present invention is therefore to provide a stable (storage-stable, transport-stable, long-term stable) water-in-oil (W / O) emulsion that is sensorially attractive, PEG-free and can be incorporated into the starch as a microparticulate sensory additive, while fulfilling all the requirements of a modern facial care product.

[0008] Overall, the main problem remains that water-in-oil emulsions tend to be instability. Known problems of this kind include oil separation and phase separation. The problem is exacerbated when microparticulate raw materials need to be incorporated. While this can be counteracted by using known stabilizers (e.g., hectorites) or by reducing the proportion of the oil phase, this then introduces other disadvantages, such as the difficulty in incorporating polar lipophilic substances like UV filters.

[0009] The object of the present invention was therefore to counteract these problems. A particularly interesting emulsifier is sold by Dow Corning under the INCI name Cetyl Diglyceryl Tris-(Trimethylsiloxy)silylethyldimethicone and under the trade name "ES-5600".

[0010] WO2018133995 A1 discloses in Example 9 a W / O emulsion containing A) 1.5% Cetyl Diglyceryl Tris-(Trimethylsiloxy)silylethyldimethicone (ES-5600), B) Cetearyl isononanoate and dimethicone as the oil phase, C) water and tapioca starch, and is therefore exempt from patent protection.

[0011] It was therefore surprising and unforeseeable for the person skilled in the art that the problems underlying the invention would be solved by cosmetic or dermatological water-in-oil emulsions comprising A) Cetyl diglyceryl tris-(trimethylsiloxy)silylethyldimethicone as an emulsifier B) an oil phase C) an aqueous phase, characterized by a content of one or more particulate and / or non-water-swellable starches and / or starch derivatives, selected from the tapioca starch group.

[0012] Starch belongs to the homoglycans. It is a polycondensation product of d-glucose. It consists of three different d-glucopyranose polymers: amylose, amylopectin, and an intermediate fraction also known as abnormal amylopectin. Starch can exist in cross-linked and non-cross-linked forms. Distarch phosphate is one such cross-linked product, in which the phosphate group forms a bridge between two starch chains. It is produced by reacting native starch in aqueous suspension with sodium trimetaphosphate, phosphorus oxychloride, or phosphorus pentachloride.

[0013] Advantageous starches or starch derivatives are selected from the following group: corn starch (Amidon De Mais MST (Wackherr), Argo Brand Corn Starch (Corn Products), Pure-Dent (Grain Processing), Purity 21C (National Starch), Farmal CS 3400 (Ingredion Brasil)), rice starch (DSA 7 (Agrana Starch), Oryzapearl (Ichimaru Pharcos)), tapioca starch (Tapioca Pure, Natrasorb W 28-1825, Dry Flo TS (Akzo Nobel)), Distarch Phosphate (Corn PO4 PH"B" (Agrana Starch)), Corn PO4 (Tri-K)), potato starch (Structure Solanace (Akzo Nobel)), sodium starch octenylsuccinate (C*EmCap 12633 (Cargill), Cleargum CO 01 (Roquette)), and calcium starch octenylsuccinate (Dry Flo BF (Akzo Nobel)).

[0014] According to the invention, the water-in-oil emulsions advantageously contain 0.01 to 20.0 wt.%, preferably 0.02 to 10.0 wt.%, particularly preferably 0.1 to 5.0 wt.%, based on the total weight of the preparation, of one or more particulate and / or non-water-swellable starches or starch derivatives.

[0015] According to the invention, water-in-oil emulsions advantageously contain 0.1 to 10.0 wt.%, preferably 0.2 to 5.0 wt.%, particularly preferably 0.5 to 4.0 wt.%, based on the total weight of the preparation, of cetyl diglyceryl tris-(trimethylsiloxy)silylethyldimethicone.

[0016] It was not to be expected that the preparations according to the invention would would be more effective than moisturizing preparations, easier to formulate, better promote skin smoothing, be characterized by better care effects, serve better as vehicles for cosmetic and dermatological active ingredients, exhibit better sensory properties such as spreadability on the skin or absorption into the skin, be better suited as vehicles for organic UV filters, exhibit higher stability against decomposition in oil and water phases and are characterized by better biocompatibility, and enable the production of stable, especially low-viscosity formulations than state-of-the-art preparations.

[0017] The preparations according to the invention are free-flowing but can also be formulated as creams, possess very good cosmetic properties, especially with regard to stickiness, and exhibit very good skin compatibility and skin care performance.

[0018] According to the invention, it is possible and advantageous to freely select the proportion of the oil phase of the preparations according to the invention in the range of 3 to 60 wt.%, based on the total weight of the preparations.

[0019] The oil or lipid phase according to the invention can contain all oils, fats, waxes and / or lipids commonly used in cosmetic preparations.

[0020] The aqueous phase of the preparations according to the invention can advantageously contain conventional cosmetic excipients, such as alcohols, in particular those with a low carbon number, preferably ethanol and / or isopropanol or polyols with a low carbon number and their ethers, preferably propylene glycol, glycerin, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, butylene glycol, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, phenoxyethanol, methylparaben, foam stabilizers, electrolytes, self-tanning agents, etc.

[0021] The following can be used as basic components of the preparations according to the invention: Water or aqueous solutions, aqueous ethanolic solutions, natural oils and / or chemically modified natural oils and / or synthetic oils; fats, waxes and other natural and synthetic fatty substances, preferably esters of fatty acids with low-carbon alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with low-carbon alkanoic acids or with fatty acids; low-carbon alcohols, diols or polyols, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products.

[0022] In particular, mixtures of the aforementioned solvents are used.

[0023] According to the present invention, the oil phase of the emulsions consists at least partly of silicone oils.

[0024] It is preferred to select the oil phase of the preparations according to the invention from the group of cyclic and / or linear silicones, which are also referred to as "silicone oils" within the scope of this disclosure. Such silicones or silicone oils can exist as monomers, which are generally characterized by structural elements as follows:

[0025] Linear silicones with multiple siloxyl units, which are advantageous to use according to the invention, are generally characterized by structural elements as follows: where the silicon atoms can be substituted with identical or different alkyl and / or aryl groups, which are represented here in a generalized way by the groups R1-R4 (meaning that the number of different groups is not necessarily limited to 4). m can take values ​​from 2 to 200,000.

[0026] Dimethicone is advantageously chosen as the silicone oil. Other silicone oils, for example cyclomethicone (octamethylcyclotetrasiloxane), phenyldimethicone, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly(methylphenylsiloxane), cetyldimethicone, behenoxydimethicone, are also advantageously suitable for use in accordance with the present invention.

[0027] However, it is possible to choose an oil component from the group of other oil components without incurring major disadvantages.

[0028] However, it is preferred to select the oil components of the oil phase of the preparations according to the invention completely or almost completely from the group of oils of synthetic and / or natural origin. These can then advantageously be selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms, or from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms.Such ester oils can then be advantageously selected from the group consisting of isopropyl myristate, isopropyl palmitate, isopropyl stearate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, cetearyl isononanoate, isodecyl neopentanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyl decyl stearate, coco-caprylate / caprate, oleyl oleate, oleylerucate, erucyl oleate, erucylerucate, as well as synthetic, semi-synthetic and natural mixtures of such esters, e.g. jojoba oil.

[0029] Furthermore, the oil phase can be advantageously selected from the group of branched and unbranched hydrocarbons and waxes, dialkyl ethers, saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, in particular triglycerides of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids with a chain length of 8 to 24, especially 12 to 18, carbon atoms. The fatty acid triglycerides can, for example, be advantageously selected from the group of synthetic, semi-synthetic, and natural oils, e.g., caprylic / capric triglyceride, cocoglycerides, sunflower oil, soybean oil, almond oil, and the like.

[0030] Mixtures of dimethicone and cetearyl isononanoate are also advantageous.

[0031] Of the hydrocarbons, paraffin oil, squalane, hydrogenated polyisobutene, isohexadecane, isododecane; C 15-19 alkane or polydecene are advantageously used in accordance with the present invention.

[0032] Preparations according to the present invention may also contain one or more additional non-silicone emulsifiers, for example advantageously selected from the group of the following substances, which generally act as W / O emulsifiers.

[0033] Sorbitan stearate, sorbitan oleate, glyceryl isostearate, polyglyceryl-3-oleate, wool wax acid mixtures, wool wax alcohol mixtures, polyglyceryl-3 diisostearate, methyl glucose dioleate, polyglyceryl-4-isostearate, cetyl dimethicone copolyol, sorbitan isostearate, Polyglyceryl-2-dipolyhydroxystearate, polyglyceryl-3-diisostearate, polyglyceryl-4-dipolyhydroxystearate, PEG-30-dipolyhydroxystearate, diisostearoylpolyglyceryl-3-diisostearate, polyglyceryl-2-dipolyhydroxystearate, polyglyceryl-3-dipolyhydroxystearate, Polyglyceryl-4-dipolyhydroxystearate.

[0034] Emulsions according to the invention, e.g. in the form of a skin protection cream, a skin lotion, a cosmetic milk, for example in the form of a sunscreen cream or a sunscreen milk, are advantageous and contain, e.g. fats, oils, waxes and / or other fatty substances, as well as water and one or more emulsifiers, as are commonly used for such a type of formulation.

[0035] It is of course known to experts that sophisticated cosmetic formulations are usually inconceivable without the usual excipients and additives. These include, for example, consistency enhancers, fillers, perfumes, colorants, emulsifiers, pigments, additional active ingredients such as vitamins or proteins, sunscreens, stabilizers, insect repellents, alcohol, water, salts, antimicrobial, proteolytic, or keratolytic substances, etc.

[0036] Mutatis mutandis, corresponding requirements apply to the formulation of medical preparations.

[0037] Topical medicinal compositions as defined in the present invention generally contain one or more drugs in an effective concentration. For the sake of simplicity, and to clearly distinguish between cosmetic and medicinal applications and corresponding products, reference is made to the legal provisions of the Federal Republic of Germany (e.g., the Cosmetics Regulation, the Food and Drug Act).

[0038] Accordingly, cosmetic or topical dermatological compositions according to the present invention can, depending on their structure, be used, for example, as skin protection cream, cleansing milk, sunscreen lotion, nourishing cream, day or night cream, etc. It is optionally possible and advantageous to use the compositions according to the invention as a basis for pharmaceutical formulations.

[0039] Cosmetic and dermatological preparations in the form of sunscreens are also advantageous. Preferably, these contain, in addition to the active ingredient used according to the invention, at least one UVA filter substance and / or at least one UVB filter substance and / or at least one inorganic pigment.

[0040] However, it is also advantageous, in the context of the present inventions, to produce cosmetic and dermatological preparations whose primary purpose is not protection from sunlight, but which nevertheless contain UV protective substances. For example, UV-A or UV-B filter substances are commonly incorporated into day creams.

[0041] Advantageously, preparations according to the invention can contain substances that absorb UV radiation in the UVB range, wherein the total amount of the filter substances is, for example, 0.1 wt.% to 30 wt.%, preferably 0.5 to 10 wt.%, in particular 1 to 6 wt.%, based on the total weight of the preparations.

[0042] UVB filters can be oil-soluble or water-soluble. Examples of oil-soluble substances include: Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) esters; esters of salicylic acid, preferably salicylic acid (2-ethylhexyl) esters, salicylic acid (4-isopropylbenzyl) esters; derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; 2,4,6-trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazine

[0043] The following substances are advantageous as water-soluble substances: 2-Phenylbenzimidazole-5-sulfonic acid and its salts, e.g. sodium, potassium or triethanolammonium salts; sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; sulfonic acid derivatives of 3-benzylidene camphor, such as 4-(2-oxo-3-bornylidenemethyl)benzenesulfonic acid, 2-methyl-5-(2-oxo-3-bornylidenemethyl)sulfonic acid and its salts.

[0044] The list of UVB filters mentioned that can be used according to the invention is of course not intended to be limiting.

[0045] It can also be advantageous to use UVA filters in preparations according to the invention that are commonly found in cosmetic and / or dermatological preparations. Such filter substances are preferably derivatives of dibenzoylmethane, in particular 1-(4'-tert-butylphenyl)-3-(4'-methoxyphenyl)propane-1,3-dione and 1-phenyl-3-(4'-isopropylphenyl)propane-1,3-dione. Preparations containing these combinations are also the subject of the invention. The same amounts of UVA filter substances can be used as those mentioned for UVB filter substances.

[0046] Cosmetic and / or dermatological preparations according to the present invention may also contain inorganic pigments commonly used in cosmetics to protect the skin from UV radiation. These include oxides of titanium, zinc, iron, zirconium, silicon, manganese, aluminum, chromium, cerium, and mixtures thereof, as well as modifications in which the oxides are the active agents. Ultramarine blue and pearlescent pigments may also be used. Pigments based on titanium dioxide are particularly preferred. The quantities mentioned for the above combinations may be used.

[0047] The cosmetic and dermatological preparations according to the invention may contain cosmetic active ingredients, excipients and / or additives such as are commonly used in such preparations, e.g. antioxidants, preservatives, bactericides, perfumes, antifoaming agents, dyes, pigments with coloring effects, thickeners, surfactants, emulsifiers, softening, moisturizing and / or humectant substances, fats, oils, waxes or other usual components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, organic solvents or silicone derivatives.

[0048] The following examples are intended to illustrate the present invention without limiting it. Unless otherwise stated, all quantities, proportions, and percentages are based on the weight and total quantity or total weight of the preparations.

[0049] To produce the emulsions according to the invention, the W / O emulsifier is added to the oil phase. The components of the oil phase are mixed together with a suitable stirrer until homogeneity of the phase is achieved, optionally with gentle heating.

[0050] The sodium chloride and the respective starch are dispersed in the water phase. The water phase is then slowly added to the oil phase while stirring, and subsequently mixed intensively for approximately 2 minutes using a high-speed mixer (e.g., an ESGE immersion blender).

[0051] To determine storage stability, all emulsion samples are stored in screw-top 30 ml glasses at different temperatures: at room temperature (RT) (approx. 20 °C), at +40 °C and at +50 °C.

[0052] Stability was visually assessed after 7 days, 14 days, 21 days (T) and 1 month (M). Example recipe / temperatures + 40 °C + 50 °C RT 1 - Formula basis without strength Stable Slightly unstable from 7T Slightly unstable from 1 meter 2 - Base with Aluminum Starch Octenylsuccinate Slightly unstable from 7T Unstable from 7T Slightly unstable from 7T 3 - Base with Nylon-12 (Classic powder raw material) ) Slightly unstable from 7T Unstable from 7T Slightly unstable from 1 meter 4 - Base with Tapioca starch Stable Slightly unstable from 7T Stable "Stable" means that there is no or only slight phase separation and no or only slight oil separation. "Slightly unstable" means that there is moderate, visible phase separation or clearly visible oil separation. "Unstable" means rapid, complete phase separation.

[0053] These experiments have shown that the W / O emulsions with Dow Corning's ES-5600 were best stabilized or less destabilized by the strengths according to the invention compared to other established sensor additives such as nylon or aluminium starchoctenyl succinate.

[0054] The following examples are intended to illustrate the invention in more detail. Unless otherwise stated, the values ​​given are percentages by weight. Only the example recipes containing tapioca starch are according to the invention. Example recipes / wt.% 1 2 3 4 Aluminum Starch Octenylsuccinate 4 Nylon-12 4 Tapioca starch 4 Cetyl Diglyceryl Tris-(Trimethylsiloxy)silyle-thyldimethicone ("ES-5600") 1 1 1 1 Cetearyl isononanoate 5 5 5 5 Dimethicon 15 15 15 15 Glycerin 7 7 7 7 Sodium chloride 0,5 0,5 0,5 0,5 Water Ad 100 Ad 100 Ad 100 Ad 100 Example recipe 5 % by weight Distarch phosphates 4 ES-5600 1 Cetearyl isononanoate 5 Dimethicon 15 Glycerin 7 Sodium chloride 0,5 Water Ad 100 Example recipe 6 % by weight Cetyl Diglyceryl Tris-(Trimethylsiloxy)silylethyldimethicone (ES-5600) 1 Natriumstärkeoctenylsuccinate 4 Isononylisononanoate 15 Dimethicone 5 Glycerin 5 Natriumchlorid 1 Wasser Ad 100 Beispielrezeptur 7 Gew.-% Cetyl Diglyceryl Tris-(Trimethylsiloxy)silylethyldimethicone (ES-5600) 2 Distärkephosphate 2 Caprylic / Capric Triglyceride 3 Cocoglycerides 2 Dimethicone 10 Disteardimonium Hektorit 0,2 Propylene Carbonat 0,05 Butylmethoxydibenzoylmethan 1 Octocrylen 2 Octylsalicylat 2 Natriumascorbylphosphate 0.1 Ubiquinon 0.1 Butylenglycol 2 Tocopherolacetat 0.1 Farbpigmente (CI 77891, CI 77492, CI 77491, CI 77499, CI 77007) 6 Panthenol 0.5 Phenoxyethanol 0.3 EDTA 1 Glycerin 5 Natriumchlorid 2 Wasser Ad 100 Beispielrezepturen 8 Gew.-% Cetyl Diglyceryl Tris-(Trimethylsiloxy)silylethyldimethicone (ES-5600) 2 Tapicoa Stärke 2 Caprylic / Capric Triglyceride 2 C12-15 Alkylbenzoat 2 Isohexadecan 2 Dimethicone 5 Cetearylisononanoate 2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazin 1 Octocrylen 2 Ethylhexylmethoxyzinnamat 2 Phenylbenzimidazolsulfonsäure 1 Kreatin 0.2 Octandiol 0.3 Methylpropandiol 2 Phenoxyethanol 0.3 EDTA 1 Glycerin 5 Natriumchlorid 2 Wasser Ad 100

Claims

1. Cosmetic or dermatological water-in-oil emulsions, comprising A) Cetyl Diglyceryl Tris(Trimethylsiloxy)silylethyl Dimethicone as emulsifier, B) an oil phase, C) an aqueous phase, characterized by a content of one or more particulate and / or non-water-swellable starches and / or starch derivatives, selected from the group of tapioca starch, where a formulation as follows: % by weightES-5600 (Cetyl Diglyceryl Tris(Trimethylsiloxy)silylethyl Dimethicone)1.5Cetearyl isononanoate8Dimethicone5Silica3Tapioca starch4Sodium chloride1Glycerin9Phenoxyethanol0.8Mineral pigments [Silica + (CI 77491, CI 77891)] - Ronaflair® Flawless2Colour pigments (CI 77891, CI 77492, CI 77491, CI 77499, CI 77007)5Waterto 100 is excluded from patent protection.

2. Emulsions according to Claim 1, characterized in that they comprise 0.1% to 10.0% by weight, preferably 0.2% to 5.0% by weight, particularly preferably 0.5% to 4.0% by weight, based on the total weight of the preparation, of Cetyl Diglyceryl Tris(Trimethylsiloxy)silylethyl Dimethicone.

3. Emulsions according to either of the preceding claims, characterized in that they comprise 0.01% to 20.0% by weight, preferably 0.02% to 10.0% by weight, particularly preferably 0.1% to 5.0% by weight, based on the total weight of the preparation, of one or more particulate and / or non-water-swellable starches and / or starch derivatives.