EP3585353A1

EP3585353A1 - Cosmetic or dermatological preparations containing inorganic pigments which are coated with hydrophobic silica, and non-ionic emulsifiers

Info

Publication number: EP3585353A1
Application number: EP18700101.1A
Authority: EP
Inventors: Delphine CHANTY; Thomas Raschke
Original assignee: Beiersdorf AG
Current assignee: Beiersdorf AG
Priority date: 2017-02-27
Filing date: 2018-01-05
Publication date: 2020-01-01
Also published as: WO2018153556A1; DE102017203115A1

Abstract

The invention relates to cosmetic and dermatological preparations containing a) at least one pigment from the group of inorganic white, coloured or multi-coloured pigments which are coated with hydrophilic silica and b) one or more non-ionic emulsifiers.

Description

description

Cosmetic or dermatological preparations containing inorganic pigments coated with hydrophilic silica, and nonionic

emulsifiers

The invention relates to cosmetic or dermatological preparations containing inorganic pigments coated with hydrophilic silica and nonionic emulsifiers.

The desire to look beautiful and attractive has been rooted in people for thousands of years. Even though the ideal of beauty has undergone changes over time, the pursuit of an impeccable appearance has always been the goal of man, since a sympathetic appearance enhances their self-esteem and attraction to their fellow human beings.

The term "decorative cosmetics" derives from the Latin "decoratio" - the highlighting of the beautiful - with the help of dyes, individual parts of the body, especially on the face, are highlighted and color inconsistencies are lessened Give appearance, refresh pale skin, compensate for color irregularities of the skin as well as emphasize eyes and lips.

In addition to facial powders and rouge as powdered cosmetics and stick-shaped preparations cream-like preparations, such as day creams and cream make-up based on emulsion or hydrodispersion base are used. A particular embodiment is the so-called Foundation. Foundation is liquid or semisolid make-up that is mostly skin colored and applied to the face. They give a uniform, healthy, tinted or reddish appearance. Their color is usually obtained by a mixture of pigments from the group of inorganic white, colored and / or colored pigments. To a uniform To produce a skin appearance, the prior art requires relatively large amounts of these inorganic whitening, coloring and / or colored pigments. The larger the proportion of these pigments in the preparation, the better the skin appearance is balanced. Redness and other visual skin irregularities are masked.

A disadvantage of the prior art, however, is the fact that foundations based on O / W emulsions (oil-in-water emulsions) can only be formulated with a relatively low pigment content, since with an increasing content of insoluble particles or pigments Instabilities or rheological changes of the emulsion, such as decrease in viscosity occur. On the other hand, however, the desired decorative effects can only be achieved with sufficiently high amounts of pigments.

It was therefore an object of the present invention to develop a foundation based on an O / W emulsion, which has a high stability, can be distributed well on the skin and after application to the skin leads to a uniform skin appearance and all optical irregularities effectively covered.

The object is surprisingly achieved by a cosmetic O / W emulsion containing a) at least one pigment from the group of inorganic whitening, dyeing and / or colored pigments which are coated with hydrophilic silica and

b) one or more nonionic emulsifiers.

Particularly advantageous inorganic pigments which are coated with hydrophilic silica are the so-called "Primrose" pigments from Miyoshi Kasei Inc.

Preferred representatives of these silica-coated, hydrophilic, inorganic pigments have an average particle size of 1 .0 - 3.0 μm and have the following typical composition: 85.0-90.0% of inorganic pigments as the core and 10.0-15.0% of silicon dioxide (silica) as coating.

Typical metal oxides used in the inorganic pigments are titanium dioxide, iron oxide, chromium oxide and manganese oxide. The different oxidation states of the metal oxide, especially the iron oxide, are responsible for the different colors, with the following classes, which are summarized in the so-called Color Index: Cl 77499 (black), Cl 77491 (red), Cl 77492 (yellow). These inorganic whitening, coloring and / or coloring pigments are combined with each other in the present invention to obtain a certain hue. Cosmetic or dermatological preparations according to the invention preferably contain from 0.01 to 50% by weight, preferably from 0.05 to 30% by weight, particularly preferably from 0.1 to 20% by weight, of one or more of the pigments of the invention Group of inorganic whitening, coloring or colored pigments which are coated with hydrophilic silica, based on the total composition of the preparations.

Among the nonionic emulsifiers are preferably a) partial fatty acid esters and fatty acid esters of polyhydric alcohols and their ethoxylated derivatives (eg glyceryl monostearates, sorbitan stearates, glyceryl stearate citrate, sucrose stearates) and b) ethoxylated fatty alcohols and fatty acids, preferably PEG-100 stearate, PEG-40 Steatrate, ceteareth-20, ceteth-20, steareth-20, ceteareth-12, ceteth-12, steareth-12 and esters of mono-, oligo- or polysaccharides with fatty acids, preferably cetearyl glucoside and methyl glucose distearate. c) fatty acid esters of oligoglycerols and mixtures of the substances mentioned under a), b) and c).

Particularly preferred are glyceryl stearate citrate, polyglyceryl-3-methyl glucose distearate, polyglyceryl stearate and / or PEG-40 stearate.

A preferred representative of "polyglyceryl-3-methyl-glucose distearate" (PGMS) is available under the trade name Tego® Care 450 from Evonik Industries.

PEG-40 Stearate is available, inter alia, from Evonik Industries under the trade name TEGO Acid S40P.

Glyceryl stearate citrate, (2-hydroxy-1,2,3-propanetricarboxylic acid 1,2,3-propanetriol monoocta-decanoate, INCI Glyceryl Stearate Citrate) is the citric acid ester of glyceryl stearate and is available from several manufacturers under the names Imwitor 370 or 372 , Polyglyceryl-10 stearate is available under the trade designation Polyaldo 10-1 -S from Lonza.

Cosmetic or dermatological preparations according to the invention preferably comprise 0.01-20% by weight, preferably 0.05-10% by weight, particularly preferably 0.1-5% by weight of one or more of the nonionic emulsifiers according to the invention, based on the total composition of the preparations, in particular one or more substances selected from one or more of the groups mentioned under a) to c), most preferably one or more substances selected from the group glyceryl stearate citrate, polyglyceryl-3-methylglucose distearate , Polyglyceryl-10 stearate and / or PEG-40 stearate.

Emulsions are advantageous dosage forms in the sense of the present invention, e.g. in the form of a cream, a lotion, a cosmetic 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 they are commonly used for such a type of formulation.

If the cosmetic or dermatological preparation in the sense of the present invention is a solution or emulsion or dispersion, it is possible to use as solvent:

Water or aqueous solutions

Oils, such as triglycerides of capric or caprylic acid, silicone oils;

Fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low C number or with

Fatty acids, three dimensionally crosslinked organopolysiloxanes such as siloxane nelastomer;

Alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, hexanediol, octanediol, ethylhexylglycerol, glycerylcaprylate, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, butylene glycol, methylpropanediol, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products.

In particular, mixtures of the abovementioned solvents are used. For alcoholic solvents, water can be another ingredient. The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, cetearyl isononanoate, isodecyl neopentanoate, 2-ethylhexyl palmitate, 2 Ethyl hexyl laurate, 2-hexyl decyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate and also synthetic, semi-synthetic and natural mixtures of such esters, for example jojoba oil.

Furthermore, the oil phase can be advantageously selected from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and the fatty acid triglycerides, in particular the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12 to 18 carbon atoms. For example, the fatty acid triglycerides can be advantageously selected from the group of synthetic, semi-synthetic and natural oils, e.g. Olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

Usual colorants which are suitable for use as cosmetic or dermatological compositions in the context of the present invention are lipophilic dyes (eg Sudan Red, DB & C Red 17, DB & C Green 6, β-carotene, Sudan brown, DB & C Yellow 1 1, DB & C Violet 2, DB & C Orange 5 or Annatto), hydrophilic dyes (eg beetroot juice or methylene blue), pearlescent pigments and blends of such colorants.

The pigments may be white or colored, goniochromatic or non-goniochromatic, inorganic and / or organic, coated or uncoated. Among the inorganic pigments which may be mentioned include titanium dioxide which is optionally surface-treated, zirconium oxide (ZrO 2), zinc oxide (ZnO), iron oxide (eg Fe 2 O 3), silicon oxide (SiO 2), manganese (eg MnO), aluminum ( Al 2 O 3), or ceria (eg, Ce 2 O 3), and iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, and iron blue The pearlescent pigments may be exemplified by white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica especially iron blue or chromium oxide mica, titanium mica having an organic pigment of the type mentioned above and pearlescent pigments based on Bismuth oxychloride.

Within the meaning of the present invention, the pigments can also be used advantageously in the form of commercially available oily or aqueous predispersions. Dispersants and / or solubilizers may advantageously be added to these predispersions.

The silicone elastomers according to the invention are crosslinked, optionally substituted organopolysiloxanes. The crosslinking may have been carried out by means of all common methods and crosslinkers. Particularly advantageous for the purposes of the present invention, silicone elastomers can be used in powder form, such as, for example, e.g. EP-9701 or EP 9801 to Dow Corning.

Furthermore, it is advantageous according to the invention if the preparation contains one or more fillers. According to the invention, the fillers are selected from the group of the compounds nylon 6/12, silica, silica dimethyl silylates, aluminum starch octenylsuccinates, dimethicone crosspolymer, dimethicone / vinyldimethicone crosspolymer, methyl methacrylate large polymer, talc, rice starch and all starch derivatives, lauroyl lysines , Magnesium silicate and / or polymethylsilsesquioxane.

The aqueous phase of the preparations according to the invention may advantageously contain one or more thickening agents which may be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, e.g. Hyaluronic acid, xanthan gum, cellulose ethers such as e.g. Hydroxypropylmethylcellu- lose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called Carbopols, for example, Carbopols types 980, 981, 1382, 2984, 5984, Ultrez 10, ETD 2020, acrylates / C 10-30 alkyl acrylates Crosspolymer, sodium acrylate copolymer, carbomer, either individually or in combination.

Inventive formulations which z. B. known anti-wrinkle agents such as flavone glycosides (especially α-glycosyl rutin), coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for the prophylaxis and treatment of cosmetic or dermatological skin lesions, as z. B. in skin aging such as dryness, roughness and formation of dryness lines, itching, reduced refatting (eg after washing), visible vasodilation (telangiectasia, cuperosis), slackness and development of wrinkles and fine lines, local hypo-, hypo- and false pigmentation (eg, age spots), increased susceptibility to mechanical stress (eg, cracking), and the like). Furthermore, they are advantageous against the appearance of dry or rough skin.

Preparations in the context of the present invention may preferably contain at least one further UV-A, UV-B and / or broad-spectrum filter substance. The formulations may, although not necessary, optionally also contain one or more organic and / or inorganic pigments as UV filter substances, which may be present in the water and / or the oil phase.

Particularly advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: octocrylene), 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl Salicylates) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate).

Advantageous UV-A filter substances for the purposes of the present invention are dibenzoylmeter derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which has been sold by Givaudan under the trademark Parsol ^® 1789 and sold by Merck under the trade name Eusolex® 9020.

Advantageous further UV filter substances in the context of the present invention are sulfonated, water-soluble UV filters, such as. B .:

Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81 -7), which is available, for example, under the trade name Eusolex 232 from Merck or under Neo Heliopan Hydro from Haarmann &Reimer;

1, 4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene (also: 3,3 '- (1,4-phenylenedimethylene) -bis (7,7-dimethyl-2-) oxo-bicyclo [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 10-sulfato compounds, in particular the corresponding sodium, potassium or triethanolammonium salt), also known as benzene

1, 4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) is called. Benzene-1, 4-di (2-oxo) 3-bornylidenemethyl-10-sulfonic acid) has the INCI name Terephtalidene Di-sulfo Sulfonic Acid (CAS No. 90457-82-2) and is available, for example, under the trade name Mexoryl SX from Chimex.

Advantageous UV filter substances for the purposes of the present invention are also so-called broadband filters, i. Filter substances that absorb both UV-A and UV-B radiation.

Advantageous broadband filters or UV-B filter substances are, for example, triazine derivatives, such as. B.

2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (INCI: aniso triazine), which available under the trade name Tinosorb® S from CIBA-Chemikalien GmbH;

Diethylhexylbutylamidotriazone (INCI: diethylhexylbutamidotriazone), which is available under the trade name UVASORB HEB from Sigma 3V;

4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), also: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1, 3,5-triazine (INCI: ethylhexyl triazone), which is sold by BASF Aktiengesellschaft under the trade name U-VINUL® T 150.

An advantageous broadband filter in the context of the present invention is also the 2,2'-methyl-bis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol ), which is available under the trade name Tinosorb® M from CIBA-Chemikalien GmbH.

The following examples are intended to illustrate the present invention without limiting it. Unless indicated otherwise, all amounts, proportions and percentages are based on the weight and the total amount or on the total weight of the preparations.

To prepare 1 kilogram of the emulsions according to the invention, the lipophilic phase (eg oils, waxes), thickeners, pigments and the aqueous phase are weighed in separately, the nonionic O / W emulsifier being added to the lipophilic phase (oil phase), while the anionic, water-soluble emulsifiers were added to the water phase. The oil phase is heated to 75 ° C in a water bath to the emulsifier and to dissolve the coemulsifier. The water phase is also heated to 75 ° C with stirring and then it is slowly added after the addition of the thickener phase with intensive stirring to the oil phase, wherein a coarse emulsion is formed. The silica-coated inorganic pigments are intensively homogenized in a separate vessel in about 100 ml of a solution of glycerol and water with a high-speed mixer (eg an ESG wand) for about 2 minutes and then submerged to about 60 ° C warm emulsion Stirring added. The emulsion is then homogenized a first time and then neutralized with sodium hydroxide solution to a pH of pH 6.5 - 7.3. After the emulsion has cooled to room temperature, a second homogenization is carried out.

To determine the storage stability of the pigments, all emulsion samples are stored in screw-retained 30 mL glasses at different temperatures: at room temperature (RT) (about 20 ° C.), at + 40 ° C., at + 50 ° C. and under alternating temperature conditions between -10 ° C and + 40 ° C.

The stability was assessed visually after 7, 14, 21 and 30 days (T).

Example recipe / RT + 40 ° C + 50 ° C W-10 ° C / Temperatures 40 ° C

1 a - Emulsion with PolyStable 30T Stabil 30T Stabil 30T Stabil 30T glyceryl-3 methylglucose distearate and

pigments

1 b - Emulsion 1 a Stable 30T Stable 30T Stable 30T Stable 30T without piamente N _ihiih E _l _Iih E _lttt conscem _g ao _r enonscem _g ao _r enuu

2a - Emulsion with PEG-Stabil 30T Stabil 30T Stabil 30T Light In40 Stearate stability and pigments 30T

2b - Emulsion 2a Stable 30T Stable 30T Stable 30T Stable 30T without Piamente

3a - Emulsion with Gly-Stabil 30T Stabil 30T Light InstaStabil 30T ceryl stearate citrate and 30T

pigments

3b - Emulsion 3a without Stabil 30T Stabil 30T Stabil 30T Stabil 30T pigments

4a - Emulsion with Stable 30T Sedimenta Sedimentation Slight InSodium Stearoyl Glutation of Pigder Pigments Stability Mate ments from 21 T from 21 T 30T and Pigments

4b - Emulsion 4a Stable 30T Stable 30T Stable 30T Stable 30T without Piqmente

5a - Emulsion with SoLight InSedimenta Sedimentation Stable 30T dium Cetearyl Sulfate Stability of Pigder Pigments

and pigments 30T from 14T from 14T

5b - Emulsion 5a Light InStable 30T Stabil 30T Stabil 30T without Piamente stability

30T

"Stable" means no or little phase separation, little or no oil separation, no visually discernible inhomogeneity of the pigment distribution. "Light instability" means that there is a moderate, visible phase separation or clearly visible oil separation or visually discernible Inhomogeneity is coming. "Sedimentation of the pigments" means complete and visible sedimentation of the pigments on the soil.

These experiments have shown that the silica-coated inorganic pigments emulsions have been stabilized by the non-ionic emulsifiers.

Octyldodecanol 4

Caprylic / Capric Triglycerides 4

Stearyl alcohol 2

Phenoxyethanol 0.8

Dicaprylyl ether 4

Carbomer 0.1

Glycerol 7

Sodium hydroxide solution (45%) 0.13

Silica coated inorganic pigments 6 [(Cl 77499, Cl 77491, Cl 77891, Cl 77492)

+ Silica] - PRIMROSE

Water Ad 100

Example recipe 8% by weight

Polyglyceryl-10 Stearate 1

Glyceryl Stearate 2

Cetyl alcohol 1

Octyldodecanol 3

Cetearyl Isononanoate 4

C12-15 alkyl benzoate 2

Bis-ethylhexyloxyphenolmethoxyphenyltria-1-zine

Octocrylene 5

Phenoxyethanol 0.5

Methylpropanediol 0.2

Xanthan gum 0.2

Acrylates / C 10-30 alkyl acrylate cross-poly-0.2 mer

Glycerol 6

Benzyl alcohol 0.1

Sodium hydroxide solution (45%) 0.13

Silica coated inorganic pigments 5

[(Cl 77499, Cl 77491, Cl 77891, Cl 77492)

+ Silica] - PRIMROSE

Water Ad 100

Claims

claims

Contains cosmetic or dermatological preparations

a) at least one pigment from the group of inorganic white, colored or colored pigments, which are coated with hydrophilic silica and

b) one or more nonionic emulsifiers

Preparations according to claim 1, characterized in that the one or more nonionic emulsifiers are selected from the groups

a) Partial fatty acid esters and fatty acid esters of polyhydric alcohols and their ethoxylated derivatives (for example glyceryl monostearate, sorbitan stearate, glyceryl stearate citrate, sucrose stearate)

b) ethoxylated fatty alcohols or fatty acids, preferably PEG-100 stearate, PEG-40 stearate, ceteareth-20, ceteth-20, steareth-20, ceteareth-12, ceteth-12, steareth-12 and also esters of mono-, Oligo- or polysaccharides with fatty acids, preferably cetearyl glucoside and methyl glucose distearate.

c) fatty acid esters of oligoglycerols and mixtures of the substances mentioned under a), b) and c).

Preparations according to Claim 1 or 2, characterized in that the nonionic emulsifier (s) is / are selected from the group of glyceryl stearate citrate, polyglyceryl-3-methylglucose distearate, polyglyceryl-10-stearate, PEG-40 stearate.

Preparations according to one of the preceding claims, characterized in that they contain 0.01 to 20 wt.%, Preferably 0.05 to 10 wt.%, Particularly preferably 0.1 to 5 wt.% Of one or more of the present invention nonionic emulsifiers, based on the total composition of the preparations, in particular one or more substances selected from one or more of the groups mentioned under a) to c), most preferably one or more substances selected from the group glyceryl stearate citrate, polyglyceryl-3 methyl glucose distearate , Polyglyceryl-10 stearate, and / or PEG-40 stearate.

Preparations according to one of the preceding claims, characterized in that they are 0.01-50 wt .-%, preferably 0.05-30 wt .-%, particularly preferably 0.1-20 wt .-% of one or more of the inventive Pigment from the group of the inorganic whitening, coloring or colored pigments coated with hydrophilic silica, based on the total composition of the preparations.

Use of nonionic emulsifiers as described in the preceding claims for improving the incorporation of hydrophilic silica-coated metal oxide particles as described in the preceding claims.