WO2019020241A1

WO2019020241A1 - Water-in-oil emulsions which are based on cetyl diglyceryl tris(trimethylsiloxy)silyl ethyl dimethicones as emulsifier and contain aromates

Info

Publication number: WO2019020241A1
Application number: PCT/EP2018/063647
Authority: WO
Inventors: Delphine CHANTY; Thomas Raschke
Original assignee: Beiersdorf Ag
Priority date: 2017-07-24
Filing date: 2018-05-24
Publication date: 2019-01-31
Also published as: EP3658104A1; DE102017212625A1; CN110944619A

Abstract

Disclosed are cosmetic or dermatological water-in-oil emulsions which contain A) cetyl diglyceryl tris-(trimethylsiloxy)silyl ethyl dimethicones as emulsifier, B) an oil phase, C) an aqueous phase, and are characterized by a benzoic acid moiety and/or a moiety of one or more substances of formula (I) and/or formula (II) having the following generic structure: formula (I), where X can be a branched or straight C1 - C4 alkyl chain, a hydroxy group or an O group, and the bond depicted by the dashed line indicates a double bond when X is an O group, and R, independently of X, can be a branched or straight C1 - C4 alkyl chain, a branched or straight C1 - C4 alkyl chain bridged by an oxygen atom, or a hydroxy group. formula (II)

Description

Beiersdorf Aktiengesellschaft Hamburg

description

Water-in-oil emulsions based on cetyl diglyceryl tris (trimethylsiloxy) silylethyldimethicone as an emulsifier, which have an aromatic content

The present invention relates to a cosmetic preparation preparations in the form of water-in-oil emulsions based on cetyl diglyceryl tris (trimethylsiloxy) silyl ethyldimethicone as an emulsifier, which have a content of low molecular weight aromatics.

Users place a number of demands on modern skincare products, especially in the form of face creams. They should care for the skin, in particular to provide the skin with moisture for a long time. This is usually done via "moisturizers" that bind water in the stratum corneum (e.g., glycerin), and with added lipids, the upper dander is kept supple and the transepidermal water loss is reduced.

Furthermore, users often expect an effect against the signs of aging of the skin, e.g. the development of wrinkles, the lessening of skin elasticity or the development of age spots. For this purpose, on the one hand agents are used, for example, stimulate the activity of skin cells, but also increasingly used UV filters that block especially responsible for skin aging UVA rays. All these ingredients pose a great challenge for a pleasant sensory, as they remain as a film on the skin after evaporation of the volatile constituents of the formulation, and sensed by the consumer sensory there. The sensible residues are often described negatively and prevent the feeling that the product is completely "absorbed" in the skin.

Conventional W / O emulsions are often used by consumers to condition or treat dry skin. W / O emulsions also offer advantages when incorporating color pigments, eg in tinted day creams and make-up. Unfortunately, many W / O emulsions are negative in that they leave an oily residue on the skin that is slow to penetrate. In addition, their physical Stability often limited. This is especially problematic when W / O emulsions with aromatics are to be formulated.

Silicone-based emulsifiers almost exclusively contain PEG- and PPG-containing groups as a hydrophilic component. Typical representatives are 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 W / O emulsifiers in the market. The choice of PEG-free silicone emulsifiers is limited. For example, KF-6100, KF-6104, KF-6105 or KSG-710, KSG-810, KSG-820, KSG-830 or KSG-840 from Shin Etsu or Abil EM 120 from Evonik can be found here.

Typically, these W / O silicone emulsifiers are used in high concentrations of several percent. The choice of oils for W / O emulsions and in particular for W / Si emulsions is limited, since a high proportion of non-polar oils is required for good long-term stability. Therefore, in W / Si emulsions essentially silicone oils and / or liquid hydrocarbons are used.

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 which can be sensory-attractive, PEG-free and can be incorporated into the aromatics but meets all the requirements for a modern facial care product.

Overall, the main problem remains that water-in-oil emulsions tend to be unstable. Known evils of this kind are oil separation and phase separation. The problem gets even bigger when aromatics have to be installed. Although this can be counteracted by using known stabilizers (for example hectorites), or the proportion of the oil phase can be reduced. However, other disadvantages must then be taken into account, for example, that polar lipophilic substances such as, for example, UV filters can be incorporated less easily.

Object of the present invention was therefore to counteract these evils.

A particularly interesting emulsifier is sold by Dow Corning under the INCI name cetyl diglyceryl tris- (trimethylsiloxy) silylethyldimethicone and under the trade designation ES-5600. Low molecular weight aromatics are common ingredients in cosmetic formulations. Their structure and function can be very different. Low molecular weight aromatics can be used in the group of terpenes as part of perfume oils. Again, other low molecular weight aromatics have antimicrobial or antioxidant properties. Many of these substances are good solvents which adversely affect the stability of W / O emulsions. An example of this is benzyl alcohol. It was therefore surprising and unforeseeable to those skilled in the art that other similar aromatics do not have such a strong destabilizing effect on W / O emulsions containing cetyl diglyceryl tris- (trimethylsiloxy) silylethyldimethicone as emulsifier.

It was therefore surprising and unforeseeable for the skilled worker that the objects on which the invention is based are solved by cosmetic or dermatological water-in-oil emulsions

A) Cetyl diglyceryl tris (trimethylsiloxy) silylethyldimethicone as emulsifier

B) an oil phase

C) an aqueous phase,

characterized by a content of benzoic acid and / or one or more substances of the formulas (I) and / or formula (II) which have the following generic structure:

Where X can denote a branched or unbranched C 1 -C 4 -alkyl chain, a hydroxy group or an O-group, and the dashed bond indicates a double bond, if X denotes an O-group, and R independently of X a branched one or unbranched C 1 -C 4 -alkyl chain, a branched or unbranched C 1 -C 4 -alkyl chain bridged via an oxygen atom or a hydroxy group.

Formula (II)

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

Preferably, the compound (s) of the formulas (I) and / or (II) are selected from the group of methylparaben, ethylparaben, cymenol, hydroxyacetophenone.

Cymenol, or o-cymene-5-ol, lUPAC name 3-methyl-4- (1-methylethyl) phenol has the CAS no. 3228-02-02 and is characterized by the following structure:

Formula (II)

Ethyl paraben (p-hydroxybenzoic acid ethyl ester) has the CAS no. 120-47-8 and is characterized by the following structure:

Methylparaben (p-Hydroxybenzoesäuremethylester) has the CAS no. 99-76-3 and is characterized by the following structure:

4-hydroxyacetophenone (also called piceol) has the CAS no. 99-93-4 and is characterized by the following structure:

According to the invention, water-in-oil emulsions advantageously contain from 0.001 to 5.0% by weight, preferably from 0.01 to 3.0% by weight, particularly preferably from 0.1 to 1.0% by weight, based on the Total weight of the preparation, of benzoic acid and / or one or more compounds of the formula (I) and / or (II), in particular one or more compounds from the group of methylparaben, ethylparaben, cymenol, hydroxyacetophenone.

It was not to be expected that the preparations according to the invention

work better than moisturizing preparations,

be easier to formulate

better promote skin smoothing,

characterized by better care,

better serve as a vehicle for cosmetic and dermatological agents better sensory properties, such as the skin spread or the skin's ability to absorb

better suited as a vehicle for organic UV filters

have higher stability to decay in oil and water phases and would be characterized by better biocompatibility

the preparation of stable, in particular low-viscosity formulations enable as the preparations of the prior art.

The preparations according to the invention are free-flowing but can also be formulated into creams, have very good cosmetic properties, in particular with regard to stickiness, and have very good skin compatibility and skin care performance.

According to the invention, it is possible and advantageous to freely choose the proportion of the oil phase of the preparations according to the invention in the range from 3 to 60% by weight, based on the total weight of the preparations.

The oil or lipid phase according to the invention may contain all oils, fats, waxes and / or lipids customary in cosmetic preparations.

The aqueous phase of the preparations according to the invention may advantageously comprise customary cosmetic auxiliaries, for example alcohols, in particular those of low C number, preferably ethanol and / or isopropanol or polyols of low C number and their ethers, preferably propylene glycol, glycerol, 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, foam stabilizers, electrolytes, self-tanning agents, etc.

As basic components of the preparations according to the invention can be used:

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 alcohols of low C number, for example with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low C number or with fatty acids; Alcohols, diols or polyols of low C number, 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 ,

In particular, mixtures of the abovementioned solvents are used.

The oil phase of the emulsions according to the present invention optionally consists in part of silicone oils.

It is preferred to choose 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 the present disclosure Such silicones or silicone oils can be present as monomers, which are generally available through Structural elements are characterized as follows:

Linear siloxanes having a plurality of siloxy units which are advantageously used according to the invention are generally characterized by structural elements as follows:

wherein the silicon atoms can be substituted with identical or different alkyl radicals and / or aryl radicals, which are here generalized by the radicals R1 -R4 (meaning that the number of different radicals is not necessarily limited to 4), m can thereby Assume values from 2 to 200,000. Dimethicone is advantageously chosen as silicone oil. Other silicone oils, for example cyclomethicone (octamethylcyclotetrasiloxane), phenyldimethicone, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane), cetyldimethicone, behenoxydimethicone, are to be used advantageously in the context of the present invention.

However, it is possible to accept oil components from the group of other oil components without major disadvantages.

However, it is preferred to choose the oil components of the oil phase of the preparations according to the invention wholly or largely completely from the group of oils of synthetic and / or natural origin. These can then be 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 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, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, cetearyl isononanoate, isodecyl neopentanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, coco-caprylate / caprate, Olefin oleate, oleyl erucate, erucyl oleate, erucyl erucate and synthetic, semi-synthetic and natural mixtures of such esters, eg Jojoba oil.

Furthermore, the oil phase can be advantageously selected in part from the group of branched and unbranched hydrocarbons and waxes, 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. Caprylic capric triglyceride, cocoglycerides, sunflower oil, soybean oil, almond oil and the like.

Also advantageous are mixtures of dimethicone and Cetearylisononanoate. Of the hydrocarbons, paraffin oil, squalane, hydrogenated polyisobutene, isohexadecan, isododecane; Ci ₅ -ig alkane or polydecene advantageous to use in the context of the present invention.

Formulations 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 as a rule act as W / O emulsifiers.

Sorbitan stearate, sorbitan oleate, glyceryl isostearate, polyglyceryl-3-oleate, Wollwachssäurege- mix, wool wax alcohol mixtures, polyglyceryl-3 diisostearate, methyl glucose dioleate, polyglyceryl-4 isostearate ₇ cetyl dimethicone copolyol, sorbitan isostearate, polyglyceryl-2-dipolyhyd- roxystearat, polyglyceryl-3 diisostearate , Polyglyceryl-4-dipolyhydroxystearate, PEG-30-dipolyhydroxystearate, diisostearoylpolyglyceryl-3-diisostearate, polyglyceryl-2-dipolyhydroxystearate, polyglyceryl-3-dipolyhydroxystearate, polyglyceryl-4-dipolyhydroxystearate.

Emulsions according to the invention for the purposes of the present 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 fats, as well as water and one or more emulators, as commonly used for such type of formulation.

Of course, it is known to the person skilled in the art that sophisticated cosmetic compositions are generally not conceivable without the customary auxiliaries and additives. These include, for example, bodying agents, fillers, perfume, dyes, emulsifiers, pigments, additional active ingredients such as vitamins or proteins, light stabilizers, stabilizers, insect repellents, alcohol, water, salts, antimicrobial, proteolytic or keratolytic substances, etc.

Mutatis mutandis applies appropriate requirements for the formulation of medical preparations.

Medicinal topical compositions according to the present invention usually contain one or more drugs in effective concentration. For the sake of simplicity, reference is made to the clear distinction between cosmetic and medical use and corresponding products to the statutory provisions of the Federal Republic of Germany (eg Cosmetics Regulation, Food and Medicines Act). Accordingly, cosmetic or topical dermatological compositions according to the present invention, depending on their structure, for example, be used as skin protection cream, cleansing milk, sunscreen lotion, nutrient cream, day or night cream, etc. It is possible and advantageous, the compositions of the invention as a basis for pharmaceutical To use formulations.

Also favorable are those cosmetic and dermatological preparations which are in the form of a sunscreen. In addition to the active substance used according to the invention, these preferably additionally contain at least one UVA filter substance and / or at least one UVB filter substance and / or at least one inorganic pigment.

However, it is also advantageous in the context of the present inventions to prepare such cosmetic and dermatological preparations whose main purpose is not the protection from sunlight, but which nevertheless contain a content of UV protective substances. Thus, for example, UV-A or UV-B filter substances are usually incorporated in day creams.

Advantageously, preparations according to the invention may contain substances which absorb UV radiation in the UVB range, the total amount of filter substances being e.g. 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.

The UVB filters may be oil-soluble or water-soluble. As oil-soluble substances are e.g. to call:

Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester

Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate,

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

As water-soluble substances are advantageous:

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 the 3-benzylidene camphor, such as, for example, 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and its salts.

The list of said UVB filters which can be used according to the invention should of course not be limiting.

It may also be advantageous to use UVA filters in formulations according to the invention which are customarily contained 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-dione. (4'-isopropyl-phenyl) -propane-1,3-dione. Also preparations containing these combinations are the subject of the invention. It is possible to use the same amounts of UVA filter substances which have been mentioned for UVB filter substances.

Cosmetic and / or dermatological preparations according to the present invention may also contain inorganic pigments which are commonly used in cosmetics to protect the skin from UV rays. These are 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. But also ultramarine blue and pearlescent pigments. Particular preference is given to pigments based on titanium dioxide. The amounts mentioned for the above combinations may be used.

The cosmetic and dermatological preparations according to the invention may contain cosmetic active substances, auxiliaries and / or additives such as are conventionally used in such preparations, for example antioxidants, preservatives, bactericides, perfumes, substances for preventing foaming, dyes, pigments, the coloring effect have, thickeners, surface-active substances, emulsifiers, softening, moistening and / or moisturizing substances, fats, oils, waxes or other conventional ingredients of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, organic solvents or silicone derivatives. 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 the emulsions according to the invention, both the W / Si emulsifier and the W / O emulsifier are added to the oil phase. The components of the oil phase are mixed together with a magnetic stirrer to homogeneity of the phase, optionally heating something.

The sodium chloride and the respective aromatics are dissolved in the water phase. When using ethyl paraben, the water phase may be heated slightly to dissolve the raw material. Then the water phase is slowly added with stirring to the oil phase and then thoroughly mixed with a high-speed mixer (eg a magic stick ESGE) for about 2 minutes.

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

The stability was visually evaluated after 7 days, 14 days, 21 days (T) and 1 month (M).

"Stable" means that little or no phase separation, little or no oil separation occurs.

"Easily unstable" means that there is a moderate, visible phase separation or clearly visible oil separation. "Unstable" means fast, complete phase separation.

These experiments show that W / O emulsions with ES-5600 from Dow Corning were stabilized by aromatics such as ethylparaben and hydroxyacetophenone, or at least extended the long-term stability. This is all the more surprising as W / Si emulsions with benzyl alcohol are unstable.

The following examples are intended to explain the invention in more detail. Unless otherwise indicated, the data is% by weight.

Example formulations / 1 2 3 4% by weight

Benzyl alcohol 0.2

Ethylparaben 0.2

Hydroxyacetophenones 0.2

ES-5600 1 1 1 1

Cetearyl isononanoates 15 15 15 15

Dimethicone 5 5 5 5

Glycerol 5 5 5 5

Sodium chloride 1 1 1 1

Water Ad 100 Ad 100 Ad 100 Ad 100

Example formulations 7% by weight

Cetyl diglyceryl Tris- (trimethylsiloxy) silylethyldimethicone (ES-5600) 1

Methylparaben 0.2

Isononyl isononanoates 15

Dimethicone 5

Glycerol 5

Sodium chloride 1

Water Ad 100

Example formulations 8% by weight

Cetyl diglyceryl Tris- (trimethylsiloxy) silylethyl dimethicone (ES-5600) 2

Dicaprylyl carbonates 3

Cocoglycerides 2

Dimethicone 10

Butyl methoxydibenzoylmethane 1

Octocrylene 2

Octyl salicylates 3

Disteardimonium hectorite 0.2

Propylene carbonate 0.05

Ubiquinone 0.1

Tocopherol acetate 0.1

Color pigments (Cl 77891, Cl 77492, Cl 77491, Cl 77499, Cl 77007) 6

Methyl paraben 0.1

Hexanediol 0.5

Glycerol 5

Sodium chloride 1

Water Ad 100

Claims

Claims Cosmetic or dermatological water-in-oil emulsions containing

A) Cetyl diglyceryl tris (trimethylsiloxy) silylethyldimethicone as emulsifier

B) an oil phase

C) an aqueous phase, characterized by a content of benzoic acid and / or one or more substances of the formula (I) and / or formula (II), which have the following generic structures:

Where X can denote a branched or unbranched C 1 -C 4 -alkyl chain, a hydroxy group or an O group, and the dashed bond indicates a double bond, if X denotes an O group, and R independently of X a branched or unbranched C 1 -C 4 -alkyl chain, a branched or unbranched C 1 -C 4 -alkyl chain bridged via an oxygen atom or a hydroxy group.

Formula (II) as well as benzoic acid.

2. Emulsions according to Claim 1, characterized in that the compound (s) of the formula (I) and / or (II) are selected from the group consisting of methylparaben, ethylparaben, cymenol, hydroxyacetophenone.

3. Emulsions according to claim 1 or 2, characterized in that they are 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 (trimethylsilyl) loxy) silylethyldimethicone.

4. Emulsions according to one of the preceding claims, characterized in that they 0.001 to 5.0 wt .-%, preferably 0.01 to 3.0 wt .-%, particularly preferably 0.1 to 1, 0 wt .-% , based on the total weight of the preparation, of one or more compounds of the formula (I) and / or formula (II), in particular one or more compounds from the group of methylparaben, ethylparaben, cymenol, hydroxyacetophenone and / or benzoic acid.

5. Emulsions according to one of the preceding claims, characterized in that the oils of the oil phase are preferably selected from the group of liquid at room temperature monoesters, ethers, medium-chain triglycerides, and branched-chain and linear hydrocarbons.