Description

The invention relates to a coloring cosmetic preparation with a simple structure, characterized by high water resistance and durability on the application area. Furthermore, uses for this cosmetic preparation are also specified.

From the prior art various coloring cosmetic preparations are known that are characterized by good water resistance. In order to achieve a high level of water resistance high concentrations of synthetic polymerfilm formers are used. However, in light of the poor shelf life of the cosmetic preparation, products of this type are increasingly rejected by the consumer. This is all the more so since these cosmetic preparations often comprise, in addition to the polymer film formers, other raw materials that affect shelf life, such as volatile hydrocarbons or silicone oils, in order to dilute the high proportion of synthetic polymer film formers.

Starting from this prior art one problem of the present invention is to provide a coloring cosmetic preparation that, with a simple structure, due to a minimum of essential cosmetic ingredients, exhibits very good water resistance, uniform color coverage and long durability on the application area along with a high level of wear comfort. A further problem is also to specify uses of this coloring cosmetic preparation.

The solution to these problems results by means of the independent claims. The dependent claims contain advantageous further developments and configurations of the invention.

Accordingly the problem is solved by means of a coloring cosmetic that contains the following components, which are specified by their INCI (International Nomenclature of Cosmetic Ingredients): polyurethane-99, pullulan and hydrolyzed corn starch.

Within the meaning of the present invention a coloring cosmetic preparation is understood to be a preparation that is suitable, in the broadest sense, to make up skin, hair, mucous membranes and semi-mucous membranes and therefore also includes those ingredients that are approved for this purpose. In order to achieve color coverage, the cosmetic preparation comprises in particular at least once coloring substance. This coloring substance is not limited as to particulars and can comprise natural colorants, dyes and pigments individually or in any combination desired.

The preparation pursuant to the invention is present here in the form of an O/W emulsion that comprises a lipophilic phase that is surrounded by a hydrophilic phase. The O/W emulsion may be produced in any manner desired, whereby suitable techniques are known in the prior art. In particular, any emulsifiers may be used individually or in combination in order to create the desired emulsion. In order to improve the shelf life of the cosmetic preparation and to increase the natural origin content (determined pursuant to ISO 16128-1 dated February 15, 2016 and ISO 16128-2 dated September 2017), the O/W emulsion is preferably formed with emulsifiers that are not exclusively synthetic. Among these are natural or nature-identical emulsifiers, particularly those based on fatty acids, fatty acid esters and fatty alcohols, such as (listed with INCI) trihydroxy stearin, palmitic alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, cetearyl alcohol, stearic acid, palmitic acid and hydroxy stearic acid. In addition, glyceryl ester and sugar derivatives such as in particular polyglyceryl-3 methylglucose distearate, sorbitan isostearate, sorbitan stearate and various glucosides are natural emulsifiers.

Pullulan is a polysaccharide and is already used in cosmetic preparations as a natural film former. However, pullulan has the disadvantage that the films created with it are not water resistant and can easily be washed away with water.

The same result was obtained if a cosmetic preparation was produced with hydrolyzed corn starch (INCI: Hydrolyzed Corn Starch). The films obtained were not water resistant.

Even if polyurethane-99 as a sole film former was itself used in high concentrations, the desired water resistance could not be achieved.

Surprisingly, it was found that if pullulan and hydrolyzed corn starch, as water-soluble film formers, are used in combination with polyurethane-99, the water resistance can be improved many times over. The addition of other film forming substances can be thereby be avoided, so that the coloring cosmetic preparation pursuant to the invention contains, as essential functional components, only pullulan, hydrolyzed corn starch and polyurethane-99, whereby the recipe components can be reduced to a minimum without compromising functionality.

Polyurethane-99 is a polymer that is produced in multiple process steps. In a first step an ester polyol polymer is produced through the reaction of succinic acid with 1 ,4 butanediol and neopentyl glycol. The ester polyol polymer is then further reacted with saturated methylene diphenyl diisocyanate in order to obtain a polyurethane The polyurethane is then subjected to chain elongation and made water-dispersible by means of a further reaction with the sodium salt of 2-((2-aminoethyl)amino ethane sulfonic acid and ethylenediamine. Suitable polyurethane-99 dispersions are, for example, available under the trade names Baycusan eco E1001 from covestro. In comparison to the customary polymer film formers, polyurethane-99 exhibits 56 wt.-% natural raw materials or raw materials derived from natural products as ingredients, measured by ¹⁴ C analysis.

Through the combination of the aforementioned film formers, the coloring cosmetic preparation is characterized by excellent water resistance with very good wear comfort, uniform distribution on the application area and long adhesion and thus durability on the application site.

Preferably the quantity of polyurethane-99 in relation to the total mass of the preparation is 1 to 10 mass%. Higher quantities of polyurethane-99 may impair the abrasion resistance of a film of the cosmetic preparation on the application area, in particular after the application of water. It is assumed that after the application of water to a dried film of the coloring cosmetic preparation, upon mechanical stress to the film by water, infiltration of the high quantity of polyurethane-99-containing film on the application area takes place, so that rubbing over the film can cause it to be very slightly detached. The films’ adhesion of the application area without deterioration of the water resistance can be further improved if the quantity of polyurethane-99 in relation to the total mass of the preparation is 2 to 9 mass% and in particular s to 8,4 mass%. Lower quantities of polyurethane-99 are further preferred to save on raw material costs and with regard to facilitating the production of the O/W emulsion, although quantities below 1 mass% do not create good water resistance of the film. Very good waterproof films can be obtained with quantities of polyurethane-99 of at least 2 mass% and in particular of at least 3 mass% in relation to the total mass of the preparation.

The pullulan used in combination with polyurethane-99 in the cosmetic preparation is preferably contained in a quantity, in relation to the total mass of the preparation, of 0.5 to 5 mass%, in particular of 1 to 4 mass% and in particular from 1.5 to 3 mass%. A higher content of pullulan has been proven to stabilize the emulsion, but higher quantities of pullulan may adversely affect the uniformity of application of the cosmetic preparation and thus a homogeneous color coverage. Preferably, therefore, the quantity of pullulan used lies in a range of 0.5 to 5 mass%, whereby quantities of 1 to 4 mass% and in particular of 1 .5 to 3 mass% are preferred.

Pursuant to the invention, hydrolyzed corn starch is also used as a film former. In this regard it has been shown that the quantity of hydrolyzed corn starch in relation to the total mass of the preparation preferably lies in a range of 0.75 to 7 mass%. Hydrolyzed corn starch, although not itself waterproof, not only improves water resistance in combination with pullulan and polyurethane-99, but rather, among other things, provides for uniform application of the cosmetic preparation. For this the quantity of hydrolyzed corn starch should preferably lie within a range of 0.75 to 7 mass%, in particular in a range of 1.5 to 5 mass% and in particular in a range of 2 to 4 mass%. Quantities below 7 mass% are preferred due to a reduction of the viscosity of the cosmetic preparation, so that especially homogeneous color films can be created. Quantities below 2 mass% and in particular below 1.5 mass% or even below 0.75 mass% may have disadvantageous effects on the stability of the O/W emulsion and are therefore less preferred.

Since the addition of other synthetic film formers should preferably be omitted, the water resistance of the preparation may advantageously be improved by the fact that the coloring cosmetic preparation comprises at least one wax. All the waxes that are used and are usable in cosmetics may be used as waxes, including fats and in particular hardened fatty acids or fatty alcohols. Waxes are characterized by a melting point at an air pressure of 1013 Hectopascals of at least 40 °C and may be polished by slight pressure. One wax alone or two or more waxes in combination may be used. Particularly suitable waxes within the meaning of the present invention are the following waxes, specified by their INCI, which in each case may be used individually or in any combination: abies alba leaf wax, acacia dealbata flower wax, acacia decurrens flower wax, acacia farnesiana flower wax, camellia japonica leaf wax, camellia sinensis leaf wax, cananga odorata flower wax, candelilla cera, capsicum frutescens resin, carnauba acid wax, cetyl esters, cistus ladaniferus flower wax, citrus aurantium amara (bitter orange) flower wax, citrus aurantium dulcis (orange) flower wax, citrus aurantium dulcis (orange) peel wax, citrus limon (lemon) peel wax, copernicia cerifera (carnauba) wax, copernicia cerifera cera, cytisus scoparius flower wax, eclipta prostrata wax, ericerus pela wax, euphorbia cerifera (candelilla) wax, helichrysum angustifolium wax, hydrogenated japan wax, hydrogenated jojoba oil, hydrogenated palmitic/stearic/oleic/linoleic glycerides, hydrogenated rhus verniciflua peel wax, hydrolyzed candelilla wax, hydrolyzed carnauba wax, iris florentina flower wax, jasminum grandiflorum (jasmine) flower wax, jasminum officinale (jasmine) flower wax, jasminum sambac (jasmine) flower wax, lavandula angustifolia (lavender) flower wax, lawsonia inermis (henna) wax, mink wax, montan acid wax, montan cera, montan wax, mustela cera, myrica cerifera (bayberry) fruit wax, myrica pubescens fruit wax, nelumbo nucifera flower wax, oryza sativa (rice) bran wax, palm kernel wax, pelargonium graveolens wax, persea gratissima (avocado) wax.pistacia lentiscus (mastic) leaf wax, polianthes tuberosa flower wax, prunus armeniaca (apricot) kernel wax, pyrus cydonia peel/f ruit wax, pyrus malus (apple) peel wax, rhus succedanea fruit wax, ribes nigrum (black currant) bud wax, rosa centifolia flower wax, rosa damascena flower wax, rosa hybrid flower wax, rosa multiflora flower wax, rosmarinus officinalis (rosemary) flower wax, rubus idaeus (raspberry) leaf wax, saccharum officinarum (sugarcane) wax, salvia sclarea (clary) flower/leaf/stem wax, sambucus nigra wax, simmondsia chinensis Gojoba) butter, simmondsia chinensis Gojoba) seed wax, spent grain wax, stipa tenacissima wax, viola odorata leaf wax and vitis vinifera (grape) leaf wax.

There a total share of wax is in particular 0.5 to 10 mass% and in particular 0.5 to 8 mass%, in relation to the total mass of the preparation. If multiple waxes are used in combination, the quantities specified apply to the total mass of the waxes. Quantities above 8 mass% and in particular of 10 mass% and more have proven to be less advantageous, since they increase the viscosity of the cosmetic preparation so that the application properties of the preparation are adversely affected. In particular a uniform color coverage suffers from this, particularly in such applications in which the applied preparation cannot be distributed through mechanical rubbing, such as upon application to lashes or eyebrows, or even on the inner eyelid. Quantities of at least 0.5 mass% already show a good effect on the water resistance and also improve the stability of the O/W.

Long-term durability on the application area can be improved in that the wax or all waxes used exhibit a melting point of at least 60 °C.

In order to improve the color coverage the cosmetic preparation comprises in particular at least one coloring substance and among these in particular at least one pigment. Here a coloring substance may be used alone or in any combination of coloring substances. In particular the use of pigments improves the color coverage and thus also the coloring properties of the cosmetic preparation.

To improve the sustainability of the cosmetic preparation and thus its “clean beauty” properties, the cosmetic preparation has a natural origin content, determined according to ISO 16128-1 dated February 15, 2016 and ISO 16128-2 dated September 2017, of at least 70%, in particular of at least 80% and particularly preferred, of at least 90%. The natural origin content takes into account all raw materials used, so that a determination of the natural origin content allows a reliable comparison with other customary preparations, so an environmentally conscious consumer has a suitable means for selecting the sustainable products.

As already stated above, the preparation pursuant to the invention should have a minimum of essential functional substances so that, even while having a high functionality, it is characterized by a simple structure. This effect, along with the naturalness (natural original content) of the preparation, can be further improved if the preparation is free of other polymeric synthetic components with the exception of polyurethane-99. In this embodiment polyurethane- 99 is the only synthetic polymeric compounds. Other polymeric synthetic components that should be left out include in particular at least one acrylic acid-based unit and/or one urethane- based unit and/or a unit derived from a vinyl compound and/or a unit derived from silicone, such as various polyurethane derivates, acrylic acid and acrylate derivatives, silicates, trimethyl siloxysilicate, polyethylene, polypropylene, polystyrene derivatives and the like. The aforementioned raw materials are used in particular as film formers or thickeners. The specification that the cosmetic preparation is free of other polymeric synthetic components means that these other polymeric synthetic components are not added to the cosmetic preparation. Their in relation to the total mass of the cosmetic preparation is therefore essentially 0 mass%.

To further improve the naturalness of the cosmetic preparation it is in particular free of silicone oils and hydrocarbon oils. Silicone oils pursuant to the invention are understood to be both liquid silicone oils, such as linear or cyclical silicone oils, and among them cyclotetrasiloxane, cyclopentasiloxane, cyclohexasiloxane, disiloxane and trisiloxane, but also non-liquid silicone oils such as polydimethylsiloxane and its derivatives. The term “hydrocarbon oil” means in particular crude oil-based hydrocarbon oils, such as isododecane, paraffins, isoparaffins and the like. The specification that the cosmetic preparation is free of silicone oils and hydrocarbon oils means that these silicone oils and hydrocarbon oils are not added to the cosmetic preparation. Their quantity in relation to the total mass of the cosmetic preparation is therefore essentially 0 mass%.

In the interest of a further increase in the share of natural of natural substances in the cosmetic preparation, it is advantageously free of PEG and PPG compounds, ammonium-based surfactants and silicone-based surfactants. The aforementioned raw materials and compounds are often used in customary preparations as emulsifiers or an emulsion-stabilizing additive. They are characterized by a high share of synthetic ingredients and/or a high potential to irritate the user’s skin and should therefore preferably not be used. This means, in other words, that PEG- and PPG-compounds, ammonium-based surfactants, sulfate-based surfactants and silicone-based surfactants are not added to the cosmetic preparation. Their quantity in relation to the total mass of the cosmetic preparation is therefore essentially 0 mass%.

Other additives and auxiliary materials may be added to the cosmetic preparation, in particular those based on natural raw materials, such as antioxidants, wetting agents (for example glycerin, glycols, such as pentylene glycol), preservatives, oils, skin- and/or hair-care substances. However, since preservatives are often synthetic, it is stated that the cosmetic preparation described herein is in particular free of the preservatives for cosmetics means listed in the Cosmetics Ordinance in Appendix 6 (Appendix 6 KosmetikV (concerning § 3a) Preservatives for Cosmetics, Cosmetics Ordinance). Further pursuant to the invention the use of the above-described coloring cosmetic preparation is described for making up hair and/or skin and/or mucous membranes and/or semi-mucous membranes. In this way these application areas can be particularly uniformly made up with homogeneous color, whereby the film that forms after application is characterized by outstanding water resistance, very good wear comfort and long adhesion to the application area. Moreover, the rub resistance is very good.

Likewise pursuant to the invention, the use of the above-described coloring cosmetic preparation as eyeliner, eyeshadow, mascara or eyebrow mascara is disclosed. The application in the form of an eyeliner, eyeshadow, mascara or eyebrow mascara is disclosed. The application in the form of an eyeliner, eyeshadow, mascara or eyebrow mascara has proven to be particularly advantageous, since cosmetic preparations for these uses must be particularly waterproof and durable. Furthermore, their application requires particularly even color coverage, since uniform color coverage is achievable only with great difficulty through mechanical reworking, such as rubbing with an applicator or a finger.

Examples

The following invention is described in detail using examples; however the invention should not be limited to the examples.

In addition, the examples are explained using the drawing. This shows:

Fig. 1 smears of the examples on the back of a hand and

Fig. 2 the smears from Figure 1 after rinsing with water and mechanical stress.

* pullulan from DuoLux CM; pullulan content: 94.5 mass%

** MaizeCare Style Polymer from Dow Chemical; hydrolyzed starch content: 90 mass%

** Baycusan Eco E 1001 from covestro; polyurethane-99 content: 41 mass% To produce the examples raw materials with the numbers 1 to 11 were weighed into a first beaker and melted at 80 °C under agitation until a homogeneous mass was obtained.

In a second beaker the raw materials with the numbers 12 to 19 were mixed. Then the raw materials with the numbers 20 and 21 were added and homogenized with an Ultraturrax (Rotor- Stator homogenizer) until a uniform color distribution resulted. Then the colored mass was also heated to 80 °C. Unde3r agitation the mass heated to 80 °C was transferred from the first beaker to the second beaker, whereby an O/W emulsion formed, which was noticeable by the cream rising. The mass was again homogenized with an Ultraturrax. Then the mass was cooled down to approximately 50 °C and the raw material with the number 22 was added. The mass was agitated until it reached room temperature and then filled into a screw cap container.

The masses were examined visually for homogeneity. Then the masses were smeared on the back of a hand. This smear may be seen in Figure 1 in which, from left to right, smears from the following samples may be seen:

Comparison sample 1 , Comparison sample 2, Example 1 and Example 2. Figure 1 shows that the color smear of Example 1 was very deep and uniform. Moreover, after drying a satin finish was seen. A similar result was also obtained for Example 2.

Figure 2 shows a result of a rub test, in which the smears on the back of the hand (Figure 1) were rinsed with water at 35 °C for approximately 5 minutes and then rubbed with a finger perpendicular to the length of the smear. Example 1 was the only example that showed particularly high resistance to water as well as to rubbing. The film thinned out in its width only minimally and continued to adhere well to the skin. The film of Comparison samples 1 and 2 were not waterproof and largely dissolved already upon being rinsed with water. The film from Example 2 was itself resistant to water, but upon rubbing it partially separated from the back of the hand. The very high share of polyurethane-99 in Example 2 appeared to reduce the adhesion to the skin. A maximum quantity of polyurethane-99 of 8.4 mass% appears to be a threshold value for very good water resistance and at the same time excellent rub stability. Higher contents of polyurethane-99 may lead to reduced rub resistance.