WO2023016824A1

WO2023016824A1 - Coloring cosmetic composition comprising pullulan

Info

Publication number: WO2023016824A1
Application number: PCT/EP2022/071239
Authority: WO
Inventors: Karin Hofmann; Vanessa-Nina MARKSTEINER
Original assignee: Schwan Cosmetics International GmbH
Priority date: 2021-08-11
Filing date: 2022-07-28
Publication date: 2023-02-16
Also published as: DE202021104301U1; EP4384135A1; KR20240028497A

Abstract

The invention relates to a coloring cosmetic preparation with the following cosmetic raw materials designated by INCI: pullulan and water-insoluble cellulose. The preparation further contains at least one iron oxide pigment, wherein the total amount of iron oxide pigment, based on the total amount of the preparation, is 10 to 50% by mass.

Description

COLORING COSMETIC COMPOSITION COMPRISING PULLULAN

Description

The invention relates to a coloring cosmetic preparation and its use.

The desire to look good and to wear make-up to support this has existed almost as long as mankind has existed. Especially in this day and age, looking good embodies success, health and joie de vivre. Many cosmetics are known which make human skin decorative. There is a desire here for the cosmetics to have a high level of durability over a longer wearing period of several hours on the skin and to adhere permanently to the application site without losing color intensity under environmental influences as well, such as rainy weather. In order to meet this desire, polymeric synthetic film formers, such as film-forming substances based on acrylic acid or polyurethane, have been used to date, which have high adhesion to the skin and attachment to it and thus permanently fix the color at the application site.

With increasing body and environmental awareness, however, the demand for natural cosmetics-friendly preparations that don’t require synthetic raw materials or only use them in low concentrations if absolutely necessary has been increasing for years. Film formers based on natural raw materials, such as polysaccharides, including pullulan, which are characterized by high hydrophilicity and thus water solubility as well, are used as alternatives to synthetic polymeric film formers. By way of example, DE 2448868 A1 describes cosmetic preparations, such as eye shadow, which use pullulan as a water-soluble film former. However, such compositions have disadvantages with regard to the water resistance or waterproofness of the cosmetic preparations and therefore do not meet the requirements for long-lasting, water- resistant cosmetic preparations with high resistance to water.

It is therefore an object of the invention to provide a coloring cosmetic preparation, which is characterized by the use of natural film-forming substances and yet has outstanding coloring, permanently adhesive properties and high water resistance or even waterproofness.

This problem is solved by the features of the independent claims. The dependent claims relate to advantageous developments and refinements of the invention. Accordingly, the object is achieved by a coloring cosmetic preparation, which contains the two following cosmetic raw materials, identified by their INCI (International Nomenclature of Cosmetic Ingredients) names: pullulan and water-insoluble cellulose. Surprisingly, it has been shown that the water resistance and often the waterproofness as well of the cosmetic preparation can be significantly improved by adding the water-insoluble polysaccharide cellulose when using pullulan as the water-soluble film-forming substance. The water resistance or waterproofness, respectively, is determined as described in the experimental part.

According to the present invention, “water-insoluble cellulose” means a cellulose (INCI) which is characterized by a maximum water-binding capacity of 3.8% +/- 1.0% g_Water/gceiiuiose. The water binding capacity is measured according to AACC. The cellulose used according to the invention is therefore not a hydrocolloid, such as typical cellulose types used as thickeners, and thus has essentially no water-thickening properties. In addition, the cellulose used according to the invention is in particular in fiber form with an average fiber length of about 20 pm and can be obtained in particular from Bambusa Arundinacea stalks. At the time of filing, suitable water-insoluble celluloses are available, for example, under the trade name “SENSOCEL® be 20” from CFF GmbH & Co. KG.

The water binding capacity of a cellulose that can potentially be used is determined as follows:

2.00 g of cellulose are weighed into a centrifuge beaker with a capacity of at least 50 ml. 40.00 g of distilled water are added. The centrifuge beaker is then closed and not touched for 10 minutes. The centrifuge beaker is placed in a centrifuge and spun for 15 minutes at 1000g acceleration. A filter paper (8 pm pore size) is then placed in a Buchner funnel, which is connected to an Erlenmeyer flask and a vacuum is applied. The centrifuge beaker is inverted over the filter and held over the filter for one minute until no more liquid drips. The extracted liquid is reweighed.

The water binding capacity of cellulose is calculated using the following formula: wbc in % = ((a-b)/c*100%

Here a is the water weighed in, b is the reweighed water, c is the amount of cellulosic material and wbc is the water binding capacity.

It is also surprising that the above advantageous effect is only shown to a sufficient extent for those cosmetic preparations, which contain at least one iron oxide pigment, the total amount of iron oxide pigment being 10 to 50% by mass, based on the total amount of the preparation.

In other words, this means that the coloring cosmetic preparation according to the invention comprises the combination of raw materials pullulan, water-insoluble cellulose and iron oxide. Here, pullulan is a water-soluble polysaccharide produced from starch by culturing yeast. It is known as a film-forming substance for cosmetic preparations, but according to the invention it can only achieve sufficient water resistance or even waterproofness in combination with waterinsoluble cellulose, which is a water-insoluble powder obtained from Bambus Arundinacea stalks and has hitherto only been known as an abrasive, for example in face powders and cleaning cosmetics, provided that at least one iron oxide pigment is contained in the specified amount as the coloring substance.

According to the invention, an iron oxide pigment is understood as meaning a coloring pigment, which comprises at least one iron oxide. Common iron oxide pigments used in cosmetics are, for example, yellow iron oxide, red iron oxide, black iron oxide and mixtures thereof. The iron oxide pigments used in cosmetics are often also named with their color indices (Cl) and include Cl 77489, Cl 77491 , Cl 77492 and Cl 77499. The iron oxide pigments used according to the invention also include hydrophi lically or hydrophobically modified iron oxides, but no so-called pearlescent pigments, which only comprise a very thin layer of iron oxide and, for example, one or more layers of mica or borosilicate.

The amount of iron oxide pigment that is used according to the invention in order to give the coloring cosmetic preparation not only a good coloring effect but also high water resistance or even waterproofness is at least 10% by mass, based on the total mass of the cosmetic preparation. There is essentially no upper limit to the amount of iron oxide pigment. However, in order to obtain sufficient flowability of the cosmetic preparation, which is also crucial for homogeneous color release with a uniform layer thickness, the total content of all iron oxide pigments is at most 50% by mass, also based on the total amount of the cosmetic preparation. If several iron oxide pigments are used in combination, the stated amounts and ranges of amounts apply to all iron oxide pigments together, i. e. the sum of all iron oxide pigments.

In addition to the combination of raw materials essential to the invention, the cosmetic preparation according to the invention can contain other raw materials that are customary for cosmetic preparations, such as water, solvents, stabilizers, antioxidants, preservatives, care additives, aromas, perfume and the like. In addition, other pigments not containing iron oxide or other coloring substances such as dyes, pearlescent pigments and pigments not based on iron oxide (e.g. TiC>2) can also be used to produce a desired color.

It has been shown that the cosmetic preparation according to the invention results in a stable, abrasion-resistant colored film on the application area, which is not only characterized by good and lasting stability, but also shows high water resistance or even waterproofness. The water resistance and waterproofness are determined as described in the experimental part. In addition, it was found that very small amounts of the essential raw materials in the cosmetic preparations are sufficient to achieve the desired effects. It is assumed that the raw materials complement each other in their effect and the desired durability, water resistance or waterproofness results from the synergistic effect of pullulan, water-insoluble cellulose and iron oxide pigment.

The amount of pullulan, based on the total amount of the preparation, is preferably 0.5 to 5% by mass. If the amount of pullulan is below 0.5% by mass, a very high level of water resistance or even waterproofness cannot be achieved in all cases, e.g. with any color, or with very small amounts of iron oxide pigment of around 10% by mass. The minimum amount of pullulan used is therefore particularly advantageously 1 % by mass or even 1.5% by mass. With pullulan contents of more than 5% by mass, on the other hand, no significant increase in the water resistance or waterproofness of the cosmetic preparation can be detected. In the light of a reduction in raw material costs for the cosmetic preparation, the maximum amount of pullulan is therefore in particular 4% by mass and more advantageously 3% by mass. Particularly suitable amounts of pullulan are 1 to 4% by mass and in particular 1 .5 to 3% by mass.

Due to the synergistic interaction of the raw materials, even very small amounts of waterinsoluble cellulose are sufficient according to the invention to achieve very good water resistance or even waterproofness with high stability of the applied color film. Advantageously, the amount of water-insoluble cellulose, based on the total amount of the preparation, is 0.75 to 7% by mass. Below 0.75% by mass, some manufactured colors cannot achieve particularly high water resistance or even waterproofness. The amount of water-insoluble cellulose is therefore advantageously in a range from 1 to 5% by mass and in particular in a range from 2 to 4% by mass. With a content of water-insoluble cellulose of at least 2% by mass, the dry abrasion resistance is also improved in addition to the water resistance or waterproofness. Amounts of water-insoluble cellulose of more than 4% by mass or even more than 5% by mass and 7% by mass are preferably to be avoided when weighing the beneficial effects in terms of water resistance and waterproofness and the negative effects on the stability of the preparation and its raw material costs. Particularly preferred amounts of water-insoluble cellulose are in a range from 1 to 5% by mass and in particular in a range from 2 to 4% by mass.

As already explained, it was found that sufficient water resistance or waterproofness cannot be achieved for the coloring cosmetic preparation if the total content of iron oxide pigments is below 10% by mass, based on the total amount of the cosmetic preparation. The water resistance can advantageously be improved further if the total amount of iron oxide pigment, based on the total amount of the preparation, is at least 14% by mass. In order to further increase the water resistance, and thus also to enhance the waterproofness, it is advantageous if the minimum amount of iron oxide pigment used is 20% by mass. Even more preferably, the minimum amount of iron oxide pigment used is 25% by mass. As a result, not only can the depth of color and opacity of the preparation be increased, but its waterproofness can be improved to a particular degree. To improve the flowability and homogeneity of the covering power of the preparation, the total amount of iron oxide pigment, based on the total amount of the preparation, is in particular a maximum of 40% by mass and in particular a maximum of 30% by mass. This results in the following preferred quantity ranges for iron oxide pigment: 10 to 50% by mass, 10 to 40% by mass, 10 to 30% by mass, 14 to 50% by mass, 14 to 40% by mass, 14 to 30% by mass, 20 to 50% by mass, 20 to 40% by mass, 20 to 30% by mass, 25 to 50% by mass, 25 to 40% by mass and 25 to 30% by mass.

In order to adapt the flowability of the cosmetic preparation to the desired application form, the preparation can preferably also comprise at least one natural hydrocolloid thickener. Xanthan gum, gum arabic, different types of cellulose, dextrin, gelatin, carrageenan and the like are understood to be, inter alia, customary hydrocolloid thickeners. In addition, Caesalpinia Spinosa Gum is also considered a hydrocolloid thickener. When using Caesalpinia Spinosa Gum in the coloring cosmetic preparation, however, a further unexpected advantageous effect has been shown in addition to the desired rheological adjustment of the preparation: the dry abrasion resistance of the preparation could be significantly improved even by using small amounts of Caesalpinia Spinosa Gum.

Very small amounts of Caesalpinia Spinosa Gum are sufficient to increase the dry abrasion resistance of the preparation. Very good effects were obtained when the content of Caesalpinia Spinosa Gum, based on the total amount of the preparation, was 0.05 to 0.8% by mass, in particular 0.1 to 0.5% by mass and in particular 0.15 to 0.3% by mass. In some cases, amounts of more than 0.8% by mass can have an adverse effect on the flow properties of the preparation, so that amounts of at most 0.5% by mass or even only 0.3% by mass are preferably used.

Further advantageously in the light of an improvement in the stability of the preparation, in particular during storage and transport, the preparation comprises at least one glycol, the glycol comprising a total of 4 to 8 carbon atoms and in particular 4 to 6 carbon atoms and in particular being pentylene glycol (INCI). Without being bound to a theory, it is assumed that "long-chain" glycols with at least 4 hydrocarbons have a stabilizing effect on the water-insoluble cellulose and it is therefore better kept in suspension, which means it does not settle and the cosmetic preparation therefore can fully exercise its film-forming properties even after a longer period of time.

A further stabilization of the cosmetic preparation and in particular also high iron oxide pigment proportions can advantageously be achieved by adding triheptanoin, the amount of triheptanoin, based on the total amount of the preparation, being in particular 1 to 10% by mass, in particular 2 to 8% by mass and in particular 3 to 5% by mass. The optimal amount can be chosen in the light of the amount of iron oxide pigment used.

A humectant can also be used advantageously for the wearing properties of the coloring cosmetic preparation. In particular in combination with triheptanoin, the addition of glycerol has proven to be positive, with both raw materials together improving the settling stability of the preparation particularly well. The amount of glycerol, based on the total amount of the preparation, is advantageously in particular 1 to 8% by mass, in particular 2 to 6% by mass and in particular 2.5 to 4% by mass.

To improve market acceptance and in the light of environmentally and body-conscious handling of raw materials, the preparation is preferably free of polymeric synthetic components. Polymeric synthetic components are, in particular, those which are produced by means of synthesis from monomers by a polymerization reaction, i. e. in particular by free-radical polymerization, a polyaddition reaction or a polycondensation reaction, and which comprise at least two monomers bound to one another. In particular, polymeric synthetic components to be excluded from the cosmetic preparation and thus not to be added thereto comprise at least an acrylic acid-based unit and/or a urethane-based unit and/or a unit derived from a vinyl compound and/or a unit derived from a silicone unit. In the simplest case, a unit based on acrylic acid can be (meth)acrylic acid or else comprise one or more (meth)acrylic esters. A urethane based unit can be formed from any diol with any isocyanate. A unit derived from a vinyl compound can be, for example, vinyl acetate, vinyl alcohol or styrene. A silicone-derived unit can be polydimethylsiloxane or trimethylsiloxysilicates. All of the polymeric synthetic components mentioned here are usually listed in the literature as film formers and possibly also as thickeners. Because of their synthetic nature, they are not suitable for preparations that conform to natural cosmetics, as is the aim of the coloring cosmetic preparation according to the invention.

For the above reason, the coloring cosmetic preparation is preferably also free from silicone oils and hydrocarbon oils. Silicone oils and hydrocarbon oils commonly used in cosmetics are well known and include linear and cyclic compounds that can be volatile or non-volatile under application temperatures and application pressure, such as cyclopentasiloxanes, cyclotetrasiloxanes, cyclohexasiloxanes, disiloxanes, trisiloxanes, tetrasiloxanes, isododecanes, paraffins, isoparaffins and the like. These are preferably not added to the coloring cosmetic preparation.

The physical nature of the coloring cosmetic preparation is not limited in detail. Due to the very good applicability and application properties as well as the excellent durability, the liquid phase of the preparation is advantageously a single-phase aqueous, i. e. water-containing, phase and the pigments and optional fillers are present as a dispersed phase in the aqueous phase. In other words, the coloring cosmetic preparation is preferably present as a two-phase dispersion in which the first phase is an aqueous continuous phase and the second phase is a particulate phase and thus the pigments and any optional fillers are present as a dispersed phase in the aqueous phase. It is therefore not an emulsion in which two liquid, immiscible phases are distributed in one another. Rather, a supernatant of the liquids used in the preparation is transparent and single-phase (aqueous) after standing storage.

In addition to the raw materials explicitly mentioned, the above coloring cosmetic preparation can include other common cosmetic raw materials, such as water, other solvents, and among these in particular ethanol, antioxidants, preservatives, stabilizers, pH agents, care additives, perfume, aromas and others. Examples include coco-glucosides as stabilizers and coco- caprylate/caprates as skin-softening agents.

The applicability of the coloring cosmetic preparation disclosed above is not limited. Exemplary areas of application are skin make-up and make-up for application to mucous membranes and semi-mucous membranes. Cosmetic products mentioned by way of example, which comprise the preparation according to the invention are eyeliners, lipliners, lipsticks, blushers, eyebrowliners, make-ups, body tattoos and the like. However, the coloring cosmetic preparation is particularly suitable for eyeliner and lipliner, which is due to the particularly good water resistance or waterproofness with very good color depth.

Thus, according to the invention, the use of the coloring cosmetic preparation for making up the skin and/or mucous membrane and/or semi-mucous membrane and in particular for use as eyeliner and lipliner is also disclosed.

Examples -

Unless otherwise stated, the amounts given refer to % by mass, based in each case on the total mass of the preparation.

The respective cosmetic preparations for the tests were produced as follows: All raw materials except for the pigments (e.g. black iron oxide pigment Cl 77499) were weighed into a glass beaker and mixed by stirring until a homogeneous mass was formed. The pigments were then added and the mass was homogenized with an Ultraturrax at the highest level for 2 minutes. A black liquid formed.

The "waterproof test" to determine water resistance was carried out as follows: 10 volunteers of different sexes and ages were asked to clean their forearms with soap and water. Then, for each mass to be examined, five test areas each with an area of 1 cm² were applied to each forearm of a test subject. The mass was left to dry for 15 minutes. A waterjet (35 °C +/- 1 °C; flow: 3.2 l/min; distance between water nozzle and test area: 10 cm; waterjet diameter: 6 mm) was then poured over each test area of the first forearm of a subject for five minutes, so that the test area was completely rinsed with water. The test areas of the subject's second forearm served as a reference and were not rinsed with water.

This was followed by a visual assessment of the test areas:

1 stands for very waterproof

2 stands for partially waterproof

3 means not waterproof.

A gradation was made in steps of 0.1.

For the tests carried out in Table 1 , a value of up to 1.2 was sufficient for very good waterproofness. If a value of up to 1.2 was reached, no "water resistance test" was carried out to determine water resistance.

The differences between the "waterproof test" and the "water resistance test" were that in the "water resistance test" the water only had a temperature of 25 °C +/- 1 °C and the test areas were immersed in the standing tempered water for 1 minute.

1 stands for very water resistant

2 stands for partially water resistant

3 stands for not water resistant.

A gradation was made in steps of 0.1 . A value of 1 .2 or less was considered sufficient for water resistance.

If the "waterproof test" was positive, no "water resistance test" was carried out.

To carry out the preliminary test, test areas were applied to the forearms of a test subject, as for carrying out the "waterproof test", and left to dry for 15 minutes. Then the test areas of one forearm were rinsed with warm water at 25 °C +/- 1 °C for 1 minute. If in this preliminary test there was no difference between the test areas rinsed with water and the test areas not rinsed with water, a "waterproof test" and/or a "water resistance test" was carried out. If there were any visually recognizable differences, a "waterproof test" or a "water resistance test" could be dispensed with. Example 1: Effects of water-insoluble cellulose and pullulan

Table 1 below gives an overview of the tests carried out for Example 1.

Table 1 :

SENSOCEL® bc20 from CFF GmbH & Co. KG was used as the water-insoluble cellulose As can be seen from Table 1 , even small amounts of water-insoluble cellulose and small amounts of pullulan are sufficient to achieve very good waterproofness.

Example 2: Effects of the amount of iron oxide pigment

Table 2 gives an overview of the tests that were carried out with different iron oxide pigment contents. Table 2:

SENSOCEL® bc20 from CFF GmbH & Co. KG was used as the water-insoluble cellulose

The iron oxide pigments used in the tests for Example 2 were Cl 77499, Cl 77491 and Cl 77492. All other pigments were either pearlescent pigments or titanium dioxide (Cl 77891) and are therefore not among the iron oxide pigments used according to the invention. It can be seen from Table 2 above that a content of iron oxide pigments of at least 10% by mass, based on the total mass of the preparation, is required in order to achieve very good water resistance (see V7 compared to comparative tests 3 and 4). If the content of iron oxide pigment is increased from, for example, 11% by mass to 14% by mass (see V6 and V7), a better value can also be achieved in the “waterproof test” due to the increased content of iron oxide pigment. Iron oxide pigment contents of more than 25% by mass again led to a significant improvement in water resistance (see tests V3 to V5). Example 3: Effects of Caesalpinia Spinosa Gum

Table 3 provides an overview of a test in which the effect of Caesalpinia Spinosa Gum was examined.

Table 3:

* SENSOCEL® bc20 from CFF GmbH & Co. KG was used as the water-insoluble cellulose

Tests 8 and 9 show the influence of Caesalpinia Spinosa Gum. Caesalpinia Spinosa Gum acted as a hydrocolloid thickener in test 8. With the small amount used of 0.15% by mass, there were almost no effects on the rheology of the coloring preparation. However, Caesalpinia Spinosa Gum in the coloring cosmetic preparation improved the dry abrasion resistance significantly. The waterproofness was still very good.

The above examples show that the coloring cosmetic preparation according to the invention, which comprises pullulan and water-insoluble cellulose as film-forming substances and at least one iron oxide pigment as pigment, the total amount of iron oxide pigment, based on the total amount of the preparation, being 10 to 50 mass %, has very good water resistance or waterproofness and does not require any synthetic polymeric film formers. The preparation is characterized by a natural cosmetics-compliant composition and thus by a high level of market acceptance and sustainability.

Claims

1. Coloring cosmetic preparation comprising the following cosmetic raw materials designated with INCI:

- pullulan and

- water-insoluble cellulose and at least one iron oxide pigment, wherein the total amount of iron oxide pigment, based on the total amount of the preparation, is 10 to 50% by mass.

2. Coloring cosmetic preparation according to claim 1, wherein the amount of pullulan, based on the total amount of the preparation, is 0.5 to 5% by mass, in particular 1 to 4% by mass and in particular 1.5 to 3% by mass.

3. Coloring cosmetic preparation according to claim 1 or 2, wherein the amount of waterinsoluble cellulose, based on the total amount of the preparation, is 0.75 to 7% by mass, in particular 1 to 5% by mass and in particular 2 to 4% by mass.

4. Coloring cosmetic preparation according to any one of the preceding claims, wherein the total amount of iron oxide pigment, based on the total amount of the preparation, is at least 14% by mass, in particular at least 20% by mass and in particular at least 25% by mass, wherein the total amount of iron oxide pigment, based on the total amount of the preparation, is in particular a maximum of 40% by mass and in particular a maximum of 30% by mass.

5. Coloring cosmetic preparation according to any one of the preceding claims, further comprising at least one natural hydrocolloid thickener, in particular Caesalpinia Spinosa Gum.

6. Coloring cosmetic preparation according to claim 5, wherein the hydrocolloid thickener is Caesalpinia Spinosa Gum, and the amount of Caesalpinia Spinosa Gum, based on the total amount of the preparation, is 0.05 to 0.8% by mass, in particular 0.1 to 0. 5% by mass and in particular 0.15 to 0.3% by mass.

7. Coloring cosmetic preparation according to any one of the preceding claims, further comprising at least one glycol, wherein the glycol comprises a total of 4 to 8 carbon atoms and in particular 4 to 6 carbon atoms and is in particular pentylene glycol.

8. Coloring cosmetic preparation according to any one of the preceding claims, further comprising triheptanoin, wherein the amount of triheptanoin, based on the total amount of the preparation, is in particular 1 to 10% by mass, in particular 2 to 8% by mass and in particular 3 to 5% by mass.

9. Coloring cosmetic preparation according to any one of the preceding claims, further comprising glycerol, wherein the amount of glycerol, based on the total amount of the preparation, is in particular 1 to 8% by mass, in particular 2 to 6% by mass and in particular 2.5 to 4% by mass.

10. Coloring cosmetic preparation according to any one of the preceding claims, wherein the preparation is free from polymeric synthetic components, wherein the polymeric synthetic components include in particular at least a unit based on acrylic acid and/or a unit based on urethane and/or a unit derived from a vinyl compound and/or a unit derived from a silicone.

11. Coloring cosmetic preparation according to any one of the preceding claims, wherein the preparation is free from silicone oils and hydrocarbon oils.

12. Coloring cosmetic preparation according to any one of the preceding claims, wherein the liquid phase of the preparation is a single-phase aqueous phase and the pigments and optional fillers are present as a dispersed phase in the aqueous phase.

13. Use of the coloring cosmetic preparation according to any one of the preceding claims for making up the skin and/or mucous membrane and/or semi-mucous membrane.

14. Use of the coloring cosmetic preparation according to any one of claims 1 to 12 as an eyeliner or as a lipliner.