DE20308748U1 - Decorative cosmetic giving intense fluorescent effects under UV, contains a solvent-insoluble colorant which is especially a matrix of a polymer and an anionic or cationic dye - Google Patents

Abstract

A cosmetic composition for decorative use on the skin, lips, eyelids, hair, eyelashes or eyebrows contains a colorant which is insoluble in polar or apolar solvents but which gives fluorescent effects under UV.

Description

In the,

Heroldsberg, 4 June 2003 Reference: CS/PU/20.279/4290/nb

Schwan-STABILO Cosmetics GmbH & Co. KG

Schwanweg 1 D-90562 Heroldsberg

Preparation, especially cosmetic preparation Description

The invention relates to a preparation, in particular a cosmetic preparation according to claim 1, in particular in the form of loose or pressed powders or in the form of cast powders in stick form or in the form of extruded leads which can be produced from an extrudable mass and which have been dried by dehydration, which is suitable for cosmetic applications, in particular in the field of decorative cosmetics, for coloring and beautifying the skin, lips, eyelids, hair, eyelashes and eyebrows. Examples include make-up, in particular the so-called party effect make-up, contour pencils such as lip liners and eyeliners,

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Lip powder, cheek rouge, eye shadow, mascara, hair mascara and the like, which produce special fluorescence effects under UV light - so-called "black light". Such powders are produced by homogeneously mixing their finely powdered components and grinding them again if necessary and filling them loosely into suitable sales containers or by using an oil binder or an emulsion binder to bring them into a form suitable for compacting and pressing the resulting mixture under pressure into small sheet metal parts, so-called godets. It is also known to add plaster to the base mass, make it into a paste with water and then extrude it into leads or pour it into suitable sales containers and allow it to harden. Instead of plaster, an aqueous solution of a cellulose derivative such as carboxymethylcellulose or ethylcellulose can also be used, with the resulting product then having to undergo a drying process. Finally, it is also known to mix the powder mass with a volatile silicone oil, e.g. a cyclomethicone, and pour it into suitable molded parts, then dry the filled molded parts at an elevated temperature and then recover the evaporating solvent from a cooled water bath as a cold trap. The aforementioned processes are sufficiently known to the relevant expert from the literature.

These preparations are generally colored using colorants that are neither soluble in polar nor non-polar solvents and therefore remain at the place of application and do not bleed. There are a sufficient number of recipe examples in standard cosmetic works, such as K. Rothemann, "Das Große Rezeptbuch der Haut- und Körperpflegemittel", 1st edition 1949, G.A. Nowak, "Die Kosmetiken Präparate", 3rd edition, 1984 or H. Janistyn, "Handbuch der Kosmetika und Riechstoffe", 3rd volume, 2nd edition, 1973 or Balsam, Sagarin et al., "Cosmetics, Science and Technology", 2nd edition, 1974 and others. Pigmented preparations of the type mentioned are therefore well known to the relevant expert in many variations.

To colour these preparations, the expert generally uses colouring agents approved by the respective regional or national legislation, which have proven to be suitable in tests. Examples include pigments such as titanium dioxide, zinc oxide, iron oxides, chromium oxide, chromium oxide hydrate, ultramarine, manganese violet, ferric blue (Prussian blue), mica, titanium dioxide-coated micas, coloured micas coated with metal oxides, bismuth oxychloride, metal oxide-coated micas

coated bismuth oxychloride, platelet-shaped metal powders of aluminum, brass, bronze, copper, silver or gold, carmine and its various salts with metals, and varnishes of organic colorants with aluminum, barium, calcium, strontium or zirconium. This list is only an example and not exhaustive. The quantities used depend on the desired effects and are limited by the maximum quantities regulated in the respective national legislation. The quantity proportions of colorants are usually in a range of 0.1 to 50 wt.%, preferably in a range of 5 to 35 wt.% and particularly preferably in a range of 10 to 25 wt.%. These quantities for the colorants are given on the proviso that the sum of all ingredients of the aforementioned preparation, in particular cosmetic preparation, adds up to 100 wt.%.

The average particle size of the aforementioned colorants is in a size range of 0.5 to 10 pm, for the platelet-shaped colorants, such as micas, bismuth oxychlorides and metal powders, the average particle size can also be in a range of 5 to 150 pm. In addition to the colorants, so-called "non-coloring pigments" and other fillers, such as silicon dioxide, talc, kaolin, metal salts of fatty acids, such as Al, Mg, Ca, Zn or Sr stearate, palmitate or myristate, boron nitride, starch, organically modified starch, nylon powder, polytetrafluoroethylene powder or mixtures thereof, can also be present.

In order to avoid negative effects of prolonged storage, including during use by the end consumer - rancidity when using oil binders or emulsion binders or microbial spoilage due to contamination of the surface - additional antioxidants and preservatives that are common and permitted by the respective cosmetics legislation can be added to the preparations.

The above-mentioned preparations are available in a multitude of colors when using mixtures of the above-mentioned colorants - starting from white and going through the entire spectrum of the rainbow to black. However, these decorative preparations are very disappointing when the wearer, e.g. when visiting a disco or a party, goes into rooms that are mainly or exclusively illuminated with long-wave UV light - so-called "black light". White clothing glows

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here light blue, the titanium dioxide used in cosmetics also shimmers through a little. The color impression of decorative cosmetics in such rooms is usually very inconspicuous. If colorants from the group of laked fluoresceins, in particular halogenated fluoresceins - di-, tri- or tetrabromofluoresceins are used to make cosmetics, this very often results in bright fluorescent colors in the red tones. However, the use of laked coatings of these soluble dyes entails significant risks: healthy skin has a pH in the range of 5-6; 5.5 is said to be ideal here - the same pH range is also found in sweat. Tears, on the other hand, have a slightly basic pH in the range of 7.4. Due to the moisture in the skin, it is now possible for the dyes to bleed out of laked fluorescein-based dyes due to the possible different pH values in the product and on the skin, because they are dissolved out of the varnish. This is particularly fatal because fluoresceins are very substantive and absorb into the skin for a very long time - up to several days. In UV light, the traces of them are made even more visible. Color varnishes based on fluoresceins and halogenated fluoresceins therefore make a very interesting effect make-up for use under "black light" - due to the possible risk of bleeding, however, these preparations can have very unpleasant side effects that are also difficult to remove from skin and hair. These possible side effects become a hindrance to sales after the first bad experience with such a product. Similar observations were also made with varnishes made from soluble quinoline and anthraquinone dyes. Titanium dioxide alone or optical brighteners such as disodium distyryldiphenyl disulfonate or similar essentially only produce light blue fluorescent colors and thus only a few possibilities for variation in the range of yellow to red fluorescent colors - an overall unsatisfactory situation.

The problem thus arose of developing a preparation, in particular a cosmetic preparation in the form of loose or pressed powders or in the form of cast powders in stick form, which is suitable for cosmetic applications, in particular in the field of decorative cosmetics , for colouring and beautifying the skin, lips, eyelids, hair

as well as eyelashes and eyebrows. Examples include make-up, especially the so-called party effect make-up, contour pencils such as lip liner and eyeliner, lip powder, cheek rouge, eye shadow, mascara, hair mascara and the like, through

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Selection from the aforementioned raw materials, which are generally known to the relevant expert, and to color them with suitable colorants that are insoluble in the preparation so that they show intensive and interesting fluorescence on the skin, lips, eyelids, hair, eyelashes and eyebrows under UV light, so-called "black light", without soluble dyes being able to be dissolved out of the preparations under in-vivo conditions, e.g. by the moisture of the skin or by sweat or even by tear fluid - this is to be understood as the so-called "bleeding" - so that negative optical impressions, which are further intensified under "black light", are avoided. Under normal light conditions, especially in daylight, the use of these suitable colorants, if necessary in addition to the aforementioned colorants, should convey more intense color impressions by the fact that these colorants, which can be excited to fluorescence by UV light, are stimulated to release UV light by the UV component contained in daylight. stimulated by fluorescent light.

The stated object is achieved by using colorants which are insoluble in the above-mentioned preparation and which were obtained by salt formation, by forming a neutral salt - or by means of a true covalent bond - from a matrix made of a polymer material with at least one functional group in the side chain and a soluble dye with at least one functional group. To achieve the object, either colorants can be used which are produced, for example, by reacting polyesters which are also insoluble in the preparation and which contain at least one primary, secondary or tertiary amino group in the side chain with anionic dyes or polyesters which contain at least one acid residue in the side chain with cationic dyes. It is also conceivable to react polyacrylates or polymethacrylates or polyurethanes which have at least one of the above-mentioned amino groups or at least one acid group in the side chain with dyes with oppositely charged functional groups. It is essential for use that the dyes to be selected are stable to hydrolysis under in vivo conditions, which can be easily determined by a simple test - namely by storing the dye in a 1% aqueous solution of an organic hydroxy acid, such as lactic acid or citric acid, buffered to pH 5.5 for 24 hours at 37 ^° C.

For example, dyes are commercially available which consist of a polyester matrix obtained by the reaction of ethylene glycol, cyclohexanedimethanol, terephthalic acid, isophthalic acid and norbornanediamine as well as dyes derived from fluoresceins, quinoline dyes, triphenylmethane dyes and anthraquinone dyes. A suitable polyester matrix is also known to the person skilled in the art as "polyester-3".

Dyes such as C.I. No. 45.380 (tetrabromofluorescein), C.I. No. 45.370:1 (mixture of dibromo-, tribromo- and tetrabromofluorescein), C.I. No. 47.000 (quinophthalone, not for use on mucous membranes), C.I. No. 47.005 (quinophthalone-disulfonic acid), C.I. No. 42.090 (triphenylmethane dye), C.I. No. 60.730 (anthraquinone dye, not for use on mucous membranes), C.I. No. 61.570 (anthraquinone dye) are mentioned here.

The preparation according to the invention will now be explained in detail using the following examples, which, however, do not describe it conclusively. All quantities are given in percent by weight (wt. %), based on the total weight of the preparation. The internationally common "INCI names" or non-proprietary names generally known to the relevant expert are used as raw material names. The preparations found, in particular cosmetic preparations, are in the form of loose or pressed powders or in the form of cast powders in stick form.

Example 1 - Effect make-up (loose powder)

Clay 22,500

Calcium carbonate 12,000

Talc 20,000

Etherified starch (ANM rice) 14,000

Titanium dioxide 7,000

brown iron oxide 3,500

Sr Laurat 7,700

Mg-Myristate 5,000

-7-Example 1 - Effect make-up (loose powder) - continue

Polyester-3, Red-28 3,500

Polyester-3, Yellow 10 1,000

Aluminium oxide 3,500

Methylparaben 0.150

Propylparaben 0.050

Perfume oil 0.100

The "white" powder components are mixed in a plowshare mixer with a homogenizer while cooling, and then the preservatives and perfume oil are added. The iron oxide and fluorescent colors are then added and the mixture is mixed intensively. The mixture is then ground using a gear mill or passed through a vibrating sieve and then filled into sales containers. The loose powder is preferably applied to the skin using a brush. The result is a light, reddish-brown, very grippy powder that adheres well to the skin and shows orange to magenta fluorescence in long-wave UV light. A lighter or darker shade of the powder can be achieved by varying the amounts of red iron oxide and titanium dioxide.

Example 2 - Effect lip powder (loose powder)

Clay 33,000

Talc 18,000

Etherified starch (ANM rice) 16,300

Titanium dioxide 2,500

D & C Red 7(CL No. 15,850:1) 3,300

red iron oxide (CL-No. 77.491) 3,500

yellow iron oxide (CL-No. 77.492) 1,500

Sr Laurat 7,700

Mg-Myristate 5,000

Polyester-3, Red-28 4,500

-7-Example 2 - Effect lip powder (loose powder) - continue

Polyester-3, Yellow 10 0.500

Methylparaben 0.150

Propylparaben 0.050

Perfume oil 0.100

Alpha-Bisabolol 0.100

Na-cyclamate 0.050

Aluminium oxide 3,500

colloidal silica 0.250

The powder mixture is prepared in the same way as in example 1. The result is a matte, strong red lip powder with good grip and good adhesion, which can be applied to the lips alone or over a lipstick. It shows a clear magenta fluorescence in long-wave UV light.

Example 3 - Effect make-up (cast)

Mixture of Example 1 94,000

Binders 6,000

Binder:

Carboxymethylcellulose 2,500 Gum Arabic 2,000 Carrageenan 2,500 Ethanol (cosmetically denatured) 6,000 Dowicil 200 1,000 Water 86,000

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In a suitable container, gum arabic is poured over with ethanol. The water is heated to 80 ^° C and poured onto the gum arabic, then left to swell. Then add Dowicil 200, the carboxymethyl cellulose and the carrageenan while stirring. The mixture is left to swell, stirred until lump-free, then the binder is added to the powder mixture and everything is processed into a thick paste. If necessary, a little more water can be added. The mixture is poured into suitable, rust-proof sheet metal parts, shaken smooth if necessary and dried at 50-60°C until the weight is constant.

Example 4 - Eyeshadow (pressed)

Powder mixture: 18,000 kaolin 7,000 talc 14,500 etherified starch (ANM rice) 35,600 Mica (TiC>2 coated) 5,500 Sr-La u rat 3,500 Mg-myristate 5,000 Ultramarin 4,500 Chromium oxide hydrate green 4,000 Polyester-3, Yellow 10 2,000 Polyester-3, Blue 1 0.200 Disodium distyryldiphenyl disulfonate 0.150 Methylparaben 0.050 Propylparaben

Oil binder:

Isopropyl myristate 20,000

Isopropyl anolate 25,000

acetylated lanolin 15,000

Paraffin oil, thick 39,400

-9-Example 4 - Eye shadow (pressed) - next

Methylparaben 0.150

Propylparaben 0.050

Tocopheryl acetate 0.400

Powder Mix 82,000

Oil Binder 18,000

The oil binder is produced by slightly heating the oil phase and dissolving the preservatives in it. It can be used immediately and can also be stored.

The powder components, except for the mica, are placed in a plowshare mixer with a homogenizer and mixed intensively while cooling. Around 60% by weight of the oil binder is then added by spraying or in portions. The mica is then added, followed by the remaining oil binder in portions. The mixture is sieved using a vibrating sieve and then compacted into small metal parts (godets) using a suitable press. This gives a pearlescent, blue-green compact powder with good adhesion that exhibits a bright, yellowish fluorescence under long-wave UV light.

Example 5 - Eye shadow (extruded lead)

talc 18,500 Mica (TiO ₂ coated) 35,000 Pumice powder 18,000 Mg-myristate 4,500 Sr Laurat 5,500 Bentonite 1,000 Guar Gum 2,000 PVP highly viscous 1,000 Titanium dioxide 3,000

In the,

-10-Example 5 - Eye shadow (extruded lead) - continue

Ultramarin 3,500 Polyester-3, Blue 1 7,500 Disodium distyryldiphenyl disulfonate 0.200 Methylparaben 0.150 Dowicil 200 0.150

Guar gum and PVP are dissolved in about 10-15 parts water while heating. In a mixer, e.g. a suitable kneader, the powder components are mixed well - initially without adding the mica - then the mica is added. The aqueous solution of the binding agent is then added and the mixture is kneaded until a homogeneous, very pasty mass is formed. This is formed using an extruder into leads of, for example, 8 mm or 10 mm diameter, which are cut to length and preferably dried at a slightly higher temperature. The leads can be inserted into casings made of a sharpenable material - e.g. plastic casings or, as is known from pencil production, wood. The leads can also be wrapped in a tube made of a thermoplastic, shrinkable material in the usual way before further processing. They can also be inserted into a rotary mechanism. The above example produces a lead that produces a light blue, pearlescent line that glows light blue in long-wave UV light. By simply varying the pigment mixture using the aforementioned luminous pigments, other lead colors with different fluorescence in long-wave UV light can of course be produced.

Example 6 - Lipliner (extruded lead)

Talc 21,000

Clay 12,000

Pumice powder 18,000

Mg myristate 5,800

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Example 6 - Lipliner (extruded lead) - continue

mica 15,000 Sr Laurat 3,800 Mg stearate 4,000 Bentonite 1,000 Carboxymethylcellulose 2,500 Guar Gum 2,000 yellow iron oxide (C.I. No. 77.492) 3,000 D&C Red No. 9 (C.l. No. 15.585:1) 5,500 Polyester-3, Red 22 6,000 Dowicil 200 0.150 Na-cyclamate 0.050 Methylparaben 0.150 Propylparaben 0.050

The production is carried out analogously to example 5. The finished mass is extruded into leads with a thickness of about 4 mm, which are then processed further in the manner described. The result is a lead with a strong red line, which shows a strong yellowish-magenta fluorescence in long-wave UV light.

Example 7 - Eyeliner (extruded lead)

talc 21,000 kaolin 12,000 Pumice powder 18,500 Mg-myristate 5,800 mica 15,000 Sr Laurat 3,800 Calcium sulfate hemihydrate 3,500 Bentonite 1,200 1.2-Propylene glycol 1,500

-12- Example 7 - Eyeliner (extruded lead) - continue

Carboxymethylcellulose 2,500 Ultramarin 4,000 black iron oxide 1,200 Polyester-3, Blue 1 9,500 Disodium distyryldiphenyl disulfonate 0.150 Dowicil 200 0.150 Methylparaben 0.150 Propylparaben 0.050

The preparation is carried out analogously to the above examples 6 and 7 and extruded to form leads with a diameter of about 4 mm. It should be noted, however, that work must continue very quickly after addition, as the preparation hardens quickly and irreversibly due to the use of calcium sulfate hemihydrate. It is advisable to prepare the preparation in small portions so that it can be extruded within a few minutes. The leads are dried at a slightly higher temperature and processed further in the manner described above. A lead with a strong dark blue line is obtained, which fluoresces blue under long-wave UV light. With this preparation too, other color shades can easily be produced by simply varying the pigment mixture.

Example 8 - Effect Mascara (Cake Mascara)

Stearic acid 30,000

Isostearic acid 6,000

Carnauba wax 11,700

Beeswax 13,000

Vaseline, white 8,000

Triethanolamine 13,800

Methylparaben 0.150

Propylparaben 0.050

-13-Example 8 - Effect Mascara (Cake Mascara) - continue

Tocopheryl acetate 0.200

Perfume oil 0.100

Talc 5,000

Polyester-3, Red 28 12,000

The lipid phase is melted in a suitable vacuum stirred tank, then the triethanolamine is added and stirred well, then the powder phase is added, the mixture is homogenized and then deaerated under vacuum. The preservatives, the antioxidant and the perfume oil are then added. The mass is now poured into suitable crucibles while still hot or poured into molds to form bars. The mass can also be poured into blocks and heated again at a later time to around 75-80 ^° C and then poured out while hot. A red mass is obtained which shows an intense magenta fluorescence under long-wave UV light. It can be taken out of the crucible using a moistened brush and applied to the tips of the eyelashes. In bar form it can be used as hair mascara, for example by applying it directly to moistened hair. Any color variations are of course easily possible using the other luminous pigments mentioned above.

Claims (23)

1. Preparation, in particular cosmetic preparation for the field of decorative cosmetics for coloring and beautifying the skin, lips, eyelids, hair, eyelashes and eyebrows, characterized in that it contains at least one colorant which is insoluble in polar and non-polar solvents and produces fluorescence effects under UV light. 2. Preparation according to claim 1, characterized in that this preparation is make-up, in particular party effect make-up, contour pencils such as lip liner and eyeliner, lip powder, cheek rouge, eye shadow, mascara or hair mascara. 3. Preparation according to claim 1 or 2, characterized in that the colorant was obtained from a matrix of a polymer material having at least one functional group in the side chain and at least one soluble dye having at least one functional group by way of salt formation by formation of a neutral salt. 4. Preparation according to claim 1 or 2, characterized in that the colorant is obtained from a matrix of a polymer material having at least one functional group in the side chain and at least one soluble dye having at least one functional group by means of a true covalent bond. 5. Preparation according to claim 1 or 2, characterized in that the matrix is made of a polymer material selected from polyesters, polyacrylates, polymethacrylates or polyurethanes having at least one primary, secondary or tertiary amino group in the side chain or mixtures thereof and at least one anionic dye. 6. Preparation according to claim 1 or 2, characterized in that the matrix is made of a polymer material selected from polyesters, polyacrylates, polymethacrylates or polyurethanes with at least one acid residue in the side chain or mixtures thereof and has been reacted with at least one cationic dye. 7. Preparation according to one of claims 3 to 5, characterized in that the matrix of a polymer material was obtained by the reaction of ethylene glycol, cyclohexanedimethanol, terephthalic acid, isophthalic acid and norbornanediamine and reacted with at least one anionic dye. 8. Preparation according to claim 12, characterized in that the anionic dye is C.I. No. 42.090, C.I. No. 45.370:1, C.I. No. 45.380, C.I. No. 47.000, C.I. No. 47.005, C.I. No. 60.730, C.I. No. 61.570 or mixtures thereof. 9. Preparation according to one of claims 8 to 13, characterized in that the colorant is stable to hydrolysis and does not bleed when stored for 24 hours at 37°C in a 1% aqueous solution of an organic hydroxy acid, such as lactic acid or citric acid. 10. Preparation according to one of the preceding claims, characterized in that it optionally additionally contains at least one pigment such as titanium dioxide, zinc oxide, iron oxides, chromium oxide, chromium oxide hydrate, ultramarine, manganese violet, ferric blue (Prussian blue), mica, micas coated with titanium dioxide, colored micas coated with metal oxides, bismuth oxychloride, bismuth oxychloride coated with metal oxides, platelet-shaped metal powders of aluminum, brass, bronze, copper, silver or gold, carmine and its various salts with metals, laquering of organic colorants with aluminum, barium, calcium strontium or zirconium or mixtures of the pigments mentioned. 11. Preparation according to one of the preceding claims, characterized in that the proportions of the colorants are in a range from 0.1 to 50 wt. %, preferably in a range from 5 to 35 wt. %, very particularly preferably in a range from 10 to 25 wt. %, with the proviso that the sum of all ingredients of the preparation is 100 wt. %. 12. Preparation according to one of the preceding claims, characterized in that it may optionally also contain fillers such as silicon dioxide, talc, kaolin, metal salts of fatty acids such as Al, Mg, Ca, Zn or Sr stearate, palmitate or myristate, boron nitride, starch, organically modified starch, nylon powder, polytetrafluoroethylene powder or mixtures thereof. 13. Preparation according to one of the preceding claims, characterized in that it is a loose powder. 14. Preparation according to one of the preceding claims, characterized in that it is a pressed (compacted) powder. 15. Preparation according to one of the preceding claims, characterized in that the pressed powder can be produced in the form of an extruded lead which is then dried by dehydration. 16. Preparation according to one of the preceding claims, characterized in that it is a cast powder. 17. Preparation according to claim 15, characterized in that it is a cast powder in stick form. 18. Preparation according to claims 16 or 17, characterized in that the cast powder in stick form consists of a heat-softening mass which is pourable when hot and solidifies again when cooled. 18. Preparation according to claim 15, 17 or 18, characterized in that the leads preferably have a diameter between 4 and 10 mm. 19. Preparation according to claim 14, characterized in that it contains an oil binder as binding agent. 20. Preparation according to claim 14, characterized in that it contains an emulsion binder as binding agent. 21. Preparation according to claim 15, characterized in that it contains calcium sulfate hemihydrate as a binding agent. 22. Preparation according to claim 15, characterized in that it contains guar gum, carrageenan, carboxymethylcellulose, gum arabic or mixtures thereof as binding agents.