EP1916986A2

EP1916986A2 - Preparation containing barium sulfate

Info

Publication number: EP1916986A2
Application number: EP06764091A
Authority: EP
Inventors: Petra Biehl; Reiner Mertscheit; Heiner Schulte; Shirley Shen; Bernd Hirthe
Original assignee: Sachtleben Chemie GmbH
Current assignee: Venator Germany GmbH
Priority date: 2005-07-18
Filing date: 2006-07-06
Publication date: 2008-05-07
Also published as: CN101355921A; WO2007009887A3; KR20080043781A; WO2007009887A2; US20090060960A1; CN101355921B; BRPI0613412A2; JP2009501754A; TW200726484A

Abstract

The invention relates to a preparation containing barium sulfate, a method for the production thereof, and the use thereof.

Description

Barium sulfate containing preparation

The present invention is a barium sulfate-containing preparation, a process for their preparation and the use of this preparation.

In particular, the present invention is a barium sulfate-containing topically applicable preparation, preferably a cosmetic or dermatological formulation, a process for their preparation and the use of this preparation, preferably as an anti-wrinkle cream.

Wrinkles in the human skin are visually perceived because the possibility of diffuse light scattering in them is severely restricted, making the actual wrinkles appear darker than the surrounding skin surface. Out

For reasons of aesthetics, it is often attempted to reduce, smooth or at least optically conceal these wrinkles. For this purpose, there are many

Care products, some of which also contain barium sulfate (EP-A-14371 17, EP-A-136941 1, DE-A-10063433, WO-A-0192157).

On the one hand, barium sulfate is available inexpensively, on the other hand it can easily be incorporated into care products.

However, the barium sulfate used in the above preparations has a particle size below 100 nm, preferably below 50 nm (WO-A-0192157), or an average particle size below 100 nm, preferably between 5 and 50 nm, in particular between 15 and 30 nm (EP-A-14371 17, EP-A-136941 1, DE-A-10063433). However, barium sulfate with an average particle size of 100 nm has only a low relative scattering power for visible light, for example 0.01 in the case of light having a wavelength of 550 nm. For smaller particle sizes, the scattering power with light of this wavelength is even lower. The use of barium sulfate of these particle sizes therefore requires further, mostly expensive active ingredients and add additives to the formulations to reduce, smoothen, or visually conceal wrinkles.

The object of the present invention is to overcome the disadvantages of the prior art. In particular, it is an object of the present invention to provide a cosmetic preparation which contains barium sulfate and which is suitable for reducing, smoothing or visually concealing wrinkles. A further object of the invention is to provide a cosmetic preparation which contains barium sulfate and is also suitable without expensive active ingredients and additives for reducing, smoothing or visually concealing wrinkles. Another object of the invention is to provide a cosmetic preparation containing barium sulfate which is suitable over the entire spectrum of visible light for reducing, smoothening or visually concealing wrinkles.

According to the invention, this problem is surprisingly solved by the features of the main claim. Preferred embodiments can be found in the subclaims.

As already known from WO-A-0192157, due to its optical properties, barium sulfate (both synthetic and natural) is capable of scattering, reflecting and refracting light. Wrinkles appear darker than the surrounding skin surface due to limited diffuse light scattering. In particular, by the scattering power of barium sulfate these wrinkles are perceived optically less.

However, the relative scattering power of barium sulfate particles is strongly dependent on the mean grain size. Thus, the relative scattering power with visible light of a wavelength of 550 nm at 0.1 microns is only 0.01, at 0.2 microns already 0.04, then reaches at a mean grain size of about 1 micron, the maximum of 0.14, to drop to 0.06 at 10 nm and to approximately 0.035 at 20 nm. Corresponding dependencies are found for other areas of visible light, with shorter wavy light scattering more on smaller and longer wavy light on larger particles. Surprisingly, it has been found that the object is achieved by the use of barium sulfate having a particle size of 1 to 30 μm. The barium sulfate particles can be both aftertreated and untreated. Furthermore, it has surprisingly been found that the problem is solved by the use of barium sulfate of a particle size of 0.1 to 8 microns. The barium sulfate particles are preferably aftertreated in this case.

The aftertreatment can be either inorganic or organic as well as inorganic and organic. By post treatment is to be understood in particular coating.

The inorganic coating is preferably carried out with Al ₂ O ₃ , TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , CeO ₂ , MnO ₂ , SiO ₂ or mixtures of these and / or the corresponding hydroxides or mixtures of these. The proportion of the inorganic coating is 1 to 50 wt .-%, preferably 5 to 30 wt .-%, each based on the barium sulfate used.

The organic coating is preferably carried out with stearic acid, silicone oils, simethicones and / or silanes. The proportion of the organic coating is 1 to 20 wt .-%, preferably 2 to 10 wt .-%, each based on the barium sulfate used.

In addition, the untreated as well as the inorganic and / or organic post-treated with inorganic materials, preferably inorganic oxides such as Al ₂ O ₃ , TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , CeO ₂ , MnO ₂ , SiO ₂ or mixtures thereof and / or the corresponding hydroxides or mixtures thereof. The proportion of these inorganic additives is 1 to 50 wt .-%, preferably 5 to 30 wt .-%, each based on the barium sulfate used.

The barium sulfate according to the invention is in use concentrations of 1 to 15 wt .-%, preferably from 1 to 10 wt .-%, particularly preferably from 1 to 6 wt .-%, very particularly preferably from 1 to 4 wt .-%, in particular of 1 to 3 wt .-% of the preparation. Further advantageous according to the invention - A -

Use concentrations are 6 to 15 wt .-%, preferably 6 to 12 wt .-%, particularly preferably 7 to 10 wt .-%.

In this case, the barium sulfate used according to the invention may be natural and / or synthetic origin.

The preparation of the preparation according to the invention is carried out by methods which are known from the prior art.

In addition, it has surprisingly been found that barium sulfate can be used not only in anti-wrinkle creams, but according to the invention in a variety of care products. The care products may be based on an emulsion; they can be based on both an oil-in-water and a water-in-oil formulation. By way of example, products of day care, eye creams, sunscreen care products, personal care products, anti-cellulite products, make-up formulations, foundations, powders; All of these products can - as far as appropriate - also contain a UV protection agent.

The subject of the invention is in detail:

a topically applicable preparation which:

- contains barium sulfate;

Contains barium sulfate, wherein the barium sulfate may be of natural or synthetic origin;

Barium sulfate, wherein the barium sulfate has a particle size of 1 to 30 microns, preferably from 1 to 20 microns, more preferably from 1 to 10 microns, most preferably from 1 to 5 microns;

Contains barium sulfate, wherein the barium sulfate has a particle size of 0.1 to 8 microns, preferably from 0.15 to 5 microns, more preferably from 0.2 to 2 microns; Contains barium sulfate, the barium sulfate being untreated;

Contains barium sulfate, wherein the barium sulfate is inorganic and / or organically post-treated;

Barium sulfate containing the barium sulfate with Al ₂ O 3, TiO ₂ , ZrO ₂ , Fe ₂ Os, CeO ₂ , MnO ₂ , SiO ₂ or mixtures of two or more of these and / or the corresponding hydroxides or mixtures of two or more of these coated;

Contains barium sulfate, wherein the proportion of the inorganic coating is 1 to 50 wt .-%, preferably 5 to 30 wt .-%, in each case based on the barium sulfate used;

- Barium sulfate, wherein the barium sulfate is coated with one or more organic substances from the group of stearic acid, silicone oils, simethicones and silanes, or mixtures of two or more of these;

Contains barium sulfate, wherein the proportion of the organic coating is 1 to 20 wt .-%, preferably 2 to 10 wt .-%, in each case based on the barium sulfate used;

Barium sulfate containing the barium sulfate with inorganic substances, preferably inorganic oxides such as Al ₂ θ3, TiO ₂ , ZrO ₂ , Fe ₂ θ3, CeO ₂ , MnO ₂ , SiO ₂ or mixtures of two or more of these and / or the corresponding hydroxides or mixtures of two or more of these are mixed;

Contains barium sulfate, wherein the proportion of inorganic additives is 1 to 50 wt .-%, preferably 5 to 30 wt .-%, in each case based on the barium sulfate used; Barium sulfate, wherein the barium sulfate in a use concentration of 1 to 15 wt .-%, preferably from 1 to 10 wt .-%, particularly preferably from 1 to 6 wt .-%, most preferably from 1 to 4 wt. %, in particular from 1 to 3 wt .-% in the preparation is included;

Contains barium sulfate, wherein the barium sulfate in a use concentration of 6 to 15 wt .-%, preferably from 6 to 12 wt .-%, particularly preferably from 7 to 10 wt .-%. contained in the preparation;

- Barium sulfate, wherein the preparation is based on an emulsion;

- Barium sulfate, wherein the preparation is based on an oil-in-water formulation;

- Barium sulfate, wherein the preparation is based on a water-in-oil formulation;

Barium sulfate, the preparation comprising a cosmetic or dermatological formulation, preferably a daily care product, an anti-wrinkle preparation, an eye cream, a sunscreen care product

Personal care product, an anti-cellulite product, a make-up formulation, a foundation and / or a powder;

- Barium sulfate, wherein the preparation contains a UV-protecting agent;

a process for the production of a preparation wherein barium sulfate is added to the components known per se for conventional cosmetic preparations;

Use of the preparations according to the invention as a cosmetic or dermatological formulation, preferably as day care product, anti-wrinkle preparation, eye cream, sunscreen care product, personal care product, anti-cellulite product, in make-up formulation, foundation and / or powder. Use of barium sulfate in topically applicable preparations, preferably cosmetic or dermatological formulations, more preferably in

Day care products, anti-wrinkle preparations, in eye creams, in

Sunscreen care products, personal care products, anti-cellulite products, make-up formulations, foundations and / or powders.

The invention is explained below by examples without limiting it to:

Example 1 Production and Composition of a Barium Sulfate Coated with TiOOH and Al (OH) ₃

200 g of BaSO ₄ with an average particle size of 4 μm are stirred with a bar stirrer in about one liter of TE water (TE: partially desalted). The suspension is heated to 80 ⁰ C. 192 ml of an aqueous titanyl sulfate solution containing sulfuric acid (42.75 g of TiOSO ₄ , 51, 8 g of H ₂ SO ₄ ) are added slowly (5 ml / min) with stirring. The pH is maintained at a constant pH = 7 during the addition with the aid of 25% sodium hydroxide solution.

Subsequently, 66.7 ml of sodium aluminate solution (content equivalent to 300 g of Al ₂ O ₃ per liter) are added slowly at constant pH (5 ml / min). The pH is maintained at a constant pH = 7 with the aid of sulfuric acid during the addition. After the addition is stirred at pH = 7 and 8O ⁰ C for two hours. Thereafter, the material is filtered off with suction, the filter cake washed to a Filtratleitfähigkeit below 100 μS / cm and dried at 105 ° C in a drying oven.

Subsequently, the product can be tempered for 30 minutes in a muffle furnace at 800 ⁰ C.

Composition of the product (% by weight): 79.3% BaSO ₄ , 8.6% TiOOH, 12.1% Al (OH) ₃ . Example 2 Preparation and Composition of a Barium Sulfate Coated with TiOOH, Al (0H) ₃ and Fe (0H) ₃

200 g of BaSO ₄ with an average particle size of 4 μm are stirred in about one liter of TE water using a bar stirrer. The suspension is heated to 80.degree. 192 ml of an aqueous titanyl sulfate solution containing sulfuric acid (42.75 g of TiOSO ₄ , 51.8 g of H ₂ SO ₄ ) are added slowly (5 ml / min) with stirring. The pH is maintained at a constant pH = 7 during the addition with the aid of 25% sodium hydroxide solution. Thereafter, 75.9 ml of an aqueous FeCl ₃ solution (content equivalent to 200 g of FeCb per liter) are added slowly (5 ml / min) with stirring. The pH is again kept at a constant pH = 7 with the aid of 25% sodium hydroxide solution during the addition.

After the FeCl ₃ solution has been added, 66.7 ml of sodium aluminate solution (content equivalent to 300 g of Al ₂ O ₃ per liter) are added slowly at constant pH (5 ml / min). The pH is maintained at a constant pH = 7 with the aid of sulfuric acid during the addition. After the addition is stirred at pH = 7 and 8O ⁰ C for two hours. Thereafter, the material is filtered off with suction, the filter cake washed to a Filtratleitfähigkeit below 100 μS / cm and dried at 105 ⁰ C in a drying oven.

Composition of the product (% by weight):

76.3% BaSO ₄ , 8.2% TiOOH, 1 1, 7% Al (OH) ₃ , 3.8% Fe (OH) ₃ .

Example 3 Preparation and Composition of a TiO ₂ and Al (OH) ₃ Coated Barium Sulfate

200 g of BaSO ₄ with an average particle size of 4 μm are stirred in about one liter of TE water using a bar stirrer. The suspension is at 8O ⁰ C. heated. 100 ml of an aqueous TiO ₂ suspension (content corresponds to 200 g per liter with an average primary grain size of TiO ₂ of 35 nm) are added slowly (5 ml / min) with stirring. Subsequently, 66.7 ml of sodium aluminate solution (content equivalent to 300 g of Al ₂ O 3 per liter) are added slowly at constant pH (5 ml / min). The pH is maintained at a constant pH = 7 with the aid of sulfuric acid during the addition. After the addition is stirred at pH = 7 and 8O ⁰ C for two hours. Thereafter, the material is filtered off with suction, the filter cake washed to a Filtratleitfähigkeit below 100 μS / cm and dried at 105 ⁰ C in a drying oven.

Composition of the product (% by weight): 79.8% BaSO ₄ , 8.0% TiO ₂ , 12.2% Al (OH) ₃ .

Example 4 Preparation and Composition of a Barium Sulfate Coated with TiO ₂ , Al (OH) ₃ and Fe (OH) ₃

200 g of BaSO ₄ with an average particle size of 4 μm are stirred in about one liter of TE water using a bar stirrer. The suspension is heated to 8O ⁰ C. 100 ml of an aqueous TiO ₂ suspension (content corresponds to 200 g per liter with an average primary particle size of TiO ₂ of 35 nm) are added slowly (5 ml / min) with stirring. Thereafter, 75.9 ml of an aqueous FeCl ₃ solution

(Content equivalent to 200 g FeCl ₃ per liter) slowly (5 ml / min) added with stirring. The pH is adjusted by means of 25% sodium hydroxide solution during the

Addition kept at a constant pH = 7.

After the FeCl ₃ solution has been added, 66.7 ml of sodium aluminate solution (content equivalent to 300 g of Al ₂ O ₃ per liter) are added slowly at constant pH (5 ml / min). The pH is maintained at a constant pH = 7 with the aid of sulfuric acid during the addition. After the addition is stirred at pH = 7 and 8O ⁰ C for two hours. Thereafter, the material is filtered off with suction, the filter cake washed to a Filtratleitfähigkeit below 100 μS / cm and dried at 105 ⁰ C in a drying oven. Composition of the product (% by weight):

76.7% BaSO ₄ , 7.7% TiO ₂ , 1 1, 7% Al (OH) ₃ , 3.8% Fe (OH) ₃ .

Example 5: Preparation and Composition with Barium Sulfates Coated with TiOOH

200 g of BaSO ₄ with an average particle size of 4 μm are stirred in about one liter of TE water using a bar stirrer. The suspension is heated to 80.degree. 192 ml of an aqueous titanyl sulfate solution containing sulfuric acid (42.75 g of TiOSO ₄ , 51, 8 g of H ₂ SO ₄ ) are added slowly (5 ml / min) with stirring. The pH is maintained at a constant pH = 7 during the addition with the aid of 25% sodium hydroxide solution.

After the addition is stirred at pH = 7 and 80 ⁰ C for two hours. Thereafter, the material is filtered off with suction, the filter cake washed to a Filtratleitfähigkeit below 100 μS / cm and dried at 105 ° C in a drying oven.

Composition of the product (% by weight): 90.2% BaSO ₄ , 9.8% TiOOH.

Example 6: Preparation and composition with TiOOH and Fe (OH) ₃ coated barium sulfate

200 g of BaSO ₄ with an average particle size of 4 μm are stirred in about one liter of TE water using a bar stirrer. The suspension is heated to 80.degree. 192 ml of an aqueous titanyl sulfate solution containing sulfuric acid (42.75 g of TiOSO ₄ , 51, 8 g of H ₂ SO ₄ ) are added slowly (5 ml / min) with stirring. The pH is maintained at a constant pH = 7 during the addition with the aid of 25% sodium hydroxide solution. Thereafter, 37.9 ml of an aqueous FeCb solution (content equivalent to 200 g of FeCb per liter) are added slowly (5 ml / min) with stirring. The pH is maintained at a constant pH = 7 during the addition with the aid of 25% sodium hydroxide solution.

Subsequently, the product can be tempered for 30 minutes in a muffle furnace at 700 ⁰ C.

Composition of the product (% by weight): 88.3% BaSO ₄ , 9.5% TiOOH, 2.2% Fe (OH) ₃ .

Example 7: Composition and preparation of an oil-on-water-based anti-wrinkle cream (in% by weight)

Component Ingredient proportion

I Caprylylmethicone 1, 00%

Cetearyl alcohol 0.50%

Cetyl phosphate 1, 00%

Glyceryl stearate 0.50%

Isopropyl palmitate 7.00%

Mineral oil 8.00%

II Ammonium acryloyl dimethyl taurate / VP 1, 20% copolymer

III barium sulfate 5.00%

IV glycerin 5.00%

Sodium lauroylglutamate 0.50%

Add water to 100.00%

V tocopheryl acetate 1, 00%

Perfume as needed

Preservatives as needed

Component I is melted at about 80 ° C. Then component II is stirred into I. Thereafter, component III is dispersed in the heat in the mixture of component I and II. Immediately afterwards, component IV is added; it is stirred until the approach has cooled. Finally, component V is stirred into the batch at 30 ° C.

Claims

claims

1 . Preparation of components for topical applications, which contains barium sulfate, characterized in that the preparation barium sulfate a particle size of 1 to 30 microns, preferably from 1 to 20 microns, more preferably from 1 to 10 microns, most preferably from 1 to 5 microns ,

2. Preparation of components for topical applications containing barium sulfate, characterized in that the barium sulfate has a particle size of 0.1 to 20 microns, preferably from 0.15 to 15 microns, more preferably from 0.2 to 2 microns.

3. Preparation according to claim 1 or 2, characterized in that the barium sulfate may be natural or synthetic origin.

4. Preparation according to at least one of the preceding claims, characterized in that the barium sulfate is inorganic and / or organically post-treated.

5. A preparation according to at least one of the preceding claims, characterized in that the barium sulfate with Al ₂ O 3, TiO ₂ , ZrO ₂ , Fe ₂ Os, CeO ₂ , MnO ₂ , SiO ₂ or mixtures of two or more of these and / or the corresponding hydroxides or mixtures of two or more of these is coated.

6. Preparation according to at least one of the preceding claims, characterized in that the proportion of the inorganic coating is 1 to 50 wt .-%, preferably 5 to 30 wt .-%, in each case based on the barium sulfate used.

7. Preparation according to at least one of the preceding claims, characterized in that the barium sulfate is coated with one or more organic substances from the group of stearic acid, silicone oils, simethicones and silanes or mixtures of two or more of these.

8. Preparation according to at least one of the preceding claims, characterized in that the proportion of the organic coating is 1 to 20 wt .-%, preferably 2 to 10 wt .-%, in each case based on the barium sulfate used.

9. Preparation according to at least one of the preceding claims, characterized in that the barium sulphate with inorganic materials, preferably inorganic oxides such as Al ₂ O 3, TiO _2, ZrO _2, Fe ₂ O, CeO _2, MnO _2, SiO _2, or

Mixtures two or more of these and / or the corresponding

Hydroxides or mixtures of two or more of these is mixed.

10. Preparation according to at least one of the preceding claims, characterized in that the proportion of inorganic additives is 1 to 50 wt .-%, preferably 5 to 30 wt .-%, in each case based on the barium sulfate used.

1 1. Preparation according to at least one of the preceding claims, characterized in that the barium sulfate is untreated.

12. Preparation according to at least one of the preceding claims, characterized in that the barium sulfate in a use concentration of 1 to 15 wt .-%, preferably from 1 to 10 wt .-%, particularly preferably from 1 to 6 wt .-%, completely particularly preferably from 1 to 4 wt .-%, in particular from 1 to 3 wt .-% is contained in the preparation.

13. Preparation according to at least one of the preceding claims, characterized in that the barium sulfate in a use concentration of 6 to 15 wt .-%, preferably from 6 to 12 wt .-%, particularly preferably from 7 to 10 wt .-%. contained in the preparation.

14. Preparation according to at least one of the preceding claims, characterized in that the preparation is based on an emulsion.

15. Preparation according to at least one of the preceding claims, characterized in that the preparation is based on an oil-in-water formulation.

16. Preparation according to at least one of the preceding claims, characterized in that the preparation is based on a water-in-oil formulation.

17. Preparation according to at least one of the preceding claims, characterized in that the preparation is a cosmetic or dermatological formulation, particularly preferably a daily care product, an anti-wrinkle formulation.

Preparation, an eye cream, a sunscreen care product, a personal care product, an anti-cellulite product, a make-up formulation, a foundation and / or a powder.

18. Preparation according to at least one of the preceding claims, characterized in that the preparation contains a UV protection agent.

19. A process for the preparation of a preparation according to at least one of the preceding claims, characterized in that the known per se components for conventional cosmetic preparations barium sulfate is added.

20. Use of a preparation according to at least one of the preceding claims as a cosmetic or dermatological formulation, preferably as Day care product, anti-wrinkle preparation, eye cream, sunscreen care product, personal care product, anti-cellulite product, in make-up formulation, foundation and / or powder.

Use of barium sulfate in a preparation according to at least one of the preceding claims in cosmetic or dermatological formulations daily care products, particularly preferably in anti-wrinkle preparations, in eye creams, in sunscreen care products, in personal care products, in anti-cellulite products, in make-up formulations , in foundations and / or in powders.