SURFACE-TREATED CALCIUM CARBONATE WITH IMPROVED STABILITY IN ENVIRONMENTS WITH A PH OF 4.5 TO 7

Abstract

The present invention relates to a process for producing a surface-treated calcium carbonate with improved stability in environments with a pH of 4.5 to 7, wherein calcium carbonate, at least one acid having a pK.sub.a value from 0 to 8, when measured at 20 C., and at least one conjugate base are brought into contact to form surface-treated calcium carbonate.

Claims

1. A process for producing a surface-treated calcium carbonate with improved stability in environments with a pH of 4.5 to 7, wherein the process comprises the steps of: i) providing calcium carbonate, ii) providing at least one acid having a pK.sub.a value from 0 to 8, when measured at 20 C., iii) providing at least one conjugate base, iv) contacting the calcium carbonate of step i), the at least one acid of step ii), and the at least one conjugate base of step iii) to form surface-treated calcium carbonate, wherein the at least one acid of step ii) and/or the at least one conjugate base of step iii) are provided in form of an aqueous solution.

2. The process of claim 1, wherein step iv) comprises the steps of: a1) contacting the calcium carbonate of step i) and the at least one acid of step ii) to form a pre-treated calcium carbonate, and a2) contacting the pre-treated calcium carbonate of step a1) with the at least one conjugate base of step iii) to form surface-treated calcium carbonate, wherein at least the at least one acid of step ii) is provided in form of an aqueous solution.

3. The process of claim 1, wherein step iv) comprises the steps of: b1) contacting the calcium carbonate of step i) and the at least one conjugate base of step iii) to form a pre-treated calcium carbonate, and b2) contacting the pre-treated calcium carbonate of step b1) with the at least one acid of step ii) to form surface-treated calcium carbonate, wherein at least the at least one conjugate base of step iii) is provided in form of an aqueous solution.

4. The process of claim 1, wherein the at least one acid of step ii) and the at least one conjugate base of step iii) are provided together in form of an aqueous buffer solution, and in step iv) the calcium carbonate of step i) is contacted with the aqueous buffer solution to form surface-treated calcium carbonate.

5. The process of claim 4, wherein step iv) comprises the steps of: c1) mixing the calcium carbonate of step i), the aqueous buffer solution, and optionally water, to form an aqueous suspension of surface-treated calcium carbonate, and c2) separating the surface-treated calcium carbonate from the aqueous suspension obtained from step c1).

6. The process of claim 1, wherein the calcium carbonate of step i) is natural ground calcium carbonate, precipitated calcium carbonate, dolomite, agglomerates or aggregates thereof, or a mixture of the aforementioned materials, and preferably natural ground calcium carbonate.

7. The process of claim 1, wherein the calcium carbonate of step i) is in form of particles having a volume determined median particle size d.sub.50 from 1 to 1 500 m, preferably from 25 to 1 400 m, more preferably from 100 from 1 200 m, even more preferably from 200 to 1 000 m, and most preferably from 300 to 800 m.

8. The process of claim 1, wherein the at least one acid of step ii) is selected from the group consisting of phosphoric acid, citric acid, sulphurous acid, boric acid, acetic acid, tartaric acid, formic acid, propanoic acid, oxalic acid, phosphonic acid, their acidic salts, and mixtures thereof, preferably selected from the group consisting of phosphoric acid, citric acid, tartaric acid, oxalic acid, their acidic salts, and mixtures thereof, and most preferably selected from the group consisting of phosphoric acid, citric acid, their acidic salts, and mixtures thereof.

9. The process of claim 1, wherein the at least one conjugate base of step iii) is an alkali metal salt and/or alkaline earth metal salt of an acid having a pK.sub.a value from 0 to 8, when measured at 20 C., preferably the at least one conjugate base of step iii) is an alkali metal salt and/or alkaline earth metal salt of an acid selected from the group consisting of phosphoric acid, citric acid, sulphurous acid, boric acid, acetic acid, tartaric acid, formic acid, propanoic acid, oxalic acid, phosphonic acid, and mixtures thereof, more preferably the at least one conjugate base of step iii) is a sodium and/or potassium salt of an acid selected from the group consisting of phosphoric acid, citric acid, sulphurous acid, boric acid, acetic acid, tartaric acid, formic acid, propanoic acid, oxalic acid, phosphonic acid, and mixtures thereof, and most preferably the at least one conjugate base of step iii) is a sodium and/or potassium salt of an acid selected from the group consisting of phosphoric acid, citric acid, and mixtures thereof.

10. The process of claim 4, wherein the aqueous buffer solution has a pH value from 4.0 to 7.5, preferably from 4.5 to 6.0, and most preferably from 4.8 to 5.5.

11. The process of claim 4, wherein the aqueous buffer solution has a concentration from 0.01 mol/kg to 2 mol/kg, preferably from 0.04 to 1.0 mol/kg, more preferably from 0.06 to 0.5 mol/kg, even more preferably from 0.07 to 0.4 mol/kg, and most preferably from 0.08 to 0.2 mol/kg.

12. The process of claim 4, wherein the calcium carbonate of step i) is in form of particles having a specific BET surface area in the range of >0 to 5 m.sup.2/g, preferably in the range of >0 to 2 m.sup.2/g, and more preferably in the range of >0 to 1 m.sup.2/g.

13. The process of claim 1, further comprising a step v) of drying the surface-treated calcium carbonate.

14. A suspension of a surface-treated calcium carbonate with improved stability in environments with a pH of 4.5 to 7 obtainable by a process according to claim 1.

15. The suspension of a surface-treated calcium carbonate of claim 14, wherein the surface-treated calcium carbonate has a reduced acid consumption per hour at pH 5 and pH 6 when treated with acetic acid, the reduction being at least 25%, more preferably at least 50%, and most preferably at least 70%.

16. The suspension of a surface-treated calcium carbonate of claim 14, wherein the surface-treated calcium carbonate is in form of particles having a specific BET surface area in the range of >0 to 5 m.sup.2/g, preferably in the range of >0 to 2 m.sup.2/g, and more preferably in the range of >0 to 1.6 m.sup.2/g.

17. A dried surface-treated calcium carbonate with improved stability in environments with a pH of 4.5 to 7 obtainable by a process according claim 13.

18. The dried surface-treated calcium carbonate of claim 17, wherein the surface-treated calcium carbonate has a reduced acid consumption per hour at pH 5 and pH 6 when treated with acetic acid, the reduction being at least 25%, more preferably at least 50%, and most preferably at least 70%.

19. The dried surface-treated calcium carbonate of claim 17, wherein the surface-treated calcium carbonate is in form of particles having a specific BET surface area in the range of >0 to 5 m.sup.2/g, preferably in the range of >0 to 2 m.sup.2/g, and more preferably in the range of >0 to 1.6 m.sup.2/g.

20. An abrasive cleaning composition comprising a suspension of a surface-treated calcium carbonate according to claim 14 or a dried surface-treated calcium carbonate thereof.

21. Use of a suspension of surface-treated calcium carbonate according to claim 14 as abrasive material, preferably as abrasive material for cleaning application.

22. Use of a dried surface-treated calcium carbonate according to claim 17 as abrasive material, preferably as abrasive material for cosmetic application and/or cleaning application, more preferably as abrasive material for cosmetic application, and most preferably as abrasive material for topical skin application.

23. Use of an abrasive cleaning composition according to claim 20 for cleaning a surface, preferably for cleaning an animate surface, and more preferably for cleaning an animate surface selected from the group consisting of human skin, animal skin, human hair, animal hair, and tissues of the oral cavity such as teeth, gums, tongue or buccal surfaces.

Description

EXAMPLES

1. Measurement Methods

[0193] In the following, measurement methods implemented in the examples are described.

[0194] pH Value

[0195] a) Normal pH Measurement

[0196] The pH of a suspension or solution was measured at 25 C. using a Mettler Toledo Seven Easy pH meter and a Mettler Toledo InLab Expert Pro pH electrode. A three point calibration (according to the segment method) of the instrument was first made using commercially available buffer solutions having pH values of 4, 7 and 10 at 20 C. (from Sigma-Aldrich Corp., USA). The reported pH values are the endpoint values detected by the instrument (the endpoint was when the measured signal differed by less than 0.1 mV from the average over the last 6 seconds).

[0197] b) pH Measurement with Regard to Stability at pH 5 and 6

[0198] The pH of a suspension or solution was measured at 25 C. using a Mettler Toledo DL58 Titrator and a Mettler Toledo DG 115-SC electrode. A three point calibration (according to the segment method) of the instrument was first made using commercially available buffer solutions having pH values of 4.01, 7.00 and 9.21 at 20 C. (Duracal Buffers from Hamilton, Switzerland). The reported pH values are the endpoint values detected by the instrument (the endpoint was when the measured signal differed by less than 0.1 mV from the average over the last 2.5 seconds).

[0199] BET Specific Surface Area (SSA)

[0200] The BET specific surface area is measured via the BET process according to ISO 9277 using nitrogen, following conditioning of the sample by heating at 250 C. for a period of 30 minutes. Prior to such measurements, the sample is filtered within a Buchner funnel, rinsed with deionised water and dried at 110 C. in an oven for at least 12 hours.

[0201] Particle Size Distribution

[0202] The weight median particle size of all particulate materials, e.g. natural ground or precipitated calcium carbonate, was determined by the sedimentation method, which is an analysis of sedimentation behaviour in a gravimetric field. The measurement was made with a Sedigraph 5100, Micromeritics Instrument Corporation. The method and the instrument are known to the skilled person and are commonly used to determine grain size of fillers and pigments in the range from 0.1 to 5 m. The measurement was carried out in an aqueous solution of 0.1 wt.-% Na.sub.4P.sub.2O.sub.7. The samples are dispersed using a high speed stirrer and supersonicated.

[0203] The volume determined median particle size d.sub.50 of calcium carbonate and surface-treated calcium carbonate was evaluated using a Malvern Mastersizer 2000 Laser Diffraction System (Malvern Instruments Plc., Great Britain), using the Fraunhofer light scattering approximation. The method and instrument are known to the skilled person are commonly used to determine particle sizes of fillers and other particulate materials of >5 m. Although it is preferable to use the Sedigraph method for particle sizes of less than 5 m it is also possible to do volume based particles size determination using the Malvern Mastersizer for particle sizes as low as 1 m. The samples were dispersed using a high speed stirrer and in the presence of supersonics.

2. Materials

[0204] For the present invention the following buffer solutions were tested:

[0205] It has to be noted that for the preparation of each buffer solution deionized water was used.

[0206] Buffers Used in Lab-Scale Trials

[0207] A: Phosphate Buffer

[0208] 999.2 g of a NaH.sub.2PO.sub.4 solution (0.1 mol/kg) and 20.8 g Na.sub.2HPO.sub.4 solution (0.1 mol/kg) were mixed. The final pH of this buffer was 5.0 and the total phosphate ionic concentration was 0.1 mol/kg.

[0209] B: Phosphate Citrate Buffer

[0210] 257.3 g Na.sub.2HPO.sub.4 solution (0.2 mol/kg), 269.1 g citric acid solution (0.1 mol/kg) and 492.7 g deionized water were mixed. The final pH of this buffer was 5.0, the total phosphate ionic concentration was 0.05 mol/kg, and the total citrate ionic concentration was 0.026 mol/kg.

[0211] C: Citrate Buffer

[0212] A first solution was prepared by placing 1 000 g sodium dihydrogen citrate solution (0.1 mol/kg) in a beaker, and adding 48.2 g trisodium citrate to the beaker while stirring with a magnetic stirring bar. The total citrate concentration of said first solution was 0.27 mol/kg.

[0213] 365 g of said first solution and 635 g deionized water were combined and mixed. Then a 0.1 mol/kg citric acid solution was added until a final pH of 5.0 was reached. The final buffer solution had a total citrate ion concentration of 0.1 mol/kg.

[0214] The following chemicals were used to prepare the above solutions: Sodium di-hydrogen phosphate monohydrate (NaH.sub.2PO.sub.4.H.sub.2O, Merck KGaG), di-sodium hydrogen phosphate di-hydrate (Na.sub.2HPO.sub.4.2H.sub.2O, Merck KGaA), citric acid anhydrous (H.sub.3C.sub.6H.sub.5O.sub.7, Sigma Aldrich), sodium di-hydrogen citrate anhydrous (NaH.sub.2C.sub.6H.sub.5O.sub.7, Sigma Aldrich) and trisodium citrate di-hydrate (Na.sub.3C.sub.6H.sub.5O.sub.7.2H.sub.2O, Sigma Aldrich).

[0215] Buffers Used in Pilot-Scale Trials

[0216] The following buffer solutions were tested in pilot-scale trials. Table 1 lists the amounts of the used compounds as well as the resulting ionic concentrations. All compounds were purchased from Sigma Aldrich.

TABLE-US-00001 TABLE 1 Compounds used for preparation of different buffers and resulting ionic concentrations and pH. Phosphate Phosphate Phosphate citrate citrate citrate Phosphate Citrate buffer D buffer E buffer F buffer G buffer H Additive C.sub.6H.sub.5Na.sub.3O.sub.72H.sub.2O g 468 468 780 0 357 Masses KH.sub.2PO.sub.4 g 233 233 388 2645 0 H.sub.3PO.sub.4 (30%) g 431 431 718 0 0 NaOH g 0 0 0 45.3 0 C.sub.6H.sub.8O.sub.7 g 0 0 0 0 82.5 Solution Conditions Water-total kg 29.2 17.2 10.5 15.6 19.6 at treatment Solids CaCO.sub.3 % 34.0% 46.6% 70.4% 61.6% 56.1% Dose C.sub.6H.sub.5O.sub.7.sup.3 % 2.0% 2.0% 2.0% 0.0% 1.2% Dose PO.sub.4.sup.3 % 1.9% 1.9% 1.9% 7.4% 0.0% [C.sub.6H.sub.5O.sub.7.sup.3] mmol/kg 55 112 482 0 113 [PO.sub.4.sup.3] mmol/kg 104 214 918 1837 0 pH 5.6 5.1 4.8 4.9 5.3

[0217] Calcium Carbonate

[0218] The calcium carbonate used was a natural ground calcium carbonate from Karabiga, Turkey, having a d.sub.10 (volume determined) of 200 m, a d.sub.20 (volume determined) of 243 m, a d.sub.50 (volume determined) of 362 m, a d.sub.90 (volume determined) of 640 m, and a d.sub.98 (volume determined) of 811 m), and a BET specific surface area less than 1.0.

3. Examples

Example 1APreparation of Surface-Treated Calcium CarbonateLab-Scale

[0219] Three samples of surface-treated calcium carbonate were prepared by treating the calcium carbonate with any one of the three prepared buffer solutions as follows:

[0220] 1 000 g buffer solution was added to a beaker. Under stirring 550 g calcium carbonate was added and the mixture was stirred for 5 minutes.

[0221] After letting the mixture sit for 20 to 24 hours, the pH of the mixture was measured. The measured pH values are given in Table 2 below. Then, the mixture was filtered through a 100 m sieve. The obtained residue on the sieve was washed with approximately 500 g of tap water in a beaker for about half a minute and the mixture was filtered again. Then the residue obtained on the sieve was dried in an oven at 90 C. over night.

TABLE-US-00002 TABLE 2 pH values of solution after preparation of surface-treated calcium carbonate. BET Sample Buffer solution pH value [m.sup.2/g] 1 A 6.8 1.5 2 B 6.8 <1.0 3 C 8.0 <1.0

Example 1BPreparation of Surface-Treated Calcium CarbonatePilot-Scale

[0222] Sample 4

[0223] 30 kg of phosphate citrate buffer solution D was used. This solution was then added to kg of the above-mentioned dry calcium carbonate in a ploughshare mixer. Concentrations of the solution were such that the dose of citrate ion on calcium carbonate was 2.0% and the dose of phosphate ion on calcium carbonate was 1.9%. This slurry was then mixed for 10 minutes and emptied into a drum. One sample, T0, taken immediately after mixing was sieved at 106 m and was dried at 115 C., and a second sample, T1, was left overnight to mature, after which it was sieved at 106 m and was dried at 115 C.

[0224] Sample 5

[0225] 15 kg of the above-mentioned calcium carbonate was wet sieved at 140 m to remove the fine material and was added to a ploughshare mixer. The final wet-sieved sample had approximately 3 kg water. 15 kg of phosphate citrate buffer solution E was used. This solution was then added to the wet-sieved calcium carbonate in the ploughshare mixer. Concentrations of the solution were such that the dose of citrate ion on calcium carbonate was 2.0% and the dose of phosphate ion on calcium carbonate was 1.9%. This slurry was then mixed for 10 minutes and emptied into a drum. One sample, T0, taken immediately after mixing was sieved at 106 m and was dried at 115 C., and a second sample, T1, was left overnight to mature, after which it was sieved at 106 m and was dried at 115 C.

[0226] Sample 6

[0227] 25 kg of the above-mentioned calcium carbonate was wet sieved at 140 m to remove the fine material and was added to a ploughshare mixer. The final wet-sieved sample had approximately 5 kg of water. 5 kg of phosphate citrate buffer solution F was used. This solution was then added to the wet-sieved calcium carbonate in the ploughshare mixer. Concentrations of the solution were such that the dose of citrate ion on calcium carbonate was 2.0% and the dose of phosphate ion on calcium carbonate was 1.9%. This slurry was then mixed for 10 minutes and emptied into a drum. One sample, T0, taken immediately after mixing was sieved at 106 m and was dried at 115 C., and a second sample, T1, was left overnight to mature, after which it was sieved at 106 m and was dried at 115 C.

[0228] Sample 7

[0229] 25 kg of the above-mentioned calcium carbonate was wet sieved at 140 m to remove the fine material and was added to a ploughshare mixer. The final wet-sieved sample had approximately 11 kg of water. 5 kg of phosphate buffer solution G was used. This solution was then added to the wet-sieved calcium carbonate in the ploughshare mixer. Concentration of the solution was such that the dose of phosphate ion on calcium carbonate was 7.4%. This slurry was then mixed for 10 minutes and emptied into a drum. One sample, T0, taken immediately after mixing was sieved at 106 m and was dried at 115 C., and a second sample, T1, was left overnight to mature, after which it was sieved at 106 m and was dried at 115 C. Samples were taken both with and without a washing step after treatment, but before drying.

[0230] Sample 8

[0231] 25 kg of the above-mentioned calcium carbonate was wet sieved at 140 m to remove the fine material and was added to a ploughshare mixer. The final wet-sieved sample had approximately 5 kg of water. 15 kg of citrate buffer solution H was used. This solution was then added to the wet-sieved calcium carbonate in the ploughshare mixer. Concentration of the solution was such that the dose of citrate ion on calcium carbonate was 1.2%. This slurry was then mixed for 10 minutes and emptied into a drum. One sample, T0, taken immediately after mixing was sieved at 106 m and was dried at 115 C., and a second sample, T1, was left overnight to mature, after which it was sieved at 106 m and was dried at 115 C.

Example 2AStability of Surface-Treated Calcium CarbonateLab-Scale

[0232] The samples prepared according to Example 1A were analyzed with regard to their stability under acidic conditions at pH 5 and pH 6 by titrating the samples with acetic acid (2.0 mol/l). The untreated calcium carbonate was also analyzed as comparative sample.

[0233] Stability at pH 5

[0234] A 2.0 mol/l solution of acetic acid was prepared from concentrated acetic acid (from Sigma-Aldrich, CAS No. 64-19-7, puriss. 99-100%).

[0235] 0.9 to 1.1 g of the sample was weighted into a plastic cup, and 100 ml of an ethanol (A15-A ethanol absolutus from Alcosuisse)-water mixture (60/40 v/v) was added.

[0236] The titration of the sample was performed in triplicate with the prepared acetic acid solution over time in order to reach a pH value of 5.0 with a control band of 0.5. The titration was performed over a time period of 60 minutes.

[0237] Stability at pH 6

[0238] A 0.1 mol/l solution of acetic acid was prepared from concentrated acetic acid (from Sigma-Aldrich, CAS No. 64-19-7, puriss. 99-100%).

[0239] Exactly 1.2 g of the sample was weighted in a plastic cup (accuracy 0.1 mg), and 100 ml of an ethanol (A15-A ethanol absolutus from Alcosuisse)-water mixture (60/40 v/v) was added.

[0240] The titration of the sample was performed in triplicate with the prepared acetic acid solution over time in order to reach a pH value of 6.0 with a control band of 0.1. The titration was performed over a time period of 60 minutes.

[0241] The final results are listed in the following Table 2 (results at pH 5) and Table 3 (results at pH 6). The results given in Tables 3 and 4 show the acid consumption per hour, measured between 15 and 60 minutes.

TABLE-US-00003 TABLE 3 Acid stability at pH 5. Acid consumption Reduction of per hour acid consumption [mmol acetic per hour [%] Sample acid/kg CaCO.sub.3] [(a.sub.n/b)*100] with n = 1, 2, 3 Calcium carbonate 10 605 223 (comparative) (b) Sample 1 (a.sub.1) 2 861 168 73 Sample 2 (a.sub.2) 1 973 41 81 Sample 3 (a.sub.3) 2 232 109 79

TABLE-US-00004 TABLE 4 Acid stability at pH 6. Acid consumption Reduction of per hour acid consumption [mmol acetic per hour [%] Sample acid/kg CaCO.sub.3] [(a.sub.n/b)*100] with n = 1, 2, 3 Calcium carbonate 399 17 (comparative) (b) Sample 1 (a.sub.1) 124 5 69 Sample 2 (a.sub.2) 27 2 93 Sample 3 (a.sub.3) 35 6 91

[0242] As can be seen from the above results, both at pH 5 and pH 6, the inventive surface-treated calcium carbonate samples 1 to 3 showed less acid consumption per hour, and, thus, an improved acid stability compared to the comparative untreated calcium carbonate sample.

Example 2BStability of Surface-Treated Calcium CarbonatePilot-Scale

[0243] The samples prepared according to Example 1B were analyzed with regard to their stability under acidic conditions at pH 5 by titrating the samples with acetic acid (1.0 mol/l). The untreated calcium carbonate was also analyzed as comparative sample.

[0244] Stability at pH 5

[0245] A 1.0 mol/l solution of acetic acid was prepared from concentrated acetic acid (from Sigma-Aldrich, CAS No. 64-19-7, puriss. 99-100%).

[0246] 0.9 to 1.1 g of the sample was weighted into a plastic cup, and 100 ml of an ethanol (A15-A ethanol absolutus from Alcosuisse)-water mixture (60/40 v/v) was added.

[0247] The titration of the sample was performed in triplicate with the prepared acetic acid solution over time in order to reach a pH value of 5.0 with a control band of 0.5. The titration was performed over a time period of 60 minutes.

[0248] The final results are listed in the following Table 5. The results given in Tables 5 show the acid consumption per hour, measured between 15 and 60 minutes.

TABLE-US-00005 TABLE 5 Acid stability at pH 5. Acid consumption per hour [mmol acetic Sample pH at t = 0 min acid/kg CaCO.sub.3] Sample 4 (T0) 6.9 5 470 302 Sample 4 (T1) 6.9 3 514 52 Sample 5 (T0) 7.3 3 462 152 Sample 5 (T1) 8.1 1 025 48 Sample 6 (T0) 8.1 1 673 221 Sample 6 (T1) 8.6 228 44 Sample 7 (T0) 6.7 3 397 126 Sample 7 (T1) 7.4 3 109 14 Sample 8 (T0) 6.9 4 670 233 Sample 8 (T1) 6.8 3 855 387

Example 3APreparation of Body Scrub Formulationsfrom Abrasive Material Prepared in Lab-Scale

[0249] Each of the different body scrub formulations was prepared according to the following guide formulation:

TABLE-US-00006 wt.-% grams A) Tegin 6.00 18.00 Isopropyl Myristate 2.00 6.00 Phenonip 1.00 3.00 Lanette O 3.00 9.00 B) Water 42.50 127.50 Panthenol 75L 1.00 3.00 Akucel 3285 0.50 1.50 C) Marlinat 242/70 20.00 60.00 EUR-AMID N2 2.00 6.00 Dow Corning HMW 2220 non-ionic Emulsion 1.00 3.00 EURONAC AMF ULTRA 1.00 3.00 D) Abrasive material 20.00 60.00 100.00 300.00

[0250] The abrasive material used in part D is listed in Table 6 below.

TABLE-US-00007 TABLE 6 Composition of prepared body scrub formulations. wt.-% abrasive material, Formulation based on total weight of formulation Abrasive material 1 20 calcium carbonate (comparative) 2 20 sample 1 3 20 sample 2 4 20 sample 3

[0251] Procedure: [0252] 1. Melt part A and B separately and keep warm at 85 C. (in a water bath) [0253] 2. Mix both parts (A and B) under intensive agitation using a Heidolph RZR 2041 mixer at 800-1 000 rpm. [0254] 3. Homogenize intensively by using a ultra Turrax (from IKA, Staufen, Germany) and cool down to room temperature under agitation using a Heidolph RZR 2041 mixer (300 to 350 rpm). [0255] 4. Add part C step by step and mix under slow agitation using Heidolph RZR 2041 mixer (150 to 200 rpm) until part C is homogenously incorporated (appr. 10-15 minutes). [0256] 5. Add part D step by step and mix under slow agitation using Heidolph RZR 2041 mixer (150 to 200 rpm; appr. 10-15 minutes) until a homogeneous mixture is obtained. The final product can be filled in glass flasks.

[0257] Table 7 below is an overview over the type of product used in the above guide formulation as well as the suppliers of these compounds.

TABLE-US-00008 Ingredients INCI Nomenclature Suppliers Tegin Glyceryl Stearate SE 1) Isopropyl myristate Isopropyl Myristate 2) Phenochem Phenoxyethanol (and) Methylparaben 3) (and) Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Lanette O Cetearyl Alcohol 4) Water dem. Aqua (Water) D-Panthenol 75 L Panthenol 5) Akucell AF 3285 Cellulose Gum 6) Marlinat 242/70 Sodium Laureth Sulfate 7) Euro-Amid N2 Cocamide MIPA (and) Laureth-4 8) Dow Corning HWM Divenyldimethicone/Dimethicone 9) 2220 non-ionic Copolymer (and) C12-C13 Pareth -3 emulsion (and) C12-C13 Pareth-23 Euronac AMF Ultra Glycol Distearate (and) 8) Cocamidopropyl Betaine Omyacare S 20-KA Calcium Carbonate 10)

[0258] Suppliers:

TABLE-US-00009 1 Hnseler AG, Switzerland 2 Omya Hamburg GmbH, Germany 3 SLI Chemicals GmbH, Germany 4 Cognis GmbH, Germany 5 DSM, Switzerland 6 Akzo Nobel Functional Chemicals BV; Netherlands 7 Sasol, Germany 8 EOC Surfactants, Belgium 9 Dow Corning Corporation, USA 10 Omya AG, Switzerland 11 Clariant (Schweiz) AG, Switzerland

Example 3BPreparation of Body Scrub Formulationsfrom Abrasive Material Prepared in Pilot-Scale (Sample 6 (T0 and T1))

[0259] Each of the different body scrub formulations was prepared according to the following guide formulation:

TABLE-US-00010 wt.-% grams A) Tegin 6.00 18.00 Isopropyl Myristate 2.00 6.00 Phenonip 1.00 3.00 Lanette O 3.00 9.00 B) Water 42.50 127.50 Panthenol 75L 1.00 3.00 Akucel 3285 0.50 1.50 C) Galaxy 70-LES 20.00 60.00 Texapon WW 100 2.00 6.00 Dow Corning HMW 2220 non-ionic Emulsion 1.00 3.00 EURONAC AMF ULTRA 1.00 3.00 D) Abrasive material 20.00 60.00 100.00 300.00

[0260] The abrasive material used in part D is listed in Table 8 below.

TABLE-US-00011 TABLE 8 Composition of prepared body scrub formulations. wt.-% abrasive material, Formulation based on total weight of formulation Abrasive material 5 20 sample 6 (T1)

[0261] Procedure: [0262] 1. Melt part A and B separately and keep warm at 85 C. (in a water bath) [0263] 2. Mix both parts (A and B) under intensive agitation using a Heidolph RZR 2041 mixer at 800-1 000 rpm. [0264] 3. Homogenize intensively by using a ultra Turrax (from IKA, Staufen, Germany) and cool down to room temperature under agitation using a Heidolph RZR 2041 mixer (300 to 350 rpm). [0265] 4. Add part C step by step and mix under slow agitation using Heidolph RZR 2041 mixer (150 to 200 rpm) until part C is homogenously incorporated (appr. 10-15 minutes). [0266] 5. Add part D step by step and mix under slow agitation using Heidolph RZR 2041 mixer (150 to 200 rpm; appr. 10-15 minutes) until a homogenous mixture is obtained. The final product can be filled in glass flasks.

[0267] Table 9 below is an overview over the type of product used in the above guide formulation as well as the suppliers of these compounds.

TABLE-US-00012 Ingredients INCI Nomenclature Suppliers Tegin Glyceryl Stearate SE 1) Isopropyl myristate Isopropyl Myristate 2) Phenochem Phenoxyethanol (and) Methylparaben 3) (and) Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Lanette O Cetearyl Alcohol 4) Water dem. Aqua (Water) D-Panthenol 75 L Panthenol 5) Akucell AF 3285 Cellulose Gum 6) Galaxy 70-LES Surfactant 2) Texapon WW 100 Blend of MIPA-Laureth Sulfate, 11) Cocamide DEA (and) Laureth-4 Dow Corning HWM Divenyldimethicone/Dimethicone 9) 2220 non-ionic emulsion Copolymer (and) C12-C13 Pareth -3 (and) C12-C13 Pareth-23 Euronac AMF Ultra Glycol Distearate (and) 8) Cocamidopropyl Betaine Omyacare S 20-KA Calcium Carbonate 10)

[0268] Suppliers:

TABLE-US-00013 1 Hnseler AG, Switzerland 2 Omya Hamburg GmbH, Germany 3 SLI Chemicals GmbH, Germany 4 Cognis GmbH, Germany 5 DSM, Switzerland 6 Akzo Nobel Functional Chemicals BV; Netherlands 7 Sasol, Germany 8 EOC Surfactants, Belgium 9 Dow Corning Corporation, USA 10 Omya AG, Switzerland 11 Clariant (Schweiz) AG, 11 BASF Switzerland

Example 4Sensory Evaluation of the Prepared Body Scrub Formulations

[0269] The sensory properties of the prepared body scrub formulations 1 to 5 were tested by applying approx. 0.075 ml of the body scrub on the hand or the finger by using a small spoon. The sensory properties of the formulations mentioned below were marked with a rating from 0 to 10, wherein 0 means not good and 10 means very good.

[0270] Evaluated Sensory Properties:

[0271] Aspect

TABLE-US-00014 Descriptor Description Separation It is a visible separation between the both phases. No separation No separation is visible between the both phases. Shiny The product reflects the light under a standard lamp. No shiny The product is mat and reflects no light under a standard lamp. Reaction Presence of a reaction between the exfoliator and the emulsion. No reaction No reaction is visible between the exfoliator and the emulsion.

[0272] Hand Movement

TABLE-US-00015 Descriptor Description Fluid When the product is placed between the thumb and index finger by applying a pressure, it has no holding, flows off the fingers and moves away from the pressure zone. No resistance is felt. Non fluid When the product is placed between the thumb and index finger by applying a pressure, there is no flow between the both fingers and it moves not away from the pressure zone. A resistance is felt. Stringy When the product is placed between the thumb and index finger and a distance is slowly applied between the both fingers, it is a continuous string. It breaks when the distance between the fingers becomes too large. Non stringy When the product is placed between the thumb and index finger and a distance is slowly applied between the both fingers, there is no string/elongated filament formed. Slippery When the product is placed between the thumb and index finger and a movement of friction is made, there is no resistance of particles. The particles make the movement easier. Non slippery When the product is placed between the thumb and index finger and a movement of friction is made, there is a resistance. The particles restrict the movement.

[0273] Spread

TABLE-US-00016 Descriptor Description Spread Between 5 and 10 turns on the hand, there is a good distribution of product. Non spread Between 5 and 10 turns on the hand, there is no repartition of product. Foaming Between 10 and 15 rotations on the hand, the product forms foam. Non foaming No foaming is visible between 10 and 15 rotations on the hand. Non Soft The particles give no pleasant sensation during the (exfoliation) application on the skin. Soft (exfoliation) A pleasant and soft exfoliation is felt during the application.

[0274] After One Minute

TABLE-US-00017 Descriptor Description Greasy When the product is placed between the thumb and index finger and a movement of friction is applied, the products have an oily aspect. Non greasy When the product is placed between the thumb and index finger and a movement of friction is applied, there is no oily aspect. Sticky By performing a pressure with index finger on the hand, there is an adhesion. Non sticky By performing a pressure with index finger on the hand, there is no adhesion.

[0275] After Two Minutes

TABLE-US-00018 Descriptor Description Penetrating The product is disappearing and no residue is detected when touching skin after two minutes. Non penetrating There can still a residue be detected on the skin after touching the skin after two minutes.

[0276] During Cleaning

TABLE-US-00019 Descriptor Description Greasy Under water, when the product is placed between the thumb and index finger and a movement of friction is applied, the products give oily aspect. Non greasy Under water, when the product is placed between the thumb and index finger and a movement of friction is applied, there is no oily aspect. Slippery Under water, by performing a pressure with index finger on the hand, there is no resistance and good sliding. Non slippery Under water, by performing a pressure with index finger on the hand, there is a resistance and no sliding on the hand.

[0277] After Rinsing and Drying

TABLE-US-00020 Descriptor Description Greasy After one minute, when the skin is drying, an oily aspect is felt when a movement is made between the thumb and index fingers. Non greasy After one minute, when the skin is drying, no oily aspect is felt when a movement is made between the thumb and index fingers. Soft After one minute, when the index finger makes a sliding on the hand, the skin is soft and a dry touch is felt. Non soft After one minute, when the index finger makes a sliding on the hand, the skin is rough and no soft touch is felt.

[0278] Results:

TABLE-US-00021 TABLE 10 Sensory properties after 6 weeks storage at room temperature. Formulation 1 2 3 4 5 Aspect Shiny 8 8 8 7 n.d. Reaction 0 0 0 0 n.d. Hand movement Fluid 4 5 5 4 0 Stringy 7 6 2 3 2 Slippery 5 7 4 4 5 Spread Foaming 5 6 6 6 8 Spread 4 7 6 6 3 Soft (exfoliation) 2 3 3 3 2 After one minute Greasy 4 6 4 3 2 Sticky 5 6 4 5 After two minutes Penetrating 8 8 8 8 8 During cleaning Greasy 6 6 6 6 3 Slippery 7 8 8 7 8 After rinsing and drying Soft 8 9 9 8 9 Greasy 5 4 4 4 1 n.d. = not determined

TABLE-US-00022 TABLE 11 Sensory properties after 6 weeks storage at 5 C. Formulation 1 2 3 4 5 Aspect Shiny 8 8 8 8 n.d. Reaction 0 0 0 0 n.d. Hand movement Fluid 4 5 4 6 0 Stringy 3 1 2 4 2 Slippery 7 8 4 6 4 Spread Foaming 6 6 6 6 6 Spread 4 7 5 5 4 Soft (exfoliation) 2 2 2 2 2 After one minute Greasy 2 3 3 2 2 Sticky 2 2 3 2 1 After two minutes Penetrating 8 8 8 8 9 During cleaning Greasy 6 7 7 7 2 Slippery 7 8 8 7 6 After rinsing and drying Soft 8 8 8 8 9 Greasy 5 2 3 4 1

TABLE-US-00023 TABLE 12 Sensory properties after 6 weeks storage at 40 C. Formulation 1 2 3 4 5 Aspect Shiny 7 8 8 8 n.d. Reaction 0 0 0 0 n.d. Hand movement Fluid 7 6 7 7 0 Stringy 3 4 3 3 2 Slippery 7 6 6 7 5 Spread Foaming 6 7 7 6 8 Spread 7 6 7 6 4 Soft (exfoliation) 4 4 4 3 2 After one minute Greasy 3 2 2 3 3 Sticky 2 4 2 2 1 After two minutes Penetrating 8 8 8 7 8 During cleaning Greasy 6 7 6 6 6 Slippery 8 8 8 7 8 After rinsing and drying Soft 8 8 8 8 8 Greasy 6 2 2 2 3

[0279] As can be gathered from the results compiled in Tables 10 to 12 above, compared to the others formulation, inventive formulation 2 showed the best slippery effect on the skin. Foaming is similar for all, but better at 5 C. and 40 C. Spread is improved for the samples stored at 40 C., because the viscosity decreased at the higher storage temperature. The best spread remains the same for the formulations 2 and 4.

[0280] After rinsing and cleaning of the skin, the evaluation of the softness (descriptor soft) gave practically the same results for all formulae. A greasy aspect leads to a noticeable difference between the samples under peeling.

[0281] It has to be noted that formulation 5 cannot be compared with formulations 1 to 4 since different components has been used as ingredient C, however, this formulation also shows a good performance.

[0282] In conclusion, all inventive body scrub formulations showed good sensory performance, confirming that the surface-treated calcium carbonate obtained by the process of the present invention is suitable for cosmetic products such as body scrub.