Abrasive cleaning composition

Abstract

The present invention relates to an abrasive cleaning composition comprising at least 6 wt.-%, based on the total weight of the composition, of a surface-reacted calcium carbonate as an abrasive material, wherein the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid.

Claims

1. An abrasive household surface cleaning composition comprising: 25 to 80 wt.-%, based on the total weight of the composition, of a surface-reacted calcium carbonate as an abrasive material, wherein the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid, the surface-reacted calcium carbonate comprises an insoluble, at least partially crystalline calcium salt of an anion of the at least one acid which is formed on the surface of the natural or synthetic calcium carbonate; and from 0.1 to 10 wt.-%, based on the total weight of the composition, of a surfactant chosen from a non-ionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, a cationic surfactant, a water-soluble salt of a C10-C18 alkyl sulphate, sodium lauryl sulphate, a sulphonated monoglyceride of a fatty acid, sodium monoglyceride sulphonate, a fatty acid amide of taurine, sodium N-methyl-N-palmitoyltauride, a fatty acid ester of isethionic acid, an aliphatic acylamide, sodium N-lauroyl sarcosinate, cocamidopropyl betaine, and any mixture thereof wherein the household surface cleaning composition is in the form of a liquid comprising a cream.

2. The composition according to claim 1, wherein the composition further comprises at least one additional abrasive material.

3. The composition according to claim 2, wherein the at least one additional abrasive material is selected from the group consisting of silica, precipitated silica, alumina, aluminosilicate, metaphosphate, tricalcium phosphate, calcium pyrophosphate, natural ground calcium carbonate, precipitated calcium carbonate, sodium bicarbonate, bentonite, kaolin, aluminium hydroxide, calcium hydrogen phosphate, hydroxylapatite, and any mixture thereof.

4. The composition according to claim 1, wherein the at least one acid is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid, and any mixture thereof.

5. The composition according to claim 1, wherein the at least one acid is phosphoric acid.

6. The composition according to claim 1, wherein the surface-reacted calcium carbonate is in form of particles having a weight median particle size d.sub.50 from 0.1 to 100 m.

7. The composition according to claim 1, wherein the surface-reacted calcium carbonate is in form of particles having a weight median particle size d.sub.50 from 0.5 to 50 m.

8. The composition according to claim 1, wherein the surface-reacted calcium carbonate is in form of particles having a weight median particle size d.sub.50 from 1 to 20 m.

9. The composition according to claim 1, wherein the surface-reacted calcium carbonate is in form of particles having a weight median particle size d.sub.50 from 2 to 10 m.

10. The composition according to claim 1, wherein the surface-reacted calcium carbonate is in form of particles having a weight median particle size d.sub.50 from 5 to 10 m.

11. The composition according to claim 1, wherein the composition is a household hard surface cleaner for cleaning refrigerators, freezers, washing machines, dryers, ovens, ceramic cook tops, bathroom fittings, dish washers, dishes, cutlery, cutting boards, pans or automobiles.

12. The composition according to claim 1, wherein the composition does not contain additional calcium carbonate-based materials.

13. The composition according to claim 1, wherein the surfactant is present in an amount from 1 to 5 wt.-%, based on the total amount of the composition.

14. The composition according to claim 1, wherein the surfactant is selected from group consisting of a water-soluble salt of a C10-C18 alkyl sulphate, sodium lauryl sulphate, a sulphonated monoglyceride of a fatty acid, sodium monoglyceride sulphonate, a fatty acid amide of taurine, sodium N-methyl-N-palmitoyltauride, a fatty acid ester of isethionic acid, an aliphatic acylamide, sodium N-lauroyl sarcosinate, and cocamidopropyl betaine.

15. The composition according to claim 1, which further comprises a solvent.

16. The composition according to claim 15, wherein the solvent is selected from the group consisting of an aliphatic alcohol, an ether having from 4 to 14 carbon atoms, a di ether having from 4 to 14 carbon atoms, a glycol, an alkoxylated glycol, a glycol ether, an alkoxylated aromatic alcohol, an aromatic alcohol, a terpene, a natural oil, and any mixture thereof.

17. The composition according to claim 1, which further comprises a detergent builder.

18. The composition according to claim 17, wherein the detergent builder is sodium tripolyphosphate or sodium aluminium silicate.

19. The composition according to claim 1, wherein the composition further comprises one or more dispersing agents, thickeners, preservatives, foaming agents, fragrances, colorants, biocides, disinfecting agents, and buffeting systems.

20. The composition according to claim 1, wherein the composition further comprises a solvent, a detergent builder, and one or more dispersing agents, thickeners, preservatives, foaming agents, fragrances, colorants, biocides, disinfecting agents, and buffering systems.

21. The composition according to claim 1, wherein the surface-reacted calcium carbonate is a reaction product of natural calcium carbonate with carbon dioxide and at the least one acid.

22. The composition according to claim 21, wherein the at least one acid is phosphoric acid.

23. The composition according to claim 1, having a pH of from 10 to 11.

24. The composition according to claim 1, wherein the surface-reacted calcium carbonate has a specific surface area of from 5 m.sup.2/g to 200 m.sup.2/g.

25. The composition according to claim 1, further comprising from 0.5 to 5 wt.-% of a thickener based on the total weight of the composition.

26. The composition according to claim 25, wherein the thickener comprises hydroxyethylcellulose, sodium carboxymethylcellulose, gum karaya, gum arabic, gum tragacanth, xanthan gum, cellulose gum, colloidal silicate, or a mixture thereof.

Description

DESCRIPTION OF THE FIGURE

(1) FIG. 1 shows a photograph of toothpaste samples according to the present invention, which were applied to a paper cloth on the day of production.

EXAMPLES

1. Measurement Methods

(2) In the following, measurement methods implemented in the examples are described.

(3) Particle Size Distribution

(4) The particle size distribution of the abrasive material particles was measured using a Sedigraph 5100 from the company Micromeritics, USA. The method and the instrument are known to the skilled person and are commonly used to determine grain size of fillers and pigments. The measurement was carried out in an aqueous solution comprising 0.1 wt.-% Na.sub.4P.sub.2O.sub.7. The samples were dispersed using a high speed stirrer and supersonics. For the measurement of dispersed samples, no further dispersing agents were added.

(5) pH Value

(6) The pH of a suspension 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).

(7) Relative Radioactive Dentin Abrasion (RDA)

(8) The relative RDA of an abrasive material was determined by using a modified washability and scrub resistance tester (Model 494, Erichsen GmbH & Co. KG, Germany) equipped with a toothbrush head and a Plexiglas surface mounted on a stainless steel plate. The toothbrush head was brushing 5000 times the Plexiglas surface, which was covered with a slurry containing abrasive cleansing particles as e.g. calcium carbonate or silica. The abrasion on the Plexiglas plates was evaluated by measuring the roughness of the surface and the depth of the scratches caused by the abrasive particles. For the measurement, an electron microscopy was used. 10 measurements were carried out per plate. The measurement points were randomly selected.

(9) For application of the slurry on the Plexiglas surface, a peristaltic pump was used to pump 200 g slurry (mixture of 15% abrasive material and a saliva replacement without enzymes) in a loop. The setting of the pump was 30, which corresponded to a pumped volume of approx. 200 ml water per minute. A silicone tube with an inner diameter of 6 mm was used. The machine was angled such that the direction for the outlet in respect to the stainless steel sample mounting plate was at an inclination of 2%, in order to have a proper slurry flow.

(10) Five plates of Plexiglas were placed in the middle of the stainless steel plate and fixed on the sides using tape (Plexiglas GS, 3 mm thickness, colour: orange 2C04, pre-cut to a size of 80 mm80 mm). Five plates were necessary to ensure always the same height for the brushes brushing the surface. Only the plate in the middle (number 3) was used for the final evaluation of the abrasion. The other plates were just used to adjust the height, and so they could be used several times.

(11) A toothbrush head (Paro, Switzerland) was placed above the middle of the stainless steel plate. All bristles of the toothbrush had the same length, were rounded and made of nylon. The fixture itself was made of stainless steel and had, including the toothbrush head, a total weight of approx. 157 g.

(12) To quantify and qualify the abrasion of the tested calcium carbonate particles, it was necessary to establish a calibration curve. To generate such a curve, the abrasion of a placebo was measured first, which was just the saliva mixture without cleansing particles. This test also took the influence of the toothbrush on the abrasion into consideration. In addition, the abrasion using the aforementioned system was measured for two silicas (Sorbosil AC 39 and Sorbosil AC 33), which are both well documented and established abrasives in the toothpaste industry. Their officially measured abrasion values (RDA) are published and known. The abrasion values obtained by the measurement described herein were then related to the published data, which made it possible to compare the data from the herein described measurements with the values obtained by the official standard method ISO 11609.

(13) The calibration curves started with the placebo at abrasion=0 and went stepwise up to an abrasion value of 180, wherein Sorbosil AC 39 had a value of 105 and Sorbosil AC 33 a value of 180.

(14) Brookfield Viscosity

(15) The Brookfield viscosity of the abrasive material particles suspension or abrasive cleaning composition was measured after one hour of production and after one minute of stirring at 20 C.2 C. at 100 rpm by the use of a Brookfield viscometer type RVT equipped with an appropriate disc spindle, for example spindle 2 to 5.

(16) Gloss Measurement

(17) The gloss measurements were carried out with the haze meter Haze-Gloss (BYK Gardener GmbH, Germany).

2. Materials

(18) MCC1: A blend of 100 parts surface-reacted calcium carbonate, based on GCC1 and phosphoric acid, and 20 parts GCC2. Properties: d.sub.50=8.6 m, d.sub.98=20.2 m, relative RDA=37, low level of abrasion.

(19) MCC2: surface-reacted calcium carbonate based on GCC2 and phosphoric acid. Properties: d.sub.50=6.3 m, d.sub.98=15.8 m, relative RDA=11, very low level of abrasion.

(20) MCC3: surface-reacted calcium carbonate based on GCC1 and phosphoric acid. Properties: d.sub.50=6.5 m, d.sub.98=16.8 m, relative RDA=61, medium level of abrasion.

(21) MCC4: surface-reacted calcium carbonate based on GCC1 and phosphoric acid. Properties: d.sub.50=3.8 m, d.sub.98=11.0 m, relative RDA=23, low level of abrasion.

(22) GCC1: natural ground calcium carbonate obtained from Orgon limestone. Properties: d.sub.50=3 m, d.sub.98=12, relative RDA=81, medium level of abrasion.

(23) GCC2: natural ground calcium carbonate obtained from Avenza marble. Properties: d.sub.50=1.7 m, d.sub.98=8.0, relative RDA=100, high level of abrasion.

(24) GCC3: natural ground calcium carbonate obtained from Avenza marble. Properties: d.sub.50=8.86 m, d.sub.98=50.0 m.

3. Examples

Example 1

Toothpaste Compositions

(25) Toothpaste samples 1 to 6 were produced according to the following procedure using the ingredients and amounts compiled in Table 1 below.

(26) Step A: Water and sorbitol were mixed in a beaker. Xanthan gum, sodium benzoate, fluorophosphate (phoskadent Na 211, BK Guilini, Germany) and sodium saccharine were mixed and the obtained mixture was added to the beaker.

(27) Step B: Surface-reacted calcium carbonate and titanium dioxide were wetted with water and subsequently added to the mixture of step A. The mixture was homogenized until a smooth mixture was obtained.

(28) Step C: The silica Sorbosil TC 15 (PQ Corporation, USA) was added to the mixture of step B under homogenizing conditions, whereby the mixture was heating up strongly. The mixture was stirred until it was cooled down to room temperature.

(29) Step D: The surfactant sodium lauryl sulphate was added in form of a 25% solution to the mixture of step C under slow agitation.

(30) Step E: 0.8 wt.-% (2.4 g) spearmint flavour was added to the mixture of step D.

(31) The phase stability was evaluated by visual inspection, and the pH value measurements were carried out as described above. The mouthfeel was evaluated by brushing teeth with the toothpaste samples. The samples were tested on the day of production. The results are compiled in Table 2 below, which shows that all samples were stable and had a good texture and a smooth surface. Furthermore, all samples had an acceptable pH.

(32) TABLE-US-00001 TABLE 1 Ingredients and amounts of toothpaste samples 1 to 6. The percentages refer to weight percentages based on the total weight of the composition. Ingredients Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sorbitol 70% 28.0% 28.0% 25.0% 30.0% 31.0% 31.0% (84.0 g) (84.0 g) (75.0 g) (90.0 g) (93.0 g) (93.0 g) Water 34.3% 32.8% 32.3% 27.4% 30.0% 30.0% (102.9 g) (98.4 g) (96.9 g) (82.2 g) (90.0 g) (90.0 g) Phoskadent 1.1% 1.1% 1.1% 1.1% 1.1% 1.1% Na 211 (3.3 g) (3.3 g) (3.3 g) (3.3 g) (3.3 g) (3.3 g) Xanthan gum 0.8% 0.8% 0.8% 0.8% 0.8% 0.8% (2.4 g) (2.4 g) (2.4 g) (2.4 g) (2.4 g) (2.4 g) Sodium 0.1% 0.1% 0.1% 0.2% 0.1% 0.1% saccharin (0.3 g) (0.3 g) (0.3 g) (0.6 g) (0.3 g) (0.3 g) Sodium 0.2% 0.2% 0.2% benzoate (0.6 g) (0.6 g) (0.6 g) MCC 1 35.0% (105.0 g) MCC 2 30.0% 35.0% (90.0 g) (105.0 g) MCC 3 30.0% 30.0% (90.0 g) (90.0 g) MCC 4 30.0% (90.0 g) Titanium 0.5% 2.0% 0.5% 0.5% 2.0% 2.0% dioxide (1.5 g) (6.0 g) (1.5 g) (1.5 g) (6.0 g) (6.0 g) Sorbosil TC 3.0% 3.0% 3.0% 3.0% 3.0% 3.0% 15 (9.0 g) (9.0 g) (9.0 g) (9.0 g) (9.0 g) (9.0 g) Sodium 2.0% 2.0% 2.0% 2.0% 2.0% 2.0% lauryl (6.0 g) (6.0 g) (6.0 g) (6.0 g) (6.0 g) (6.0 g) sulphate (25% solution)

(33) TABLE-US-00002 TABLE 2 Results obtained for samples 1 to 6. Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Phase Stable Stable Stable Stable Stable Stable stability pH 8.57 8.45 8.85 8.65 8.51 8.4 Appearance/ Good Good Good Good Good Good mouthfeel texture, texture, texture, texture, texture, texture, smooth smooth smooth smooth smooth smooth surface, a surface, a surface, surface surface surface, a little little liquid a little little liquid liquid liquid

Example 2

Toothpaste Compositions

(34) Toothpaste samples 7 to 9 were produced according to the following procedure using the ingredients and amounts compiled in Table 3 below.

(35) Step A: Water, sorbitol, fluorophosphate (phoskadent Na 211, BK Guilini, Germany), cellulose gum (Akucell AF 2985, AkzoNobel N.V., The Netherlands), and sweetener (Sunett, Celanese Corp., USA) were mixed in a beaker.

(36) Step B: Surface-reacted calcium carbonate and titanium dioxide were wetted with water and subsequently added to the mixture of step A. The mixture was homogenized until a smooth mixture was obtained.

(37) Step C: The silica Sorbosil TC 15 (PQ Corporation, USA) was added to the mixture of step B under homogenizing conditions, whereby the mixture was heating up strongly. The mixture was stirred until it was cooled down to room temperature.

(38) Step D: The surfactant Tego Betaine ZF (Evonik Industries AG, Germany) was added in form of a 25% solution to the mixture of step C under slow agitation.

(39) Step E: 0.8 wt.-% (2.4 g) spearmint flavour was added to the mixture of step D.

(40) The phase stability was evaluated by visual inspection, and the pH value measurements were carried out as described above. The mouthfeel was evaluated by brushing teeth with the toothpaste samples. The samples were tested on the day of production, after 6 weeks, 12 weeks, 6 months and 12 months. The results are compiled in Tables 4 to 6 below, which show that all samples were stable and had a good texture and a smooth surface. Furthermore, all samples had an acceptable pH, even after a long storage period. FIG. 1 presents a photograph of samples 7 to 9 applied to a paper cloth on the day of production, which shows that the texture of the samples is very smooth and cream-like.

(41) TABLE-US-00003 TABLE 3 Ingredients and amounts of toothpaste samples 7 to 9. The percentages refer to weight percentages based on the total weight of the composition. Ingredients Sample 7 Sample 8 Sample 9 Sorbitol 70% 35.0% (105.0 g) 35.0% (105.0 g) 25.0% (75.0 g) Water 27.6% (82.8 g) 26.1% (78.3 g) 36.1% (108.3 g) Phoskadent Na 1.1% (3.3 g) 1.1% (3.3 g) 1.1% (3.3 g) 211 Akucell AF 0.7% (2.1 g) 0.7% (2.1 g) 0.7% (2.1 g) 2985 Sunett 0.1% (0.3 g) 0.1% (0.3 g) 0.1% (0.3 g) MCC 4 30.0% (90.0 g) 30.0% (90.0 g) 30.0% (90.0 g) Titanium 0.5% (1.5 g) 2.0% (6.0 g) 2.0% (6.0 g) dioxide Sorbosil TC 15 3.0% (9.0 g) 3.0% (9.0 g) 3.0% (9.0 g) Tego Betaine 2.0% (6.0 g) 2.0% (6.0 g) 2.0% (6.0 g) ZF

(42) TABLE-US-00004 TABLE 4 Results obtained for sample 7. production day 6 weeks 12 weeks 6 months 12 months Phase Stable Stable Stable Stable Stable stability pH 8.58 8.63 8.64 8.75 8.83 Appearance/ Good Good Good Good Good mouthfeel texture texture texture texture texture

(43) TABLE-US-00005 TABLE 5 Results obtained for sample 8. production day 6 weeks 12 weeks 6 months 12 months Phase Stable Stable Stable Stable Stable stability pH 8.37 8.61 8.61 8.7 8.78 Appearance/ Smooth, Smooth, Smooth, Smooth, Smooth, mouthfeel good good good good good texture, texture, texture, texture, texture, cream- cream- cream- cream- cream- like like like like like texture texture texture texture texture

(44) TABLE-US-00006 TABLE 6 Results obtained for sample 9. production day 6 weeks 12 weeks 6 months 12 months Phase Stable Stable Stable Stable Stable stability pH 8.44 8.5 8.52 8.65 8.72 Appearance/ Smooth, Smooth, Smooth, Smooth, Smooth, mouthfeel very very very very very good good good good good texture, texture, texture, texture, texture, cream- cream- cream- cream- cream- like like like like like texture texture texture texture texture

Example 3

Scouring Cream

(45) Scouring cream samples 10 to 12 were produced according to the following procedure using the ingredients and amounts compiled in Table 7 below.

(46) Step 1: Water and a thickener (Rheosolve 633, Coatex SAS, France) were added to a beaker fitted with an agitator (speed: 380 rpm). The pH was adjusted between 10 and 11 using sodium hydroxide (50% solution).

(47) Step 2: The surface-reacted calcium carbonate or ground calcium carbonate (as comparative example) was added stepwise to the mixture of step 1 under high agitation (speed 2, 250-300 rpm). The mixture was stirred until it was homogeneous.

(48) Step 3: A cocoglycoside surfactant (Plantacare 818 UP, BASF, Germany) was added in form of a 20% solution to the homogeneous mixture of step 2. Subsequently, lemon essential oil and Polysorbate 60 were added under slow stirring (speed 1, 70 rpm).

(49) TABLE-US-00007 TABLE 7 Ingredients and amounts of scouring cream samples 10 to 12. The percentages refer to weight percentages based on the total weight of the composition. Sample 10 Ingredients (comparative) Sample 11 Sample 12 Water add. 100 add. 100 add. 100 Rheosolve 633 0.85 wt.-% 0.85 wt.-% 0.85 wt.-% Sodium hydroxide 0.13 wt.-% 0.13 wt.-% 0.13 wt.-% (50% solution) GCC3 50 wt.-% MCC1 50 wt.-% MCC2 50 wt.-% Plantacare 818 UP 5 wt.-% 5 wt.-% 5 wt.-% (20% solution) Lemon essential oil 0.1 wt.-% 0.1 wt.-% 0.1 wt.-% Tween 60V Pharma 0.2 wt.-% 0.2 wt.-% 0.2 wt.-%

(50) The abrasion of the obtained scouring cream samples was tested within 24 h at a temperature of 23 C. according to the following procedure:

(51) The abrasion was determined by using a washability and scrub resistance tester (Model 494, Erichsen GmbH & Co. KG, Germany) equipped with a fastening with plastic plate to fix a cloth (Erichsen GmbH & Co. KG, Germany). Three weights (400 g) were fixed on the fastening so that the fastening including the weights and the plate had a weight of about 580 g. A cloth square (size: 99.1 cm) was fixed on the plastic plate with an adhesive (Scotch.sup.3M) tape and was put in the notches of the fastening.

(52) In the tester, a glass plate was fixed in a horizontal position in the space provided for this purpose. A Plexiglas plate (size: 4 cm30 cm, Steba Kunststoffe AG, Swiss) was taped with adhesive Scotch tape on the glass plate. The distance between the top of the tray and the plate was about 3.9 cm and between the bottom of the tray and the plate about 4.5 cm. 2 g water was added on the cloth fixed on the fastening. 25 g scouring agent were added onto the Plexiglas plate. The fastening was positioned on the Plexiglas plate with the tension cable. The testing machine was set to 200 cycles and started. At the end of the test, the Plexiglas plate was removed and rinsed. The frame of the machine and the glass plate were cleaned with hot water, followed by deionized water. Every sample was tested three times.

(53) The abrasion of the scouring cream samples was determined by measuring the gloss of the Plexiglas plate at 20 using the haze meter Haze-Gloss (BYK Gardener GmbH, Germany). The measurement was carried out at 8 different points in the centre of the plate by slightly moving the plate left to right and from top to bottom. The average gloss value for every sample is given in Table 8 below. The abrasiveness of a sample was calculated by subtracting the average gloss value measured for the Plexiglas plate that has been treated with the respective sample from the average gloss value measured for the untreated Plexiglas plate. The abrasion value and level for every sample is given in Table 8 below.

(54) TABLE-US-00008 TABLE 8 Results obtained for scouring cream samples 10 to 12. Untreated Sample 10 Plexiglas plate (comparative) Sample 11 Sample 12 Abrasion value 16.2 4.5 2.5 Abrasion level medium low low Gloss value 77.5 61.3 73 75 Gloss level low very high very high

(55) It can be gathered from Table 8 that the abrasive cleaning compositions including the surface-reacted calcium carbonate abrasive according to the present invention had a lower abrasion value and caused lower damage to the cleaned surface (indicated by the higher gloss value) compared to the comparative example cleaning composition containing the ground calcium carbonate.