SURFACE-REACTED MAGNESIUM CARBONATE AS CARRIER MATERIAL FOR THE RELEASE OF ONE OR MORE ACTIVE AGENT(S) IN A HOME CARE FORMULATION

Abstract

The present invention relates to a surface-reacted magnesium carbonate, a delivery system for the release of one or more active agent(s) in a home care formulation comprising the surface-reacted magnesium carbonate, a home care formulation comprising the delivery system for the release of one or more active agent(s), a method for preparing the surface-reacted magnesium carbonate and a method for preparing the delivery system for the release of one or more active agent(s) in a home care formulation, as well as the use of the surface-reacted magnesium carbonate as a carrier material for the release of one or more active agent(s) in a home care formulation and the use of the delivery system for the release of one or more active agent(s) in a home care formulation.

Claims

1. Surface-reacted magnesium carbonate, wherein the surface-reacted magnesium carbonate is obtained by treating the surface of magnesium carbonate with one or more compound(s) selected from the group consisting of sulphuric acid, phosphoric acid, carbonic acid, carboxylic acids containing up to six carbon atoms, preferably selected from formic acid, acetic acid, propionic acid, lactic acid and mixtures thereof; and di-, and tri-carboxylic acids where the carboxylic acid groups are linked by a chain of 0-4 intermittent carbon atoms, preferably selected from oxalic acid, citric acid, succinic acid, maleic acid, malonic acid, tartaric acid, adipic acid, fumaric acid and mixtures thereof, or a corresponding salt thereof.

2. The surface-reacted magnesium carbonate according to claim 1, wherein the magnesium carbonate is selected from the group consisting of anhydrous magnesium carbonate or magnesite (MgCO.sub.3), hydromagnesite (Mg.sub.5(CO.sub.3).sub.4(OH).sub.2.4H.sub.2O), artinite (Mg.sub.2(CO.sub.3)(OH).sub.2.3H.sub.2O), 15 dypingite (Mg.sub.5(CO.sub.3).sub.4(OH).sub.2.5H.sub.2O), giorgiosite (Mg.sub.5(CO.sub.3).sub.4(OH).sub.2.5H.sub.2O), pokrovskite (Mg.sub.2(CO.sub.3)(OH).sub.2.0.5H.sub.2O), barringtonite (MgCO.sub.3.2H.sub.2O), lansfordite (MgCO.sub.3.5H.sub.2O), dolocarbonate and nesquehonite (MgCO.sub.3.3H.sub.2O)

3. The surface-reacted magnesium carbonate according to claim 1, wherein the magnesium carbonate has a) a BET specific surface area in the range from 10 to 100 m.sup.2/g, preferably from 12 to 50 m.sup.2/g, and most preferably from 17 to 40 m.sup.2/g, measured using nitrogen and the BET method according to ISO 9277:2010, and/or b) an intra-particle intruded specific pore volume in the range from 0.9 to 2.3 cm.sup.3/g, preferably from 1.2 to 2.1 cm.sup.3/g, and most preferably from 1.5 to 2.0 cm.sup.3/g, calculated from mercury porosimetry measurement, and/or c) a d.sub.50(vol) in the range from 1 to 75 μm, preferably from 1.2 to 50 μm, more preferably from 1.5 to 30 μm, even more preferably from 1.7 to 15 μm and most preferably from 1.9 to 10 μm, as determined by laser diffraction, and/or d) a d.sub.98(vol) in the range from 2 to 150 μm, preferably from 4 to 100 μm, more preferably from 6 to 80 μm, even more preferably from 8 to 60 μm and most preferably from 10 to 40 μm, as determined by laser diffraction.

4. The surface-reacted magnesium carbonate according to claim 1, wherein the magnesium carbonate has a ratio of intra-particle intruded specific pore volume, calculated from mercury porosimetry measurement, to BET specific surface area, measured using nitrogen and the BET method according to ISO 9277:2010, of more than 0.01 cm.sup.3/m.sup.2, preferably more than 0.05 cm.sup.3/m.sup.2, and most preferably more than 0.06 cm.sup.3/m.sup.2, such as from 0.06 to 0.25 cm.sup.3/m.sup.2.

5. The surface-reacted magnesium carbonate according to claim 1, wherein the magnesium carbonate contains up to 25 000 ppm Ca.sup.2+ ions.

6. The surface-reacted magnesium carbonate according to claim 1, wherein the surface-reacted magnesium carbonate is obtained by treating the surface of the magnesium carbonate with the one or more compound(s) or a corresponding salt thereof in an amount from 0.1 to 20 wt.-%, based on the total dry weight of the magnesium carbonate.

7. The surface-reacted magnesium carbonate according to claim 1 is a carrier material for the release of one or more active agent(s) in a home care formulation.

8. A delivery system for the release of one or more active agent(s) in a home care formulation, the delivery system comprising the surface-reacted magnesium carbonate according to claim 1 and one or more active agent(s) which is loaded on the carrier material.

9. The delivery system according to claim 8, wherein the one or more active agent(s) is/are loaded onto and/or loaded into the ore volume of the surface-reacted magnesium carbonate.

10. The delivery system according to claim 8, wherein the one or more active agent(s) is selected from the group of active agents mentioned in the Regulation (EC) No 648/2004 of the European Parliament and of the Council of 31 Mar. 2004 on detergents, preferably the one or more active agent(s) is selected from the group comprising anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, phosphates, phosphonates, softener, sequestrants, builders, processing aids, enzymes, oxygen-based bleaching agents, chlorine-based bleaching agents, anti-scaling agents, complexing agents, dispersing agents, nitrilotriacetic acid and salts thereof, phenols, halogenated phenols, paradichlorobenzene, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, soap, zeolites, polycarboxylates, disinfectants, optical brightener, defoamers, colorants, fragrances and mixtures thereof.

11. The delivery system according to claim 8, wherein the delivery system comprises the one or more active agent(s) in an amount ranging from 10 to 300 wt.-%, preferably from 40 to 290 wt.-%, more preferably from 60 to 280 wt.-%, and most preferably from 80 to 260 wt.-%, e.g. from 90 to 200 wt.-%, based on the total weight of the carrier material.

12. The delivery system according to claim 8, wherein the delivery system is in the form of a free flowing powder, a tablet, a pellet, or granules, preferably a free flowing powder.

13. Home care formulation comprising a delivery system for the release of one or more active agent(s) according to claim 8.

14. The home care formulation according to claim 13, wherein the formulation is in form of a liquid, a free flowing powder, a paste, a gel, a bar, a cake, a pouch or a moulded piece, such as a tablet.

15. The home care formulation according to claim 13, wherein the formulation is a washing formulation, preferably for cleaning of laundry, fabrics, dishes and hard surfaces; a pre-washing formulation; a rinsing formulation; a bleaching formulation; a laundry fabric-softener formulation; a cleaning formulation; and mixtures thereof.

16. A method for preparing a surface-reacted magnesium carbonate according to claim 1, the method comprising at least the steps of: i) providing magnesium carbonate, ii) providing one or more compound(s) selected from the group consisting of sulphuric acid, phosphoric acid, carbonic acid, carboxylic acids containing up to six carbon atoms, preferably selected from formic acid, acetic acid, propionic acid, lactic acid and mixtures thereof; and di-, and tri-carboxylic acids where the carboxylic acid groups are linked by a chain of 0-4 intermittent carbon atoms, preferably selected from oxalic acid, citric acid, succinic acid, maleic acid, malonic acid, tartaric acid, adipic acid, fumaric acid and mixtures thereof, or a corresponding salt thereof, and iii) treating the surface of the magnesium carbonate of step a), under mixing, in one or more steps, with the one or more compound(s) or a corresponding salt thereof of step b) such that a reaction is achieved by the one or more compound(s) or the corresponding salt thereof and the surface of said magnesium carbonate.

17. A method for preparing a delivery system for the release of one or more active agent(s) in a home care formulation according to claim 8, the method comprising the steps of a) providing a surface-reacted magnesium carbonate which is obtained by treating the surface of the magnesium carbonate with one or more compound(s) selected from the group consisting of sulphuric acid, phosphoric acid, carbonic acid, carboxylic acids containing up to six carbon atoms, preferably selected from formic acid, acetic acid, propionic acid, lactic acid and mixtures thereof; and di-, and tri-carboxylic acids where the carboxylic acid groups are linked by a chain of 0-4 intermittent carbon atoms, preferably selected from oxalic acid, citric acid, succinic acid, maleic acid, malonic acid, tartaric acid, adipic acid, fumaric acid and mixtures thereof, or a corresponding salt thereof, b) providing one or more active agent(s) in the form of a liquid or dissolved in a solvent, c) contacting the surface-reacted magnesium carbonate of step a) with the one or more active agent(s) of step b), and d) optionally removing the solvent by evaporation if used in step b).

18. Use of a surface-reacted magnesium carbonate according to claim 1 as a carrier material for the release of one or more active agent(s) in a home care formulation.

19. Use of a delivery system according to claim 8 for the release of one or more active agent(s) in a home care formulation.

Description

EXAMPLES

1. Measurement Methods

[0235] In the following, measurement methods implemented in the examples are described.

Particle Size Distribution

[0236] Volume determined median particle size d.sub.50(vol) and the volume determined top cut particle size d.sub.98(vol) was evaluated using a Malvern Mastersizer 3000 Laser Diffraction System (Malvern Instruments Plc., Great Britain) equipped with a Hydro LV system. The d.sub.50(vol) or d.sub.98(vol) value indicates a diameter value such that 50% or 98% by volume, respectively, of the particles have a diameter of less than this value. The powders were suspended in 0.1 wt.-% Na.sub.4O.sub.7P.sub.2 solution. 10 mL of 0.1 wt.-% Na.sub.4O.sub.7P.sub.2 was added to the Hydro LV tank, then the sample slurry was introduced until an obscuration between 10-20% was achieved. Measurements were conducted with red and blue light for 10 s each. For the analysis of the raw data, the models for non-spherical particle sizes using Mie theory was utilized, and a particle refractive index of 1.57, a density of 2.70 g/cm.sup.3, and an absorption index of 0.005 was assumed. The methods and instruments are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments.

Specific Surface Area (SSA)

[0237] The specific surface area was measured via the BET method according to ISO 9277:2010 using nitrogen as adsorbing gas on a Micromeritics ASAP 2460 instrument from Micromeritics. The samples were pretreated in vacuum (10.sup.−5 bar) by heating at 150° C. for a period of 60 min prior to measurement.

Porosimetry

[0238] The specific pore volume was measured using a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter having a maximum applied pressure of mercury 414 MPa (60 000 psi), equivalent to a Laplace throat diameter of 0.004 μm nm). The equilibration time used at each pressure step is 20 seconds. The sample material is sealed in a 3 cm.sup.3 chamber powder penetrometer for analysis. The data are corrected for mercury compression, penetrometer expansion and sample material compression using the software Pore-Comp (Gane, P. A. C., Kettle, J. P., Matthews, G. P. and Ridgway, C. J., “Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper-Coating Formulations”, Industrial and Engineering Chemistry Research, 35(5), 1996, p 1753-1764.).

[0239] The total pore volume seen in the cumulative intrusion data can be separated into two regions with the intrusion data from 214 μm down to about 1-4 μm showing the coarse packing of the sample between any agglomerate structures contributing strongly. Below these diameters lies the fine interparticle packing of the particles themselves. If they also have intraparticle pores, then this region appears bi modal, and by taking the specific pore volume intruded by mercury into pores finer than the modal turning point, i.e. finer than the bi-modal point of inflection, the specific intraparticle pore volume is defined. The sum of these three regions gives the total overall pore volume of the powder, but depends strongly on the original sample compaction/settling of the powder at the coarse pore end of the distribution.

[0240] By taking the first derivative of the cumulative intrusion curve the pore size distributions based on equivalent Laplace diameter, inevitably including pore-shielding, are revealed. The differential curves clearly show the coarse agglomerate pore structure region, the interparticle pore region and the intraparticle pore region, if present. Knowing the intraparticle pore diameter range it is possible to subtract the remainder interparticle and interagglomerate pore volume from the total pore volume to deliver the desired pore volume of the internal pores alone in terms of the pore volume per unit mass (specific pore volume). The same principle of subtraction, of course, applies for isolating any of the other pore size regions of interest.

Amount of Surface-Treatment Layer

[0241] The amount of the treatment layer on the magnesium and/or calcium ion-containing material is calculated theoretically from the values of the BET of the untreated magnesium and/or calcium ion-containing material and the amount of the one or more compound(s) that is/are used for the surface-treatment. It is assumed that 100% of the one or more compound(s) are present as surface treatment layer on the surface of the magnesium and/or calcium ion-containing material.

2. Materials Used

[0242] The materials used for the present invention had the characteristics set out in the following table 1.

TABLE-US-00001 TABLE 1 Characterization of the magnesium carbonates d.sub.50/ d.sub.98/ S.sub.BET/ V.sub.pore, Hg/ V.sub.pore, Hg/S.sub.BET/ # Sample μm μm m.sup.2 g.sup.−1 cm.sup.3 g.sup.−1 cm.sup.3 m.sup.−2 #A Hydromagnesite 25 73 25.0 1.711 0.068 #A1 Citr/hydromagnesite 20 58 24.8 — — #A2 Sulph/hydromagnesite 20 58 19.5 — — #A3 Sulph/hydromagnesite 2 12.5 27 40.5 1.416 0.035

[0243] For the surface reactions, 11 L of a 10 wt. % slurry of the hydromagnesite (#A) was prepared. To this slurry, the desired quantity of sodium sulphate 99%, Sigma Aldrich, 238597-1KG) or sodium dihydrogencitrate (99%, Sigma-Aldrich, 234265-1KG) was added to attain a nominal loading of 5 wt. % based on the dry weight of the hydromagnesite. The slurry was stirred for 1 h at room temperature and subsequently spray-dried in a GEA Niro A/S spray dryer with an inlet temperature of 270° C., and an outlet temperature of 110° C. Throughout this report, the surface-reacted samples are referred to as Citr/hydromagnesite (#A1) and Sulph/hydromagnesite (#A2) for the sodium sulphate and sodium dihydrogencitrate reacted samples, respectively. The characteristics for the surface-reacted samples obtained are also set out in table 1.

3. Loading and Release Experiments

[0244] The loading-release experiments were conducted using Hoesch AE 50, a sodium dodecylbenzolsulphonate surfactant typically used for dishwashing. For the loading trials, the desired amount of magnesium carbonate (10 g) was weighed into a beaker. Subsequently, the surfactant (10 g) was added drop-wise using a pipette. The added quantity was monitored gravimetrically. The magnesium carbonate and the liquid were mixed thoroughly for 5 min. The loading was calculated as detailed in Equation (1).

[00001]$\begin{array}{cc}\mathrm{Loading}\left[\%\right]=\frac{\mathrm{mass}\mathrm{of}\mathrm{surfactant}\left[g\right]}{\mathrm{mass}\mathrm{of}\mathrm{powder}\left[g\right]}.Math.100& \left(1\right)\end{array}$

[0245] For the release experiments, the loaded samples (0.5 g) were dispersed in water (1 L) using a magnetic stirrer (300 rpm) for 1 h at room temperature. The amount of loaded sample was selected to attain a concentration of 0.25 g L.sup.−1 of Hoesch AE 50 based on a 100% recovery. Afterwards, the suspensions were filtered using a syringe filter (0.2 μm). The concentration of the surfactant in the liquids were determined by UV spectroscopic evaluation conducted in a Hach Lange DR6000 spectral photometer based on the absorbance at a wavelength λ=224 nm. The concentration was calculated based on a corresponding calibration curve of 5 samples of known concentrations.

[0246] All samples were loaded with 100 wt. % of the surfactant, and release tests were conducted at a target concentration of 0.25 g L.sup.−1, which represents an approximation of the surfactant concentration in real washing trials. The recovery of the surfactant is defined as the amount measured in solution using UV-VIS spectroscopy, divided by the theoretical amount introduced. The utilized loading and the corresponding release data for all samples are provided in the following Table 2.

TABLE-US-00002 TABLE 2 Loading and release (recovery) data of the tested samples Loading.sup.a/ C.sub.loaded mineral.sup.a/ C.sub.Tensid.sup.a/ Recovery/ Sample % g L−1 g L−1 % #A (comparative) 100.3 0.502 0.251 59.1 #A1 100.4 0.506 0.253 82.6 (Citr/ hydromagnesite) (inventive) #A2 101.1 0.502 0.252 80.6 (Sulph/ hydromagnesite) (inventive) .sup.aCalculated values based on recorded weights

[0247] All samples were tested at identical concentration and loading to facilitate the direct comparison between the materials.

[0248] It should be considered that for a given material, a higher loading results in a higher recovery, so the selection of an optimal magnesium carbonate should be conducted under consideration of the maximum attainable loading.

[0249] It can be gathered from table 2 that the comparative material, #A, attained a recovery of about 60% with surfactant. In contrast, if the surface of the same magnesium carbonate is treated with 5 wt. % of sodium citrate, the recovery of the surfactant is increased to about 83% (see sample #A1). While this difference might sound small, it essentially means that the quantity of “lost” surfactant is reduced by 57.5%. Without wishing to be bound by theory, it is assumed that the sodium citrate adsorbs on the surface and thereby quenches the acidic surface of the magnesium carbonate. A similar effect was observed for sodium sulphate, where the recovery was increased to about 81% (see sample #A2).

[0250] In view of this, a surface-reacted magnesium carbonate according to the present invention provides an increased recovery of surfactants.

4. Application Trials in Automated Dishwashing

4.1 Dishwashing Formulations

[0251] Two formulations were prepared for automated dishwashing trials as summarized in Table 3. Formulation #F1 is analogous to commercial All-in-one dishwashing powders, and corresponding raw materials are well known to a person skilled in the art. The surfactant used was a nonionic, low-foaming surfactant based on modified fatty alcohol polyglycol ether. The complexing agent was a dicarboxymethyl alaninate salt. The builder used is a mixture of sodium carbonate and citric acid.

[0252] Formulation #F2 is an exact copy of formulation #F1, except that the quantities of surfactant and complexing agent were reduced, and the quantity of loaded hydromagnesite was increased correspondingly, so that the quantity of surfactant in the formulation remained unchanged.

TABLE-US-00003 TABLE 3 Composition of the dishwashing formulations. Material #F1 #F2 Surfactant  3 wt. % — Loaded Hydromagnesite —  6 wt. % Complexing agent 10 wt. %  7 wt. % Builders 50 wt. % 50 wt. % Enzymes  1 wt. %  1 wt. % Processing additives  5 wt. %  5 wt. % Sodium sulfate 31 wt.-% 31 wt.-%

4.2 Preparation of Loaded Hydromagnesite

[0253] Hydromagnesite #A3 (Sulph/hydromagnesite) was loaded with 100.1 wt. % of the a nonionic, low-foaming surfactant based on modified fatty alcohol polyglycol ether utilized for the preparation of the dishwashing formulation #F1. The loading was conducted by adding the pre-heated surfactant (60° C.) to the hydromagnesite pre-heated (60° C.) and stirred (500 rpm) in a Somakon lab mixer.

4.3 Drying Performance Test

[0254] The drying performance of the formulations #F1 and #F2 was assessed in dedicated dishwashing trials. The testing conditions are summarized in Table 4.

TABLE-US-00004 TABLE 4 Drying performance test conditions and evaluation. Dishwasher Bosch SMS 086 Program 50° C. Eco, deactivated 3-in-1—function Repetitions 3 (cumulative) Water Hardness 21 ± 1° dH Ballast soil 50 g of a frozen mixture of tomato ketchup, mustard, gravy, potato starch, benzoic acid, egg yolk, margarine, milk, water Machine  9 China-dish—plates (Arzberg) Loading  8 China-dish—soup plates (Arzberg)  7 China-dish—dessert plates (Arzberg) 10 china-dish—cups (Arzberg)  6 Willy beakers (Ruhrglas)  6 glass beakers (Duran)  6 PP—plates (VNaca)  3 Tupper ware (PP)  3 Tupper ware blue (PP)  1 stainless steel dipper (wmf)  1 stainless steel server (wmf) 10 stainless steel knives (wmf) 10 stainless steel forks (wmf) 10 stainless steel spoons (wmf) 10 stainless steel teaspoons (wmf) Evaluation 0 = no spots 1 = 1 spot (<25 mm.sup.2) 2 = 2 spots (<50 mm.sup.2) 3 = 3 spots (<100 mm.sup.2) 4 = 4 spots (<150 mm.sup.2) 5 = 5 spots (<200 mm.sup.2) 6 = >5 spots (>200 mm.sup.2)

[0255] Before the tests, the dishes were pre-cleaned with alkali and citric acid and rinsed with water. The ion-exchanger of the dishwasher was deactivated, and water was provided via an external tank. The 3-in-1-function was deactivated by filling the rinse aid dispenser with water. The front door was kept closed 30 min after completion of the program, subsequently the door was fully opened and the evaluation started. The arithmetical mean of three repetitions is reported. The results are summarized in Table 5. A difference is considered significant.

TABLE-US-00005 TABLE 5 Drying performance test results. Material Porcelain Glass Plastics Stainless steel Mean #F1 0.6 0.1 3.8 0.0 1.1 #F2 0.3 0.0 0.7 0.0 0.2

[0256] As can be gathered from the data in Table 5, the drying performance for plastics was significantly improved, while otherwise the performance was unchanged.

4.4 Rinse Aid Performance Test

[0257] The rinse aid performance of the formulations #F1 and #F2 was assessed in dedicated dishwashing trials. The testing conditions are summarized in Table 6.

TABLE-US-00006 TABLE 6 Rinse aid test conditions and evaluation. Dishwasher Miele GSL 2 Program 50° C., 8 min, 65° C. Rinsing Cycle Repetitions 3 (cumulative) Water hardness 21 ± 1° dH Ballast soil 50 g of a frozen mixture of ketchup, milk, starch, fat, egg yolk, benzoic acid, water Machine 6 Plastic Plates Melamin, blue loading 3 Plates Glass, black (Arcoroc) 3 Plates Porcelain, black (Schönwald) 3 Plates Ceramic, black (Friesland) 4 Longdrink Glasses (Schott Paris 79) 4 Juice Glasses (Schott Paris 12) 1 Butter Plate Stainless Steel 4 Knives Stainless Steel (WMF) 4 Knives Stainless Steel (BSF) Evaluation visual grading according to an 8-point scale for filming for filming 8 = no filming 1 = very strong filming, glass is only a little transparent Evaluation visual grading according to an 8-point scale for for spotting water and salt spots 8 = free of spots and stripes 7 = few very slight stripes and/or few very small spots 6 = few slight stripes and/or some small spots 5 = slight or medium stripes and/or few medium sized spots 4 = few medium stripes and/or medium sized spots 3 = medium stripes and/or few large spots 2 = few large stripes and/or large spots 1 = large stripes and/or numerous large spots 0 = very large stripes and/or very numerous large spots

[0258] The glasses, plates and knives were pre-washed with Neodisher detergent commercially available from Dr. Weigert in combination with citric acid, and two cycles with the test detergent. The ion-exchanger of the dishwasher was deactivated, and water was provided via an external tank. The 3-in-1-function was deactivated by filling the rinse aid dispenser with water. The front door was kept closed 10 min after completion of the program, subsequently the door was fully opened and the dishwasher racks fully pulled out. The evaluation was started after 20 min. The arithmetical mean of three repetitions is reported. The results are summarized in Table 7. A difference ≥0.9 is considered significant.

TABLE-US-00007 TABLE 7 Rinse aid performance test results. Effect Filming Spotting #F1 4.6 6.9 #F2 4.1 6.9

[0259] As can be gathered from the data in Table 7, the rinse aid performance was comparable for both formulations.

4.5 Cleaning Performance Test

[0260] The cleaning performance of the formulations #F1 and #F2 was assessed in dedicated dishwashing trials. The testing conditions are summarized in Table 8.

TABLE-US-00008 TABLE 8 Cleaning performance test conditions and evaluation. Dishwasher Miele GSL 2 Program 45° C., 8 min Repetitions 30 Water hardness 21 ± 1° dH Ballast soil 50 g per cycle, frozen, ingredients according to IKW- Association Method, attachment 3 dated 27 Jun. 06 1997 Machine loading  6 Plates (Arzberg)  6 Cups (Bauscher)  6 Beakers (JENA)  6 Stainless Steel Slides (WMF) 12 Glass Plates (Arcoroc) 18 Dessert Plates (Arzberg) Soiling Minced Minced meatand beef is mixed with egg, this mixture is mixed meat with water and 3 g are applied on dessert plates. The plates are dried for 2 hours at 130° C. Milk skin 6 beakers with 100 mL milk are placed in microwave (600 W) and heated up to 85° C. Beakers are cooled down to 35° C. Milk is poured out slowly; milk skin sticks to glass walls. Afterwards, they are dried for 2 hours at 80° C. Tea In a beaker 6 g of tea and 1 L boiling water are added, left to draw for 5 min. The tea is drained through a sieve. 100 ml of tea is put into each cup, 20 mL of tea is removed every 5 min until all cups are empty. This procedure is done twice. Crème Ready mix is heated up in a pot to 60° C. The cream is Brulée distributed on dessert plates (3.5 g). After drying crème for 2 hours at room temperature, creme is baked in oven for 2 hours at 140° C. Egg Yolk 1.5 g of the egg yolk mixture is applied on stainless-steel slides. The slides are immersed for 30 s in boiling, demineralised water. After drying for 30 min at 80° C. and cooling down, slides are weighted. Starch Mix 16.3 g of potato starch, sweet corn starch, rice starch, and wheat starch are mixed with 2000 g water and heated. 29.5 g of the mixture is applied onto plates and aged under defined conditions. Pasta 50 g cooked pasta and 200 mL distilled water are mixed. 3 g of this mixture are applied on plates and dried for 2 hours at 120° C. Cereals Cereals are cooked in milk and left to swell. 15 g of this mixture is applied on dessert plates and dried for 2 hours at 80° C. Evaluation Soiled chinaware, glasses: Visual rating following a 10 step scale, 10 = totally clean, 1 = totally soiled. Soiled stainless-steel slides, glass plates: Gravimetric, 100 = totally clean, 0 = totally soiled.

[0261] The arithmetical mean of 30 trials is reported. The results are summarized in Table 9. A difference ≥0.9 is considered significant.

TABLE-US-00009 TABLE 9 Cleaning performance test results. Creme Minced Milk Tea Egg Effect Pasta Cereals Brulee Meat Skin Yolk Starch Mean #F1 8.6 7.3 6.7 7.3 8.0 5.0 5.7 6.5 6.9 #F2 8.6 7.0 6.4 7.5 7.3 4.1 5.9 6.9 6.7

[0262] As can be gathered from the data in Table 9, the cleaning performance was comparable for both formulations. However, the comparative sample performs slightly better with tea.