CARRIER MATERIAL FOR THE RELEASE OF ONE OR MORE ACTIVE AGENT(S) IN A HOME CARE FORMULATION

Abstract

The present invention relates to a carrier material for the release of one or more active agent(s) in a home care formulation, a delivery system for the release of one or more active agent(s) in a home care formulation, a home care formulation comprising the delivery system for the release of one or more active agent(s), 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 delivery system for the release of one or more active agent(s) in a home care formulation.

Claims

1. A carrier material for the release of one or more active agent(s) in a home care formulation, the carrier material consisting of magnesium carbonate having a specific surface area of 25 m.sup.2/g, measured using nitrogen and the BET method according to ISO 9277:2010.

2. The carrier material according to claim 1, wherein the magnesium carbonate has a specific surface area in the range from 25 to 150 m.sup.2/g, measured using nitrogen and the BET method according to ISO 9277:2010.

3. The carrier material according to claim 2, wherein the magnesium carbonate has an intra-particle intruded specific pore volume in the range from 0.9 to 2.3 cm.sup.3/g, calculated from mercury porosimetry measurement.

4. The carrier material according to claim 1, wherein the magnesium carbonate has a d.sub.50(vol) in the range from 1 to 75 m, as determined by laser diffraction.

5. The carrier material according to claim 1, wherein the magnesium carbonate has a d.sub.98(vol) in the range from 2 to 150 m, as determined by laser diffraction.

6. The carrier material according to claim 1, wherein the magnesium carbonate contains up to 15 000 ppm Ca.sup.2+ ions.

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

8. The delivery system according to claim 7, wherein the one or more active agent(s) is/are adsorbed onto and/or adsorbed and/or absorbed into the carrier material.

9. The delivery system according to claim 7, wherein the one or more active agent(s) is/are 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, 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, sequestrants, 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.

10. The delivery system according to claim 7, wherein the delivery system comprises the one or more active agent(s) in an amount ranging from 10 to 300 wt. %, based on the total weight of the carrier material.

11. The delivery system according to claim 7, wherein the delivery system is in the form of a powder, a tablet, a pellet, or granules.

12. A home care formulation comprising a delivery system for the release of one or more active agent(s) according to claim 7.

13. The home care formulation according to claim 12, wherein the formulation is in form of a liquid, a powder, a paste, a gel, a bar, a cake, a pouch, a moulded piece or a tablet.

14. The home care formulation according to claim 12, wherein the formulation is a washing formulation; a washing formulation 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.

15. 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 7, the method comprising a) providing magnesium carbonate having a specific surface area of 25 m.sup.2/g, measured using nitrogen and the BET method according to ISO 9277:2010, b) providing one or more active agent(s) in the form of a liquid or dissolved in a solvent, and c) contacting the magnesium carbonate of step a) with the one or more active agent(s) of step b).

16. The delivery system according to claim 7, wherein the delivery system provides a release efficiency for the one or more active agent(s) represented by the following formula (I) $\begin{array}{cc}\mathrm{release}.Math..Math.\mathrm{efficiency}=100*\frac{m\left(\mathrm{active}.Math..Math..Math.\mathrm{agent}.Math..Math.\mathrm{released}\right)}{m\left(\mathrm{active}.Math..Math..Math.\mathrm{agent}.Math..Math.\mathrm{loaded}\right)}& \left(I\right)\end{array}$ of 50%.

17. The delivery system according to claim 16, wherein the delivery system provides a release efficiency for the one or more active agent(s) $\mathrm{release}.Math..Math.\mathrm{efficiency}=100*\frac{m\left(\mathrm{active}.Math..Math..Math.\mathrm{agent}.Math..Math.\mathrm{released}\right)}{m\left(\mathrm{active}.Math..Math..Math.\mathrm{agent}.Math..Math.\mathrm{loaded}\right)}$ of 72%.

18. The delivery system according to claim 16, wherein the delivery system provides a release efficiency for the one or more active agent(s) of 80%.

19. The delivery system according to claim 16, wherein the release efficiency is attained within a time period of 15 min.

20. The carrier material according to claim 1, wherein the magnesium carbonate has a specific surface area in the range from 35 to 120 m.sup.2/g, measured using nitrogen and the BET method according to ISO 9277:2010.

21. The carrier material according to claim 2, wherein the magnesium carbonate has an intra-particle intruded specific pore volume in the range from 1.1 to 2.1 cm.sup.3/g, calculated from mercury porosimetry measurement.

22. The delivery system according to claim 7, wherein the delivery system comprises the one or more active agent(s) in an amount ranging from 40 to 290 wt.-%, based on the total weight of the carrier material.

23. The delivery system according to claim 7, wherein the delivery system comprises the one or more active agent(s) in an amount ranging from 90 to 200 wt.-%, based on the total weight of the carrier material.

Description

EXAMPLES

[0191] In the following, measurement methods implemented in the examples are described.

Particle Size Distribution

[0192] 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 and the system was ultrasonicated at the 40% setting for 1 min. 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 with the Fraunhofer assumption 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)

[0193] The specific surface area was measured via the BET method according to ISO 9277:201 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 100 C. for a period of 120 min prior to measurement.

Intra-Particle Intruded Specific Pore Volume (in Cm.SUP.3./g)

[0194] 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 m (nm). The equilibration time used at each pressure step was 20 seconds. The sample material was sealed in a 3 cm.sup.3 chamber powder penetrometer for analysis. The data were 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, p1753-1764.).

[0195] The total pore volume seen in the cumulative intrusion data can be separated into two regions with the intrusion data from 208 m down to about 1-4 m showing the coarse packing of the sample between any agglomerate structures contributing strongly. Below these diameters lies the fine inter-particle packing of the particles themselves. If they also have intra-particle 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 intra-particle 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.

[0196] 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 inter-particle pore region and the intra-particle pore region, if present. Knowing the intra-particle pore diameter range it is possible to subtract the remainder inter-particle and inter-agglomerate 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.

Chemical Oxygen Demand Analysis

[0197] For chemical oxygen demand (COD) analysis, suspensions were filtered (Chromafil Xtra RC-20/25 syringe filter) and adequately diluted for the analysis. Active concentrations were determined using a cell test (according to ISO 15705; Spectroquant for non Merck photometers; 0-1500 mg L.sup.1) in an Aqualytics COD250 vario photometer. For each sample, 5 readings were taken and the result averaged. The concentration of the samples was calculated based on a calibration curve with previously prepared standard solutions.

1. Carrier Materials

[0198] PHM-A and PHM-B are precipitated hydromagnesites produced by Omya International AG based on published protocols (see e.g. M. Pohl, C. Rainer, M. Esser; Omya Development AG, EP2322581 (A1)). MgCO.sub.3 light (Magnesium carbonate, light) and MgCO.sub.3, heavy (Magnesium carbonate, heavy) were purchased from Sigma-Aldrich. Dolomite (Microdol 200 KN) is a natural Dolomite supplied by Omya International AG.

TABLE-US-00001 TABLE 1 Properties of used carrier materials Intra-particle intruded specific d.sub.50(vol) d.sub.98(vol) SSA pore volume Products (m) (m) (m.sup.2/g) (cm.sup.3/g) PHM-A 8.4 91.3 58.8 1.293 PHM-B 22 63 39.5 1.711 MgCO.sub.3, light 9.8 30 33.3 1.069 MgCO.sub.3, heavy 27 76 16.5 0.610 Dolomite 2.2 9.8 5.00 0.00

2. Other MaterialsTradenames/Suppliers

[0199]

TABLE-US-00002 TABLE 2 List of active agents utilized for the loading trials Trade name Characterization Role CAS Registry Suppliers Hoesch sodium Anionic 25155-30-0 1) AE 50 dodecylbenzenesulfonate surfactant solution (50 wt. %) Sokalan copolymer from maleic acid Softener 52255-49-9 2) CP 5 and acrylic acid, sodium salt Sokalan acrylic acid homopolymer, Anti-scaling 68479-09-4 2) PA 25 sodium salt (50 wt. %) agent Na.sub.4HEDP tetrasodium etidronate Complexing 3794-83-0 3) agent Lutensol alkoxylated C12-15 alcohols Nonionic 68002-97-1 2) AO 3 surfactant Plurafac modified fatty alcohol Nonionic not 2) LF 731 alkoxylate, in water, surfactant available predominantly unbranched fatty alcohols Trilon M sodium methylglycine Builder 164462-16-2 4) diacetate Sequestrant Pluriol E Polyethylene glycol, molar Dispersant 25322-68-3 2) 4000 mass ca. 4000 g/mol 1) Hoesch 2) BASF 3) Biesterfeld 4) Coatex

3. Loading of the Carrier Materials

[0200] For loading experiments, 10 g of the carrier material was weighed into a beaker and mechanically stirred. Then, the desired amount of active solution was added drop-wise using a pipette. Solid actives were dissolved in water at a suitable concentration before the loading procedure. The nominal loading of actives was calculated according to equation (1).

[00003]$\begin{array}{cc}\mathrm{Loading}.Math.\left[\%\right]=\frac{\mathrm{mass}.Math..Math.\mathrm{of}.Math..Math.\mathrm{surfactant}.Math.\left[g\right]}{\mathrm{mass}.Math..Math.\mathrm{of}.Math..Math.\mathrm{powder}.Math.\left[g\right]}.Math.100& \left(I\right)\end{array}$

TABLE-US-00003 TABLE 3 Preparation of delivery systems Trial Carrier material Active agent Loading (%) A.1 PHM-A Hoesch AE 50 100 A.2 PHM-A Plurafac LF 731 100 A.3 PHM-A Lutensol AO 3 100 A.4 PHM-A HEDP 100 A.5 PHM-A Pluriol E 4000 100 A.6 PHM-A Trilon M 100 B.1 PHM-B Hoesch AE 50 150 B.2 PHM-B Hoesch AE 50 125 B.3 PHM-B Hoesch AE 50 100 B.4 PHM-B Plurafac LF 731 150 B.5 PHM-B Plurafac LF 731 125 B.6 PHM-B Lutensol AO 3 150 B.7 PHM-B HEDP 150 B.8 PHM-B Pluriol E 4000 150 B.9 PHM-B Trilon M 150 C.1 MgCO.sub.3, light Plurafac LF 731 100 D.1 (comparative) MgCO.sub.3, heavy Plurafac LF 731 20 E.1 (comparative) Dolomite Plurafac LF 731 1

[0201] Comparison of the data in Tables 1 and 3 evidences that carrier materials providing a high BET surface (25 m.sup.2/g) optionally in combination with a high intra-particle intruded specific pore volume (0.9 cm.sup.3/g) can accommodate higher loadings of actives (100%) compared to their counterparts having lower surface areas or porosity (Experiments D.1 and E.1). This translates into a technical advantage, as the quantity of carrier material required to convey a specific quantity of an active agent is reduced.

4. Release Trials with the Loaded Carrier Materials (Delivery Systems)

[0202] For release trials, the amount of active-loaded carrier materials required to achieve the indicated concentration was dispersed in 1 L demineralized water for 10 min at room temperature. Subsequently, an aliquot was taken and the concentration of the active was determined by COD analysis as detailed above. The release efficiency was calculated according to equation (II).

[00004]$\begin{array}{cc}R.Math.\mathrm{elease}.Math..Math.\mathrm{efficiency}.Math.\left[\%\right]=\frac{\begin{array}{c}\mathrm{concentration}.Math..Math.\mathrm{of}.Math..Math.\mathrm{active}.Math.\\ \mathrm{in}.Math..Math.\mathrm{solution}.Math.\left[g.Math..Math.L^{-1}\right].Math.\end{array}.Math.}{\begin{array}{c}\mathrm{concentration}.Math..Math.\mathrm{of}.Math..Math.\mathrm{active}\\ .Math.\mathrm{introduced}.Math.\left[g.Math..Math.L^{-1}\right]\end{array}.Math.}.Math.100& \left(\mathrm{II}\right)\end{array}$

TABLE-US-00004 TABLE 5 Release trials conducted with loaded carrier materials Active Release Loaded carrier concentration efficiency Trial material (g L.sup.1) (%) A.A A.1 0.63 48.8 A.B A.2 0.25 73.2 A.C A.3 0.53 63.4 A.D A.4 0.063 96.2 A.E A.5 0.063 90.1 A.F A.6 2.0 98.3 B.A B.1 0.63 80.7 B.B B.2 0.63 75.9 B.C B.3 0.63 74.9 B.D B.4 0.25 87.1 B.E B.5 0.25 93.2 B.F B.6 0.53 81.7 B.G B.7 0.063 90.8 B.H B.8 0.063 104 B.I B.9 2.0 98.6 C.A C.1 0.25 58.9 D.A (comparative) D.1 0.25 71.0 E.A (comparative) E.1 0.25 36.1

[0203] Comparison of the data in Tables 1 and 5 evidences that carrier materials providing a high BET surface (25 m.sup.2/g) optionally in combination with a high intra-particle intruded specific pore volume (0.9 cm.sup.3/g) can attain higher release efficiencies compared to their counterparts having lower surface areas or porosity (Experiment E.1). This translates into a technical advantage, as the quantity of active agent required to convey a specific concentration of active is reduced.