阅读说明：本技术 作为用于释放家用护理制剂中的一种或更多种活性剂的载体材料的经表面反应的碳酸镁 (Surface-reacted magnesium carbonate as a carrier material for the release of one or more active agents in home care formulations ) 是由 托比亚斯·谢勒 塞缪尔·伦奇 塔尼娅·布德 于 2020-04-30 设计创作，主要内容包括：本发明涉及经表面反应的碳酸镁、包含所述经表面反应的碳酸镁的用于释放家用护理制剂中的一种或更多种活性剂的递送体系、包括用于释放一种或更多种活性剂的所述递送体系的家用护理制剂、用于制备所述经表面反应的碳酸镁的方法和用于制备用于释放家用护理制剂中的一种或更多种活性剂的所述递送体系的方法、以及所述经表面反应的碳酸镁作为用于释放家用护理制剂中的一种或更多种活性剂的载体材料的用途和所述递送体系用于释放家用护理制剂中的一种或更多种活性剂的用途。(The present invention relates to a surface-reacted magnesium carbonate, a delivery system for releasing one or more active agents in a home care formulation comprising the surface-reacted magnesium carbonate, a home care formulation comprising the delivery system for releasing one or more active agents, a process for preparing the surface-reacted magnesium carbonate and a process for preparing the delivery system for releasing one or more active agents in a home care formulation, as well as the use of the surface-reacted magnesium carbonate as a carrier material for releasing one or more active agents in a home care formulation and the use of the delivery system for releasing one or more active agents in a home care formulation.)

1. A surface-reacted magnesium carbonate, wherein the surface-reacted magnesium carbonate is obtained by treating the surface of magnesium carbonate with one or more compounds selected from the group consisting of: sulfuric acid; phosphoric acid; carbonic acid; a carboxylic acid comprising up to six carbon atoms, preferably selected from formic acid, acetic acid, propionic acid, lactic acid, and mixtures thereof; and di-and tricarboxylic acids in which the carboxylic acid groups are connected by a chain of 0 to 4 intervening carbon atoms, the di-and tricarboxylic acids preferably being selected from oxalic acid, citric acid, succinic acid, maleic acid, malonic acid, tartaric acid, adipic acid, fumaric acid, and mixtures 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)₃) Hydromagnesite (Mg)₅(CO₃)₄(OH)₂·4H₂O), Long-noded magnesite (Mg)₂(CO₃)(OH)₂·3H₂O), 15-ball carbon magnesium stone (Mg)₅(CO₃)₄(OH)₂·5H₂O), isohydromagnesite (Mg)₅(CO₃)₄(OH)₂·5H₂O), magnesium leucomalachite (Mg)₂(CO₃)(OH)₂·0.5H₂O), brucite (MgCO)₃·2H₂O), magnesium pentahydrate (MgCO)₃·5H₂O), dolomite carbonate and magnesite trihydrate (MgCO)₃·3H₂O)。

3. The surface-reacted magnesium carbonate according to claim 1 or 2, wherein the magnesium carbonate has

a) Using nitrogen and according to ISO9277: measured at 10m by the BET method of 2010²G to 100m²Per g, preferably 12m²G to 50m²/g, and most preferably 17m²G to 40m²BET specific surface area in the range of/g; and/or

b) Calculated at 0.9cm by mercury porosimetry measurement³G to 2.3cm³G, preferably 1.2cm³G to 2.1cm³In g, and most preferably 1.5cm³G to 2.0cm³Specific pore volume of intragranular invasion in the range of/g; and/or

c) D in the range of 1 μm to 75 μm, preferably 1.2 μm to 50 μm, more preferably 1.5 μm to 30 μm, even more preferably 1.7 μm to 15 μm, and most preferably 1.9 μm to 10 μm, as determined by laser diffraction₅₀(volume), and/or

d) D in the range of 2 μm to 150 μm, preferably 4 μm to 100 μm, more preferably 6 μm to 80 μm, even more preferably 8 μm to 60 μm, and most preferably 10 μm to 40 μm as determined by laser diffraction₉₈(volume).

4. The surface-reacted magnesium carbonate according to any of the preceding claims, wherein the magnesium carbonate has an intra-particle intrusion specific pore volume calculated from mercury porosimetry measurements in combination with the use of nitrogen and a reaction temperature according to ISO9277: a ratio of BET specific surface area measured by BET method of 2010 of more than 0.01cm³/m²Preferably greater than 0.05cm³/m²And most preferably greater than 0.06cm³/m²For example, 0.06cm³/m²To 0.25cm³/m²。

5. The surface-reacted magnesium carbonate according to any of the preceding claims, wherein the magnesium carbonate comprises up to 25000ppm Ca²⁺Ions.

6. The surface-reacted magnesium carbonate according to any of the preceding claims, wherein the surface-reacted magnesium carbonate is obtained by treating the surface of the magnesium carbonate with the one or more compounds or their respective salts in an amount of 0.1 to 20 wt. -%, based on the total dry weight of the magnesium carbonate.

7. Surface-reacted magnesium carbonate according to any of the preceding claims, being a carrier material for the release of one or more active agents in a home care formulation.

8. A delivery system for the release of one or more active agents in a home care formulation, the delivery system comprising a surface-reacted magnesium carbonate according to any one of the preceding claims and one or more active agents supported on a carrier material.

9. The delivery system according to claim 8, wherein the one or more active agents are loaded on and/or into the pore space of the surface-reacted magnesium carbonate.

10. The delivery system according to claim 8 or 9, wherein the one or more active agents are selected from the group of active agents mentioned in the european parliament and council on detergents regulation (EC) No. 648/2004, 3/31/2004, preferably the one or more active agents are selected from the group comprising: anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, phosphate esters, phosphonate esters, softeners, chelants, builders, processing aids, enzymes, oxygen-based bleaches, chlorine-based bleaches, soil resists, complexing agents, dispersants, nitrilotriacetic acid and its salts, phenols, halogenated phenols, p-dichlorobenzene, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, soaps, zeolites, polycarboxylates, disinfectants, optical brighteners, defoamers, colorants, fragrances, and mixtures thereof.

11. The delivery system according to any one of claims 8 to 10, wherein the delivery system comprises the one or more active agents in an amount within the following ranges, based on the total weight of the carrier material: 10 to 300 wt%, preferably 40 to 290 wt%, more preferably 60 to 280 wt%, and most preferably 80 to 260 wt%, for example 90 to 200 wt%.

12. The delivery system according to any one of claims 8 to 11, wherein the delivery system is in the form of a free-flowing powder, tablet, pellet or granule, preferably in the form of a free-flowing powder.

13. A home care formulation comprising a delivery system for release of one or more active agents according to any one of claims 8 to 12.

14. The home care formulation of claim 13, wherein the formulation is in the form of a liquid, free flowing powder, paste, gel, stick, block, pouch, or molded piece, such as a tablet.

15. The home care formulation according to claim 13 or 14, wherein the formulation is a washing formulation, preferably a washing formulation for laundry, fabric, ware and hard surface cleaning; pre-washing the formulation; rinsing the formulation; a bleaching agent; laundry fabric softener formulations; cleaning the formulation; and mixtures thereof.

16. A process for the preparation of a surface-reacted magnesium carbonate according to any of claims 1 to 7, comprising at least the steps of:

i) providing magnesium carbonate, namely providing magnesium carbonate,

ii) providing one or more compounds selected from the group consisting of: sulfuric acid; phosphoric acid; carbonic acid; a carboxylic acid comprising up to six carbon atoms, preferably selected from formic acid, acetic acid, propionic acid, lactic acid, and mixtures thereof; and dicarboxylic acids and tricarboxylic acids in which the carboxylic acid groups are linked by a chain of 0 to 4 intervening carbon atoms, the dicarboxylic acids and tricarboxylic acids preferably being selected from oxalic acid, citric acid, succinic acid, maleic acid, malonic acid, tartaric acid, adipic acid, fumaric acid, and mixtures thereof, and

iii) treating the surface of the magnesium carbonate of step a) with the one or more compounds of step b) or their respective salts under mixing in one or more steps such that a reaction is achieved by the one or more compounds or their respective salts and the surface of the magnesium carbonate.

17. A process for preparing a delivery system for release of one or more active agents in a home care formulation according to any one of claims 8 to 12, the process comprising the steps of:

a) providing a surface-reacted magnesium carbonate obtained by treating the surface of magnesium carbonate with one or more compounds selected from the group consisting of: sulfuric acid; phosphoric acid; carbonic acid; a carboxylic acid comprising up to six carbon atoms, preferably selected from formic acid, acetic acid, propionic acid, lactic acid, and mixtures thereof; and dicarboxylic acids and tricarboxylic acids in which the carboxylic acid groups are linked by a chain of 0 to 4 intervening carbon atoms, the dicarboxylic acids and the tricarboxylic acids preferably being selected from oxalic acid, citric acid, succinic acid, maleic acid, malonic acid, tartaric acid, adipic acid, fumaric acid, and mixtures thereof,

b) providing one or more active agents in liquid form or dissolved in a solvent,

c) contacting the surface-reacted magnesium carbonate of step a) with the one or more active agents of step b), and

d) optionally, if a solvent is used in step b), the solvent is removed by evaporation.

18. Use of a surface-reacted magnesium carbonate according to any of claims 1 to 7 as a carrier material for the release of one or more active agents in a home care formulation.

19. Use of a delivery system according to any of claims 8 to 12 for releasing one or more active agents in a home care formulation.

Examples

1. Measuring method

Hereinafter, the measurement method implemented in the examples is described.

Particle size distribution

Volume-defined median particle size d₅₀(volume) and volume-determined top-cut particle size d₉₈Volume was evaluated using a Malvern Mastersizer 3000 laser diffraction system (Malvern Instruments plc, uk) equipped with a Hydro LV system. d₅₀(volume) value or d₉₈The (volume) values represent diameter values: which is such that 50% or 98% by volume of the particles have a diameter less than this value, respectively. Suspending the powder in 0.1 wt% Na₄O₇P₂In solution. 10mL of 0.1 wt% Na₄O₇P₂Added to the Hydro LV tank and then the sample slurry was introduced until a 10% to 20% blur was reached. The measurements were performed for 10 seconds with each of the red and blue light. For the analysis of the raw data, a model for non-spherical particle size using the mie theory was utilized and it was assumed that the particle refractive index was 1.57 and the density was 2.70g/cm³And an absorption index of 0.005. The methods and apparatus are known to the skilled person and are generally used to determine the particle size distribution of fillers and pigments.

Specific Surface Area (SSA)

Measurement of a ratiometric chart on a Micromeritics ASAP 2460 instrument from Micromeritics via the BET method according to ISO9277:2010 using nitrogen as adsorption gasArea. Before measurement, under vacuum (10)^-5Bar) samples were pretreated by heating at 150 ℃ for a period of 60 minutes.

Porosity determination method

Specific pore volume was measured using a Micromeritics Autopore V9620 mercury porosimeter with maximum applied pressure of mercury of 414MPa (60000psi) (equivalent to a Laplace throat diameter of 0.004 μm (. about.nm)) using mercury intrusion porosimetry measurements. The equilibration time used for each pressure step was 20 seconds. Sealing the sample material at 3cm³Chamber powder penetrometer for analysis. Data for mercury compression, penetrometer expansion and sample material compression were corrected using the software Pore-Comp (gain, p.a.c., key, j.p., Matthews, g.p., and Ridgway, c.j., "volume Space Structure of compressive polymers Spheres and coherent Calcium Carbonate Paper-Coating Formulations", Industrial and Engineering Chemistry Research,35(5),1996, pages 1753 to 1764).

The total pore volume seen in the cumulative invasion data can be divided into two regions, with invasion data from 214 μm down to about 1 μm to 4 μm showing that coarse packing of the sample between any agglomerated structures plays an important role. Below these diameters is the fine interparticle packing of the particles themselves. If they also have intraparticle pores, then the region appears bimodal, and the specific intraparticle pore volume is defined by taking the specific pore volume from the intrusion of mercury into pores finer than the peak inflection point (i.e., finer than the bimodal inflection point). The sum of these three regions gives the total pore volume of the powder, but strongly depends on the initial sample compaction/settling of the powder at the end of the coarse pores of the distribution.

By taking the first derivative of the cumulative invasion curve, a pore size distribution based on equivalent laplace diameters that inevitably includes pore shielding is revealed. The differential curves clearly show the coarse agglomerate pore structure region, the interparticle pore region and, if present, the intraparticle pore region. Knowing the intra-particle pore diameter range, the remaining inter-particle pore volume and inter-agglomerate pore volume can be subtracted from the total pore volume to give the desired pore volume of the inner pores alone, in terms of pore volume per unit mass (specific pore volume). Of course, the same principles of subtraction apply to separating any other pore size region of interest.

Amount of surface treatment layer

The amount of the treated layer on the material containing magnesium ions and/or calcium ions is theoretically calculated from the BET value of the untreated material containing magnesium ions and/or calcium ions and the amount of the compound or compounds used for the surface treatment. It is assumed that 100% of the one or more compounds are present as a surface treatment layer on the surface of the material comprising magnesium ions and/or calcium ions.

2. Materials used

The materials used in the present invention have the characteristics set forth in table 1 below.

Table 1: characterization of magnesium carbonate

For the surface reaction, 11L of a 10 wt% slurry of hydromagnesite (# a) was prepared. To this slurry was added the desired amount of sodium sulfate (. gtoreq.99%, Sigma Aldrich, 238597-1KG) or sodium dihydrogen citrate (99%, Sigma-Aldrich, 234265-1KG) to obtain a nominal loading of 5 wt% based on the dry weight of hydromagnesite. The slurry was stirred at room temperature for 1 hour, followed by spray drying in a GEA Niro A/S spray dryer with an inlet temperature of 270 ℃ and an outlet temperature of 110 ℃. Throughout the report, the surface treated samples were referred to as Citr/hydromagnesite (# a1) and Sulph/hydromagnesite (# a2), respectively, for samples reacted with sodium sulfate and sodium dihydrogen citrate. The characteristics of the obtained surface-reacted samples are also set forth in table 1.

3. Loading and Release experiments

Load-release experiments were performed using Hoesch AE 50, typically using sodium dodecylbenzenesulfonate surfactant for dishwashing. For the load test, the desired amount of magnesium carbonate (10g) was weighed into a beaker. Subsequently, the surfactant (10g) was added dropwise using a pipette. The amount added was monitored gravimetrically. The magnesium carbonate and liquid were mixed thoroughly for 5 minutes. According to the computational load detailed in equation (1).

For the release experiments, the loaded sample (0.5g) was dispersed in water (1L) at room temperature for 1 hour using a magnetic stirrer (300 rpm). The amount of sample loaded was selected to obtain 0.25g L based on 100% recovery^-1Hoesch AE 50 at concentration of (a). The suspension was then filtered using a syringe filter (0.2 μm). The concentration of surfactant in the liquid was determined by UV spectroscopic evaluation in a Hach Lange DR6000 spectrophotometer based on the absorbance at wavelength λ 224 nm. Concentrations were calculated based on the corresponding calibration curves for 5 samples of known concentration.

All samples were loaded with 100 wt% surfactant and were at 0.25g L^-1The release test is performed at a target concentration that represents an approximation of the surfactant concentration in an actual wash test. Recovery of surfactant is defined as the amount measured in solution using UV-VIS spectroscopy divided by the theoretical amount introduced. The load utilized and corresponding release data for all samples are provided in table 2 below.

Table 2: load and release (recovery) data for samples tested

^aCalculated values based on recorded weight

All samples were tested at the same concentration and loading to facilitate direct comparison between materials.

It should be considered that for a given material a higher loading results in a higher recovery and therefore the selection of the best magnesium carbonate should be made under consideration of the maximum obtainable loading.

As can be seen from table 2, comparative material # a achieved about 60% recovery in the case of surfactant. In contrast, if the surface of the same magnesium carbonate is treated with 5 wt% sodium citrate, the recovery of surfactant increases to about 83% (see sample # a 1). Although this difference may sound small, it essentially means that the amount of "lost" surfactant is reduced by 57.5%. Without wishing to be bound by theory, it is hypothesized that sodium citrate adsorbs on the surface, thereby quenching the acidic surface of the magnesium carbonate. A similar effect was observed for sodium sulfate, with recovery increased to about 81% (see sample # a 2).

In view of this, the surface-reacted magnesium carbonate according to the invention provides for increased recovery of surfactant.

4. Application test in automated dishwashing

4.1 dishwashing formulations

As summarized in table 3, two formulations were prepared for the automated dish wash test. Formulation # F1 is similar to a commercial all-in-one dishwashing powder, and the corresponding raw materials are well known to those skilled in the art. The surfactants used are nonionic low-foaming surfactants based on modified fatty alcohol polyglycol ethers. The complexing agent is dicarboxymethylalaninate. The builder used is a mixture of sodium carbonate and citric acid.

Formulation # F2 is an exact replica of formulation # F1, except that the amount of surfactant and complexing agent is reduced and the amount of hydromagnesite loaded is correspondingly increased so that the amount of surfactant in the formulation remains the same.

Table 3: composition of tableware washing preparation

Material	#F1	#F2
			Surface active agent	3% by weight	-
Loaded hydromagnesite	-	6% by weight
			Complexing agents	10% by weight	7% by weight
Builder	50% by weight	50% by weight
			Enzyme	1% by weight	1% by weight
Adding additives	5% by weight	5% by weight
			Sodium sulfate	31% by weight	31% by weight

4.2 preparation of loaded hydromagnesite

Hydromagnesite # A3 (Sulph/hydromagnesite) was loaded with 100.1% by weight of the modified fatty alcohol polyglycol ether based nonionic low-foaming surfactant used for the preparation of the dishwashing formulation # F1. The loading was carried out by adding preheated surfactant (60 ℃) to preheated hydromagnesite (60 ℃) and stirring in a Somakon laboratory mixer (500 rpm).

4.3 drying Property test

The drying performance of formulation # F1 and formulation # F2 was evaluated in a dedicated dishwashing test. The test conditions are summarized in table 4.

Table 4: drying performance test conditions and evaluations.

Prior to testing, the ware was pre-washed with alkali and citric acid and rinsed with water. The ion exchanger of the dishwasher is deactivated and water is supplied through the external tank. The 3-in-1 function is rendered ineffective by filling the rinse aid dispersant with water. The front door was kept closed for 30 minutes after completion of the procedure, after which the door was fully opened and the evaluation started. The arithmetic mean of three replicates is reported. The results are summarized in Table 5. The difference ≧ 1 was considered significant.

Table 5: and (5) drying performance test results.

Material	Porcelain ware	Glass	Plastic material	Stainless steel	Mean value of
						#F1	0.6	0.1	3.8	0.0	1.1
#F2	0.3	0.0	0.7	0.0	0.2

As can be derived from the data in table 5, the drying properties of the plastic are significantly improved, while the properties are otherwise unchanged.

4.4 rinse-aid Performance test

The rinse aid performance of formulation # F1 and formulation # F2 was evaluated in a dedicated dishwashing test. The test conditions are summarized in table 6.

Table 6: rinse aid test conditions and evaluation.

Glasses, dishes and cutlery were pre-washed with neodissher detergent commercially available from dr. weibert in combination with citric acid and two cycles with test detergent. The ion exchanger of the dishwasher is deactivated and water is supplied through the external tank. The 3-in-1 function is rendered ineffective by filling the rinse aid dispersant with water. The front door is kept closed for 10 minutes after the procedure is completed, and then the door is fully opened and the dish rack is fully pulled out. Evaluation was started after 20 minutes. The arithmetic mean of three replicates is reported. The results are summarized in table 7. The difference ≧ 0.9 was considered significant.

Table 7: and (5) a rinsing assistant performance test result.

Effect	Film forming	Get up dirty spot
			#F1	4.6	6.9
#F2	4.1	6.9

As can be derived from the data in table 7, the rinse aid performance was comparable for both formulations.

4.5 cleaning Performance test

The cleaning performance of formulation # F1 and formulation # F2 was evaluated in a dedicated dishwashing test. The test conditions are summarized in table 8.

Table 8: cleaning performance test conditions and evaluations.

The arithmetic mean of 30 trials is reported. The results are summarized in Table 9. The difference ≧ 0.9 was considered significant.

Table 9: and (5) cleaning performance test results.

As can be derived from the data in table 9, the cleaning performance was comparable for both formulations. However, in the case of tea, the comparative sample performed slightly better.