阅读说明：本技术 作为口腔护理组合物中的白色颜料的经表面处理的含镁离子或含钙离子材料 (Surface treated magnesium ion-containing or calcium ion-containing materials as white pigments in oral care compositions ) 是由 托比亚斯·谢勒 塔尼娅·布德 塞缪尔·伦奇 于 2020-04-22 设计创作，主要内容包括：本发明涉及经表面处理的含镁离子材料,所述经表面处理的含镁离子材料通过用选自以下的一种或更多种化合物处理含镁离子材料的表面而获得：磷酸、多磷酸盐、包含最多至六个碳原子的羧酸、其中羧酸基团由0至4个间断碳原子的链连接的包含最多至六个碳原子的二羧酸和三羧酸、水不溶性聚合物、水不溶性蜡、含硅酸盐/酯基团和/或铝酸盐基团的化合物、及其相应的盐。本发明还涉及包含经表面处理的含镁离子材料和/或经表面处理的含钙离子材料的口腔护理组合物,以及经表面处理的含镁离子材料和/或经表面处理的含钙离子材料在口腔护理组合物中作为乳浊剂和/或增白色素的用途或用于改善氟离子的利用率的用途。(The present invention relates to a surface-treated magnesium ion-containing material obtained by treating a surface of a magnesium ion-containing material with one or more compounds selected from the group consisting of: phosphoric acid, polyphosphates, carboxylic acids containing up to six carbon atoms, di-and tricarboxylic acids containing up to six carbon atoms in which the carboxylic acid groups are linked by a chain of 0 to 4 interrupted carbon atoms, water-insoluble polymers, water-insoluble waxes, compounds containing silicate/ester and/or aluminate groups, and the corresponding salts thereof. The present invention also relates to oral care compositions comprising surface treated magnesium ion containing material and/or surface treated calcium ion containing material and the use of the surface treated magnesium ion containing material and/or surface treated calcium ion containing material in oral care compositions as an opacifying agent and/or whitening pigment or for improving the availability of fluoride ions.)

1. A surface-treated magnesium ion-containing material obtained by treating a surface of a magnesium ion-containing material with one or more compounds selected from the group consisting of: phosphoric acid, polyphosphates, carboxylic acids containing up to six carbon atoms, di-and tricarboxylic acids containing up to six carbon atoms in which the carboxylic acid groups are linked by a chain of 0 to 4 interrupted carbon atoms, water-insoluble polymers, water-insoluble waxes, compounds containing silicate/ester and/or aluminate groups, and the corresponding salts thereof.

2. The surface-treated magnesium-ion containing material of claim 1, wherein the magnesium-ion containing material is selected from anhydrous magnesium carbonate or magnesite (MgCO)₃) Hydromagnesite (Mg)₅(CO₃)₄(OH)₂·4H₂O), Long-noded magnesite (Mg)₂(CO₃)(OH)₂·3H₂O), magnesium carbide (Mg)₅(CO₃)₄(OH)₂·5H₂O), isohydromagnesite (Mg)₅(CO₃)₄(OH)₂·5H₂O), semi-hydrated magnesium carbonate (Mg)₂(CO₃)(OH)₂·0.5H₂O), brucite (MgCO)₃·2H₂O), magnesium pentahydrate (MgCO)₃·5H₂O), magnesium hydrogen carbonate (MgCO)₃·3H₂O), brucite (Mg (OH)₂) Dolomite (CaMg (CO)₃)₂) Dolomite carbonate and mixtures thereof, preferably selected from anhydrous magnesium carbonate or magnesite (MgCO)₃) Dolomite (CaMg (CO)₃)₂) Hydromagnesite (Mg)₅(CO₃)₄(OH)₂·4H₂O), brucite (Mg (OH)₂) And mixtures thereof.

3. The surface treated magnesium-ion containing material of claim 1 or 2, wherein the magnesium-ion containing material is in the form of particles having:

a) a volume median particle diameter (d) of 150nm or more, preferably 150nm to 40 μm, more preferably 0.2 μm to 35 μm, even more preferably 0.3 μm to 30 μm, and most preferably 0.4 μm to 27 μm as determined by laser diffraction₅₀) And/or

b) Top cut particle size (d) determined from a volume determined by laser diffraction equal to or less than 100 μm, preferably from 1 μm to 90 μm, more preferably from 1.5 to 85, and most preferably from 1.5 μm to 80 μm₉₈)。

4. The surface treated magnesium-ion containing material of any of the preceding claims, wherein the magnesium-ion containing material is in the form of particles that are modified according to ISO9277:2010 BET specific surface area of 2m measured using nitrogen and the BET method²G to 200m²In g, preferably 2m²G to 100m²G, and most preferably 3m²G to 75m²In the range of/g.

5. The surface treated magnesium-ion containing material of any of the preceding claims, wherein the magnesium-ion containing material comprises up to 25000ppm of Ca²⁺Ions.

6. The surface treated magnesium-ion containing material of any of the preceding claims, wherein the surface treated magnesium-ion containing material is obtained by treating the surface of the magnesium-ion containing material with the one or more compounds in an amount of 0.1 to 25 wt.% based on the total dry weight of the magnesium-ion containing material.

7. The surface treated magnesium ion containing material according to any of the preceding claims, wherein the compound comprising silicate/ester groups and/or aluminate groups is selected from the group comprising alkali metal silicates, alkali metal aluminates, silicon alkoxides and aluminium alkoxides, preferably selected from sodium silicate, potassium silicate, sodium aluminate, potassium aluminate, tetramethyl orthosilicate, tetraethyl orthosilicate, aluminium methoxide, aluminium ethoxide, aluminium isopropoxide and mixtures thereof, and more preferably selected from sodium silicate, tetraethyl orthosilicate and aluminium isopropoxide.

8. An oral care composition comprising a surface-treated magnesium-ion containing material and/or a surface-treated calcium-ion containing material, the surface-treated magnesium-ion containing material being obtained by treating a surface of a magnesium-ion containing material with one or more compounds selected from the group consisting of: phosphoric acid, polyphosphates, carboxylic acids comprising up to six carbon atoms, di-and tricarboxylic acids comprising up to six carbon atoms in which the carboxylic acid groups are connected by a chain of 0 to 4 interrupted carbon atoms, water-insoluble polymers, water-insoluble waxes, compounds comprising silicate/ester groups and/or aluminate groups, and corresponding salts thereof, the surface-treated calcium-ion containing material being obtained by treating the surface of the calcium-ion containing material with one or more compounds selected from the group consisting of: polyphosphates, carboxylic acids comprising up to six carbon atoms, di-and tricarboxylic acids comprising up to six carbon atoms in which the carboxylic acid groups are linked by a chain of 0 to 4 interrupted carbon atoms, water-insoluble polymers, water-insoluble waxes, compounds containing silicate/ester and/or aluminate groups, and the corresponding salts thereof.

9. The oral care composition according to claim 8, wherein the oral care composition further comprises a fluoride compound, preferably the fluoride compound is selected from the group consisting of sodium fluoride, stannous fluoride, sodium monofluorophosphate, potassium fluoride, potassium stannous fluoride, sodium fluorostannate, stannous chlorofluoride, amine fluoride, and mixtures thereof, and more preferably the fluoride compound is sodium monofluorophosphate and/or sodium fluoride.

10. The oral care composition according to claim 8 or 9, wherein the oral care composition further comprises a remineralizing and/or whitening agent, preferably selected from silica; hydroxyapatite, such as nano-hydroxyapatite; calcium carbonates, such as amorphous calcium carbonate, ground calcium carbonate, precipitated calcium carbonate, surface-reacted calcium carbonate, and combinations thereof; calcium silicate; and mixtures thereof.

11. The oral care composition according to any one of claims 8 to 10, wherein the oral care composition is a toothpaste, tooth gel, tooth powder, varnish, adhesive gel, cement, resin, spray, foam, balm, composition on a buccal strip or an oral adhesive patch, chewable tablet, chewable lozenge, chewing gum, lozenge, beverage or mouthwash, preferably chewing gum, lozenge, toothpaste, tooth powder or mouthwash, and most preferably a toothpaste.

12. The oral care composition according to any one of claims 8 to 11, wherein the pH of the oral care composition is from 6.8 to 10, preferably from 7.5 to 9, and most preferably from 8 to 9.

13. The oral care composition according to any one of claims 8 to 12, wherein the oral care composition comprises the surface-treated magnesium-containing ionic material and/or the surface-treated calcium-containing ionic material in an amount of from 0.1 to 40 weight%, preferably from 0.5 to 10 weight%, based on the total weight of the composition.

14. Use of a surface-treated magnesium ion-containing material and/or a surface-treated calcium ion-containing material as an opacifying agent and/or whitening pigment in an oral care composition, wherein the surface-treated magnesium ion-containing material is obtained by treating the surface of a magnesium ion-containing material with one or more compounds selected from the group consisting of: phosphoric acid, polyphosphates, carboxylic acids containing up to six carbon atoms, di-and tricarboxylic acids containing up to six carbon atoms in which the carboxylic acid groups are linked by a chain of 0 to 4 interrupted carbon atoms, water-insoluble polymers, water-insoluble waxes, compounds containing silicate/ester and/or aluminate groups, and the corresponding salts thereof; and/or the surface-treated calcium ion-containing material is obtained by treating the surface of the calcium ion-containing material with one or more compounds selected from the group consisting of: polyphosphates, carboxylic acids comprising up to six carbon atoms, di-and tricarboxylic acids comprising up to six carbon atoms in which the carboxylic acid groups are linked by a chain of 0 to 4 interrupted carbon atoms, water-insoluble polymers, water-insoluble waxes, compounds containing silicate/ester and/or aluminate groups, and the corresponding salts thereof.

15. Use of a surface treated magnesium ion-containing material and/or a surface treated calcium ion-containing material for improving the utilization of fluoride ions in an oral care composition, wherein the surface treated magnesium ion-containing material is obtained by treating the surface of a magnesium ion-containing material with one or more compounds selected from the group consisting of: phosphoric acid, polyphosphates, carboxylic acids containing up to six carbon atoms, di-and tricarboxylic acids containing up to six carbon atoms in which the carboxylic acid groups are linked by a chain of 0 to 4 interrupted carbon atoms, water-insoluble polymers, water-insoluble waxes, compounds containing silicate/ester and/or aluminate groups, and the corresponding salts thereof; and/or the surface-treated calcium ion-containing material is obtained by treating the surface of the calcium ion-containing material with one or more compounds selected from the group consisting of: polyphosphates, carboxylic acids comprising up to six carbon atoms, di-and tricarboxylic acids comprising up to six carbon atoms in which the carboxylic acid groups are linked by a chain of 0 to 4 interrupted carbon atoms, water-insoluble polymers, water-insoluble waxes, compounds containing silicate/ester and/or aluminate groups, and the corresponding salts thereof.

Examples

1. Measuring method

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

Particle size distribution

The volumetrically determined median particle size d was evaluated using a Malvern Mastersizer 3000 laser diffraction system (Malvern Instruments plc, uk) equipped with a Hydro LV system₅₀(volume) and volume-determined top-cut particle size d₉₈(volume). d₅₀(volume) or d₉₈(volume) value tableThe diameter values are shown as follows: so that 50% or 98% by volume, respectively, of the diameter of the particles is smaller than this value. 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. 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's 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. Methods and apparatus are known to the skilled person and are commonly used to determine the particle size distribution of fillers and pigments.

Specific Surface Area (SSA)

Specific surface area was measured on a Micromeritics ASAP 2460 instrument from Micromeritics via the BET method using nitrogen as the adsorption gas according to ISO9277: 2010. Before measurement, the sample is placed under vacuum (10)^-5Bar) was pretreated by heating at 150 ℃ for a period of 60 minutes.

CIELAB L of particulate material

The CIELAB L of magnesium ion containing materials and other particulate materials was dry measured according to EN ISO 116644: 2010.

Fluoride utilization rate

Toothpaste was freshly prepared as an oral care composition and aged overnight (14 hours) to establish a short term balance of fluoride concentration (i.e., fluoride utilization). Extraction is carried out by diluting the toothpaste in a glass beaker with 10 times the equivalent of demineralized water (typically 3g to 5g toothpaste diluted with 30g of 50g water), followed by vigorous stirring at 800rpm for 1 hour and filtration through a syringe filter (Chromafil Xtra, RC-20/250.2 μm). Fluoride utilization was determined in a Hach-Lange DR6000 spectrophotometer using a cuvette test (Hach Lange LCK 323, fluoride 0.1ppm to 2.5ppm) after 100-fold volume dilution (Eppendorf Research Plus micropipette). The weighted number of all dilutions was recorded and these values were used to calculate the effective (free) fluoride concentration (i.e. fluoride utilization) in the original formulation. The percentage of extractable fluoride is reported relative to a baseline experiment with unmodified (base formulation) toothpaste, which is performed for each series of experiments. The results obtained with the unmodified toothpaste were multiplied by 0.98 to illustrate the dilution of the toothpaste by the addition of minerals. Some samples were added as a filter cake with a solids content of 10 to 85 wt%, taking into account the dilution that occurred when calculating fluoride utilization.

whiteness/CIELAB L of oral care composition

The respective toothpaste was transferred to a PTFE sample holder and subsequently covered with a glass plate to obtain a reproducible, flat surface. The samples were evaluated in a Datacolor ELREPHO spectrophotometer using barium sulfate as a reference material. The values reported for whiteness are the L brightness values of the CIELAB color space according to EN ISO 116644: 2010.

Opacity of oral care compositions

The corresponding toothpaste was diluted with 15 wt% demineralised water and mixed on a high speed mixer (Hauschild DAC 150.1FVZ) at 2760rpm for 20 seconds. Subsequently, a TQC AFA Compact automatic film applicator was used for 23mm seconds^-1A300 μm layer was spread on a Leneta accessibility Chart (Form 3B-H). The film was immediately covered with a clear plastic sheet to prevent drying. Based on R per area using barium sulfate as reference in Datacolor800V spectrophotometer_yCalculating a contrast value (R) from the average of three individual measurements_{y, black}/R_{y, white}*100)。

Amount of surface treatment layer

The amount of the treatment layer on the magnesium ion-containing material and/or the calcium ion-containing material is theoretically calculated from the BET value of the untreated magnesium ion-containing material and/or calcium ion-containing material and the amount of the one or more 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 magnesium-ion containing material and/or the calcium-ion containing material.

2. Preparation of the materials used and toothpaste

The particulate materials listed in table 1 have been used as the base material for the present invention.

Table 1: particulate material for use as a base material

Base material	Name (R)	Description of the invention	Trade names or suppliers
				#M1	PHM	Precipitated Hydromagnesite (PHM)	Omya International
#M2	PCC	Precipitated calcium carbonate	Omya International
				#M3	SRCC	Surface-reacted calcium carbonate	Omya International
#M4	Dolomite	Micronized dolomite, coarse	Omya International
				#M5	Dolomite 2	Micronized dolomite, fine	Omya International

The characteristics of the particulate material are listed in table 2 below.

Table 2: characteristics of particulate materials used as base materials

Artifact of incomplete depolymerization formation on a laboratory scale

The surface-treated materials were prepared according to the methods set forth in table 3 below.

Table 3: preparation of surface-treated Material

^aTreatment was carried out with both reagents (added simultaneously).^bThe treatment was carried out with two reagents (sequential addition).

The treatment methods listed in table 3 are further described in table 4 below:

table 4: surface treatment method

The surface treatment agents are described in table 5 below.

Table 5: surface treating agent used

#	Treating agent	Suppliers of goods	Description of the invention
				A1	Citric acid with a basic value	Simga-Aldrich	Citric acid sodium salt
A2	Citric acid with three alkali values	Sigma-Aldrich	Citric acid sodium salt
				A3	Valeric acid	Sigma-Aldrich	Carboxylic acids
A4	Disodium hydrogen phosphate	Sigma-Aldrich	Phosphoric acid sodium salt
				A5	Succinic acid	Sigma-Aldrich	Organic acids
A6	Maleic acid	Sigma-Aldrich	Dicarboxylic acids
				A7	Malonic acid	Sigma-Aldrich	Dicarboxylic acids
A8	L- (+) -tartaric acid	Sigma-Aldrich	Dicarboxylic acids
				A9	Adipic acid	Sigma-Aldrich	Dicarboxylic acids
A10	Fumaric acid	Sigma-Aldrich	Dicarboxylic acids
				A11	Oxalic acid	Sigma-Aldrich	Dicarboxylic acids
A12	Lanolin	Sigma-Aldrich	Natural wax
				A13	PPG 4000	Sigma-Aldrich	Polypropylene glycol
A14	Cekol 2000	CP Kelco	Carboxymethyl cellulose
				A15	Sodium polyphosphate	Sigma-Aldrich	Polyphosphate salts, sodium salts
A16	Tetraethyl orthosilicate	Sigma-Aldrich	Tetraethoxysilane
				A17	Sodium water glass	Sigma-Aldrich	Sodium silicate solution

^＊: formula M_(n+2)P_nO_(3n+1)N in (A) is an integer of 10 to 15

The surface treated material had the characteristics listed in table 6 below.

Table 6: characteristics of the surface-treated Material

Artifact of incomplete depolymerization formation on a laboratory scale

# was not characterized due to the odor of the product.

For preparing toothpaste base preparation, IKA ULTRA was usedA disperser. The ingredients in the toothpaste base formulation are listed in table 7 below. A formulation was prepared wherein the total mass was 1 kg. In a beaker, sorbitol, sodium fluoride, sodium saccharin, sodium benzoate, propylene glycol and glycerin, and cellulose gum were mixed vigorously. Subsequently, water was added and the mixture was further stirred until a homogeneous structure was obtained. Then, Sorbosil AC35 was added stepwise under vigorous stirring and further stirred until a homogeneous structure was obtained. Then, Sorbosil TC15 was added stepwise under vigorous stirring and further stirred until a uniform structure was obtained to obtain a toothpaste base formulation. Four toothpaste masterbatches were prepared from different batches of raw materials. In order to compensate for the differences that occur (particularly in terms of optical characteristics), it is classified into batch 1(# B1), batch 2(# B2), batch 3(# B3), and batch (# B4).

TABLE 7 formulation of toothpaste base formulation.

#	Composition (I)	Amount/mass equivalent
			I1	Sorbitol 70%	23.67
I2	Softened water	25.85
			I3	Phoskadent NaF	0.34
I4	Saccharin sodium salt	0.11
			I5	Sodium benzoate	0.11
I6	Propylene glycol	10.76
			I7	Glycerol	10.76
I8	Cellulose gum	0.86
			I9	Sorbosil AC35 silica	21.52
I10	Sorbosil TC15 silica	6.02
			I11	Sodium dodecyl sulfate (15% by weight solution)	1.25
I12	Fragrant spearmint	0.80

The final toothpaste is prepared in a plastic container by adding the desired amount of the corresponding base material or surface treated material (0.25g to 2g) to 25g to 30g of toothpaste base formulation. The formulations were mixed by hand using a spatula and then homogenized for 20 seconds using a high speed mixer (Hauschild DAC 150.1FVZ) at 2760rpm or dispersed aggregates using a Polytron GT 10-35 PT disperser equipped with PT-DA 30/2 EC-F250. Subsequently, the desired amount of surfactant (I11 according to the basic formulation formula in table 7) was added using an Eppendorf Research Plus micropipette and the formulation was mixed manually using a spatula. Finally, the desired amount of flavor (I12 according to the basic formulation formula in table 7) was added using an Eppendorf Research Plus micropipette and the formulation was mixed manually using a spatula.

3. Results

The prepared toothpastes were evaluated with respect to fluoride utilization, whiteness and opacity. The results are shown in Table 8 below.

Table 8: results

For comparative reasons, the results for the materials without surface treatment (base materials) are listed in table 9 below.

Table 9: results of the base Material (comparative example)

From the results, it is considered that the surface-treated material according to the present invention provides high fluoride utilization as well as high whiteness and opacity.