DRY COMPOSITIONS AND/OR EMULSIONS FOR CHEMICAL AND PHYSICAL SUN PROTECTION AND USE THEREOF

Abstract

The present invention refers to a dry composition for chemical and physical sun protection, the composition comprising at least one mineral material selected from the group consisting of surface reacted calcium carbonate and/or hydromagnesite, and from 0.1 wt.-% to 100 wt.-%, based on the dry weight of the at least one mineral material of at least one lignin. Furthermore, the present invention refers to an emulsion comprising the inventive dry composition as well as the use of the inventive emulsion for chemical and physical sun protection in a cosmetic formulation.

Claims

1. A dry composition for chemical and physical sun protection, the composition comprising a) at least one mineral material selected from the group consisting of surface reacted calcium carbonate and/or hydromagnesite, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and one or more H.sub.3O.sup.+ ion donors, wherein the carbon dioxide is formed in situ by the H.sub.3O.sup.+ ion donors treatment and/or is supplied from an external source and b) from 0.1 wt.-% to 100 wt.-%, based on the dry weight of the at least one mineral material of step a) of at least one lignin.

2. The composition according to claim 1, wherein the at least one mineral material is surface reacted calcium carbonate and/or wherein the surface reacted calcium carbonate has a) a volume median particle size d.sub.50 from 0.1 to 90 μm, preferably from 0.1 to 75 μm, more preferably from 0.5 to 50 μm, even more preferably from 1 to 40 μm and most preferably from 1.5 to 15 μm and/or b) a volume top cut (d.sub.98) of ≤100 μm, preferably ≤60 μm, more preferably ≤45 μm and most preferably ≤20 μm, and/or c) a specific surface area (BET) of from 10 to 200 m.sup.2/g, preferably from 20 to 180 m.sup.2/g, even more preferably from 25 to 160 m.sup.2/g and most preferably from 30 to 140 m.sup.2/g, measured using nitrogen and the BET method according to ISO 9277:2010.

3. The composition according to claim 1, wherein the at least one mineral material is hydromagnesite and/or wherein the hydromagnesite has a) a volume median particle size d.sub.50 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 and/or b) a volume top cut (d.sub.98) of ≤100 μm, preferably ≤60 μm, more preferably ≤45 μm and most preferably ≤20 μm, and/or c) a specific surface area (BET) of from 25 to 200 m.sup.2/g, preferably from 30 to 150 m.sup.2/g, even more preferably from 32 to 120 m.sup.2/g and most preferably from 35 to 100 m.sup.2/g, measured using nitrogen and the BET method according to ISO 9277:2010.

4. The composition according to claim 1, wherein the at least one lignin is a water soluble or water insoluble lignin selected from the group consisting of natural lignin, klason lignin, hydrolyzed lignin, milled wood lignin, soda lignin, organosolv lignin, kraft lignin, sulphonated lignin and mixtures thereof, preferably is a water-insoluble lignin selected from the group consisting of klason lignin, kraft lignin and mixtures thereof and most preferably is kraft lignin.

5. The composition according to claim 1, wherein the at least one lignin is present in the composition in an amount from 1 to 80 wt.-%, based on the dry weight of the at least one mineral material of step a), preferably in an amount of 2 to 50 wt.-%, even more preferably in an amount of 3 to 30 wt.-% and most preferably in an amount of 5 to 25 wt.-%.

6. The composition according to claim 1, wherein the composition further comprises an organic solvent, preferably in an amount of 0.1 to 200 wt.-%, based on the dry weight of the at least one mineral material of step a), more preferably in an amount of 0.5 to 100 wt.-%, even more preferably in an amount of 0.75 to 50 wt.-% and most preferably in an amount of 1 to 25 wt.-% and/or preferably in an amount of 100 to 500 wt.-%, based on the dry weight of the at least one lignin of step b), more preferably in an amount of 150 to 450 wt.-% and most preferably in an amount of 200 to 300 wt.-%.

7. The composition according to claim 6, wherein the organic solvent is selected from the group consisting of hexane, toluene, methanol, ethanol, dioxane, acetone, dimethyl sulfoxide, dimethylformamide, ethylene glycol, ethylacetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol and mixtures thereof, more preferably is selected from the group consisting of ethylene glycol, ethylacetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol and mixtures thereof, and most preferably is γ-valerolactone.

8. The composition according to claim 1, wherein the composition further comprises at least one inorganic UV filter selected from the group consisting of titanium dioxide, zinc oxide, iron oxide, cerium oxide, calcium-doped cerium oxide, cerium phosphate, and mixtures thereof, preferably the least one inorganic UV filter is selected from the group consisting of titanium dioxide, zinc oxide, and mixtures thereof, more preferably the at least one inorganic UV filter is titanium dioxide and/or zinc oxide, and most preferably the at least one inorganic UV filter is titanium dioxide.

9. The composition of any one of the preceding claim 1, wherein the composition further comprises at least one organic UV filter, preferably the at least one organic UV filter is selected from the group consisting of derivatives of cinnamic acid and its salts, derivatives of salicylic acid and its salts, benzophenones, derivatives of aminobenzoic acid and its salts, dibenzoylmethanes, benzylidenecamphor derivatives, benzimidazole derivatives, diphenylacrylate derivatives, acrylamide derivatives, benzotriazole derivatives, triazine derivatives, benzalmalonate derivatives, aminobenzoate derivatives, octocrylene, and mixtures thereof, and more preferably the at least one organic UV filter is selected from the group consisting of derivatives of cinnamic acid and its salts, benzophenones, octocrylene, and mixtures thereof.

10. The composition according to claim 1, wherein the at least one lignin is present in the composition in the form of a mixture with or a coating on the at least one mineral material, and preferably is present as a coating on the at least one mineral material.

11. The composition according to claim 10, wherein the at least one lignin in the coating on the at least one mineral material is a water insoluble lignin, and preferably kraft lignin.

12. An emulsion for chemical and physical sun protection, the emulsion comprising a water in oil or oil in water mixture and 0.1 to 40 wt.-% of the dry composition according to claim 1, based on the weight of the water in oil or oil in water mixture.

13. A method of using the emulsion according to claim 12 for chemical and physical sun protection in a cosmetic formulation, said method comprising the step of introducing the emulsion into the cosmetic formulation, wherein the introducing step comprises mixing, dispersing and/or emulsifying said emulsion into the cosmetic formulation.

14. A method of using the emulsion according to claim 13, wherein the at least one lignin is present in the form of a coating on the at least one mineral material and/or wherein the at least one lignin is a water-insoluble lignin, preferably kraft lignin.

15. A method of using the emulsion according to claim 13, wherein the cosmetic formulation is a sunscreen product, facial makeup product, hair care product, hand care product, skin care product, body care product or mixtures thereof.

16. A method for preparing a dry composition for chemical and physical sun protection according to claim 1, the method comprising the steps of i) providing at least one organic solvent and/or at least one aqueous solution having a pH≥10, ii) providing at least one lignin, iii) providing at least one mineral material selected from the group consisting of surface reacted calcium carbonate and/or hydromagnesite, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and one or more H.sub.3O.sup.+ ion donors, wherein the carbon dioxide is formed in situ by the H.sub.3O.sup.+ ion donors treatment and/or is supplied from an external source, iv) mixing, in any order, the at least one organic solvent and/or at least one aqueous solution of step i) with the lignin of step ii), to obtain a lignin solution, v) mixing, in any order, the lignin solution obtained in step iv) with the at least one mineral material of step iii) in an amount such that the amount of dry lignin is 0.1 wt.-% to 100 wt.-%, based on the dry weight of the at least one mineral material and vi) drying the suspension obtained in step v) to obtain the dry composition according to claim 1.

17. The method according to claim 16, where in step i) an aqueous solution having a pH≥10 is provided, preferably between 10.5 and 13.5, even more preferably between 11.0 and 13.0 and most preferably between 11.5 and 12.5 and/or wherein the aqueous solution comprises caustic soda, ammonia solution, sodium hydroxide, potassium hydroxide, lye, sodium carbonate, calcium hydroxide, magnesium hydroxide and mixtures thereof and more preferably is ammonia solution.

18. The method according to claim 16, where the drying in step vi) is performed at temperatures above 75° C., preferably between 75 and 250° C., more preferably between 100 and 230° C., more preferably between 110 and 200° C. and most preferably between 120 and 180° C.

Description

FIGURES

[0311] FIG. 1 shows the Kubelka-Munk function evaluated at 300 nm wavelength as a function of the lignin content coated on or blended with the at least one mineral material.

[0312] FIG. 2 shows the Kubelka-Munk function evaluated at 300 nm wavelength as a function of the lignin amount of the obtained dry compositions comprising surface-reacted calcium carbonate or hydromagnesite.

EXPERIMENTS

[0313] Measurement Methods

[0314] In the following, measurement methods implemented in the examples are described.

[0315] Reflectance Measurements

[0316] Reflectance analysis was carried out with a double beam PerkinElmer Lambda 950 UV/Vis/NIR spectrophotometer equipped with a 150 mm integrating sphere with PMT and InGaAs detectors.

[0317] The prepared dry compositions were measured by reflectance spectroscopy as shown in FIG. 1. The analysis was performed with the dry composition loaded into a sealed aluminum cup for powder samples, which was placed flush with the reflectance port of the integrating sphere. The spectrophotometer was scanned in the range 280 nm-800 nm in steps of 2 nm. A Spectralon white standard was used as 100% baseline. To get a proxy for the absorption spectrum of the dry composition, the measured reflectance spectrum was converted using the Kubelka-Munk equation K−M=K/S=(1−R)2/2R, where R is the reflectance and K and S are the absorption and scattering coefficient, respectively.

Particle Size Distribution

[0318] The volume-based median particle size d50(vol) was measured by using a Malvern Mastersizer 2000 Laser Diffraction System (Malvern Instruments Plc., Great Britain). The raw data obtained by the measurement is analyzed using the Mie theory, with a particle refractive index of 1.57 and an absorption index of 0.005//using the Fraunhofer theory. The methods and instruments are known to the skilled person and are commonly used to determine particle size distributions.

BET Specific Surface Area (SSA) of Materials

[0319] The BET specific surface area was measured via the BET process according to ISO 9277:2010 using nitrogen, with the exception that prior to the measurement conditioning of the sample has been performed by heating the sample at 120° C. for a period of 60 minutes.

pH Measurement

[0320] The pH of the samples is measured by using a standard pH-meter at approximately 25° C.

Materials Used in the Examples and Sample Preparation

[0321] Mineral material: surface-reacted calcium carbonate having a volume median particle size d50 value of 5.5 μm and a specific surface area BET of 53 m.sup.2/g measured by the BET nitrogen method.

[0322] Hydromagnesite having a volume median particle size d50 value of 6 μm and a specific surface area BET of 45 m.sup.2/g measured by the BET nitrogen method

[0323] Lignin: alkali lignin (also known as kraft lignin), available from Sigma-Aldrich under the number 370959-100G

[0324] Organic solvent: gamma-valerolactone (GVL), available from Sigma-Aldrich under the number V403-100G.

[0325] Water: distilled water

[0326] Oil in water mixture: unguentum Alcoholum Lanae aquosum available from Caelo under the article number 3074, batch number 181705.

[0327] The following dry compositions were prepared, wherein the lignin is coated on the at least one mineral material:

[0328] detailed amounts are listed in Table 1

3 g of surface-reacted calcium carbonate or hydromagnesite were dried overnight at 100° C. Up to 2.4 g of at least one lignin were solubilized in 6 g of organic solvent. Both components were maintained under mixing, at ambient temperature, using a standard magnetic stirrer, till a full solubilisation of the alkali lignin. The so-prepared lignin solution was added dropwise to the surface-reacted calcium carbonate, while mixing the surface-reacted calcium carbonate manually for an homogeneous coating. The lignin-coated surface-reacted calcium carbonate was dried overnight at 100° C. If needed, the surface-reacted calcium carbonate was deagglomerated manually using a standard lab mortar.

[0329] The following dry compositions were prepared, wherein the lignin is mixed with the at least one mineral material:

detailed amounts are listed in Table 2
3 g of surface-reacted calcium carbonate or hydromagnesite were dried overnight at 100° C. Up to 2.4 g of at least one lignin were added to the surface reacted calcium carbonate or hydromagnesite. The so-prepared dry compositions were mixed manually.

TABLE-US-00001 TABLE 1 Lignin-coated dry compositions Amount of lignin Amount of based on dry Amount of mineral material Amount of mineral material organic solvent (g) lignin (g) (wt %) (g) 3.0 0 0 6.0 3.0 0.03 1 6.0 3.0 0.3 10 6.0 3.0 0.6 20 6.0 3.0 1.2 40 6.0 3.0 2.4 80 6.0

TABLE-US-00002 TABLE 2 Lignin-blended dry compositions Amount of lignin Amount of based on dry mineral material Amount of mineral material (g) lignin (g) (wt %) 3.0 0 0 3.0 0.03 1 3.0 0.6 20 3.0 2.4 80

[0330] Reflectance Test 01

[0331] The reflectance of the above prepared dry compositions was measured and converted to an absorption spectrum using the Kubelka-Munk function. FIG. 1 shows the Kubelka-Munk function evaluated at 300 nm wavelength as a function of the lignin amount for the lignin-coated dry compositions comprising surface-reacted calcium carbonate (empty-circles) or hydromagnesite (empty squares) and for the lignin-blended dry compositions comprising surface-reacted calcium carbonate (filled circles) or hydromagnesite (filled squares).

[0332] As can be seen from FIG. 1, for all dry compositions the UV absorption increases with increasing amount of lignin. Therefore, a dry composition comprising at least one mineral material selected from the group consisting of surface reacted calcium carbonate and/or hydromagnesite, and at least one lignin in the claimed range leads to an improved UV absorption.

[0333] Additionally, it can be concluded from FIG. 1 that a lignin coating applied on the at least one mineral material selected from the group consisting of surface reacted calcium carbonate and/or hydromagnesite leads to an improved UV absorption compared to a blend of lignin with the at least one mineral material selected from the group consisting of surface reacted calcium carbonate and/or hydromagnesite.

[0334] The following solubility tests were prepared, wherein the amount of solved alkali lignin is measured in each prepared solution:

[0335] detailed amounts are listed in Table 3

[0336] 10 ml of each solution were measured and the pH value of each of the solutions was measured. Alkali lignin was added in portions of 0.25 g until no dissolving could be detected by the human eye. The portion of 0.25 g has been dissolved in the solution when no residues could be detected by the human eye.

[0337] Lignin: alkali lignin (also known as kraft lignin), available from Sigma-Aldrich under the number 370959-100G

[0338] Solution: NaOH from Sigma Aldrich, CAS number: 228152-1 kg (≥97% ACS reagent), dissolved in water until the desired pH value [0339] Ammonium hydroxide solution, CAS number: 221228-1LA (ACS reagent 28-30%), dissolved in water until the desired pH value [0340] gamma-valerolactone (GVL), available from Sigma-Aldrich under the number V403-100G

TABLE-US-00003 TABLE 3 Amount of Volume alkali lignin Solution pH (mL) soluble (g) Distilled water 6.7 10 0 NaOH solution - pH 8 8.3 0 NaOH solution - pH 12 12.1 Low solubility (ca. 0.25) NaOH solution - pH 12.5 12.5 Low solubility (ca. 0.25) NaOH solution - pH 13 13.3 2.5-3 (Max) GVL 5.0 3 Ammonia Solution -pH 10 10.0   0.25 Ammonia Solution - pH 12 12.1 2-2.5 (Max) Commercial ammonia 12.5 2-2.5 (Max) solution (ca. 30 wt.-%)

[0341] From table 3 it can be seen that below pH 10 it is not possible to dissolve alkali lignin in an aqueous solution, whereas it can be dissolved in an organic solvent. Between pH 10 and 14, amounts between 0.25 and 3 g of alkali lignin can be dissolved in the 10 ml aqueous solutions.

[0342] The following dry compositions were prepared, by the inventive method:

[0343] detailed amounts are listed in Table 4 and Table 5

[0344] The at least one lignin is dissolved in 15 g of the at least one organic solvent and/or at least one aqueous solution having a pH≥10 and is added stepwise to 10 g of the at least one mineral material that has been dried at 125° C. for 8 h. The suspension is dried for 8 h at 125° C. and the obtained dry composition for chemical and physical sun protection is deagglomerated with a mortar. Afterwards the specific surface area (BET) is measured of the obtained dry composition.

[0345] Lignin: alkali lignin (also known as kraft lignin), available from UPM BioPiva under the number 395

[0346] Solution: Ammonium hydroxide solution, CAS number: 221228-1LA (30 wt.-%) from Sigma Aldrich, pH value 12.5

[0347] Mineral material: surface-reacted calcium carbonate having a volume median particle size d50 value of 5.5 μm and a specific surface area BET of 42.1 m.sup.2/g measured by the BET nitrogen method. [0348] Hydromagnesite having a volume median particle size d50 value of 6 μm and a specific surface area BET of 41.7 m.sup.2/g measured by the BET nitrogen method

TABLE-US-00004 TABLE 4 Surface-reacted calcium carbonate Amount of lignin Amount of based on dry mineral material Amount of mineral material BET Sample (g) Lignin (g) (wt.-%) (m.sup.2/g) 4.1 10.0 0.1 1 41.5 4.2 10.0 0.5 5 42.6 4.3 10.0 1.0 10 39.3 4.4 10.0 2.0 20 29.8 4.5 10.0 4.0 40 17.1

TABLE-US-00005 TABLE 5 Hydromagnesite Amount of lignin Amount of based on dry mineral material Amount of mineral material BET Sample (g) Lignin (g) (wt.-%) (m.sup.2/g) 5.1 10.0 0.1 1 45.8 5.2 10.0 0.5 5 49.0 5.3 10.0 1.0 10 47.0 5.4 10.0 2.0 20 41.0 5.5 10.0 4.0 40 32.7

[0349] 1 g of the obtained dry compositions has been added to 19 ml of distilled water and the pH values have been measured after 3 min, 30 min, 1 h and 2 h. The values are listed in the below table 6. In addition also the pH values of raw material are measured under the same conditions.

TABLE-US-00006 TABLE 6 pH values Sample 3 min 30 min 1 h 2 h 4.1 7.59 7.91 7.90 7.88 4.2 7.75 7.89 7.85 7.85 4.3 7.71 7.72 7.69 7.72 4.4 7.57 7.57 7.55 7.62 4.5 7.58 7.47 7.47 7.55 5.1 10.42 10.34 10.29 10.20 5.2 10.28 10.40 10.38 10.28 5.3 10.01 10.24 10.25 10.20 5.4 9.86 10.07 10.06 10.04 5.5 9.92 9.97 9.95 9.90 Surface-reacted 7.50 7.92 7.97 7.87 calcium carbonate Hydromagnesite 10.24 10.15 10.15 10.13

[0350] It can be seen that even if the dry compositions might comprise salts that might have been formed during the preparation in the at least one aqueous solution having a pH≥10, the pH after reintroducing it into water does not or only slightly vary from the raw mineral materials.

[0351] Reflectance Test 02

[0352] The reflectance of the above prepared dry compositions was measured and converted to an absorption spectrum using the Kubelka-Munk function. FIG. 2 shows the Kubelka-Munk function evaluated at 300 nm wavelength as a function of the lignin amount of the obtained dry compositions comprising surface-reacted calcium carbonate (black) or hydromagnesite (grey).

[0353] As can be seen from FIG. 2, for all dry compositions the UV absorption increases with increasing amount of lignin. Therefore, a dry composition comprising at least one mineral material selected from the group consisting of surface reacted calcium carbonate and/or hydromagnesite, and at least one lignin in the claimed range leads to an improved UV absorption.

[0354] Additionally, it can be concluded from FIG. 2 that a dry composition prepared by the inventive method has a good UV absorption even if it has been prepared in an aqueous solution.