阅读说明：本技术 用于改进皮肤的生物力学特性的经表面反应的碳酸钙 (Surface-reacted calcium carbonate for improving the biomechanical properties of the skin ) 是由 塔尼娅·布德 阿奈·埃克 于 2019-01-23 设计创作，主要内容包括：本发明涉及经表面反应的碳酸钙在化妆品和/或皮肤护理组合物中作为用于改进皮肤的生物力学特性的试剂的用途。(The present invention relates to the use of surface-reacted calcium carbonate in cosmetic and/or skin care compositions as an agent for improving the biomechanical properties of the skin.)

1. Use of surface-reacted calcium carbonate as an agent for improving the biomechanical properties of the skin in cosmetic and/or skin care compositions,

wherein the surface-reacted calcium carbonate has a volume median particle size d₅₀Is 0.1 μm to 90 μm, and

wherein the surface-reacted calcium carbonate is natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and one or more H₃O⁺Reaction products of ion donors wherein said carbon dioxide is passed through said H₃O⁺The ion donor is processed to form in situ and/or supplied from an external source.

2. The use according to claim 1, wherein the surface-reacted calcium carbonate has a volume median particle size d₅₀Is 0.5 μm to 50 μm, preferably 1 μm to 40 μm, more preferably 1.2 μm to 30 μm, and most preferably 1.5 μm to 15 μm.

3. Use according to claim 1 or 2, wherein the surface-reacted calcium carbonate has a specific surface area measured using the nitrogen and BET method of 15m²G to 200m²A/g, preferably of 20m²G to 180m²A/g, and more preferably 25m²G to 160m²/g。

4. Use according to any one of claims 1 to 3, wherein

The natural ground calcium carbonate is selected from marble, chalk, limestone and mixtures thereof, or

The precipitated calcium carbonate is selected from the group consisting of precipitated calcium carbonate having an aragonite, vaterite or calcite crystalline form, and mixtures thereof.

5.The use according to any one of claims 1 to 4, wherein at least one H₃O⁺The ion donor is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, citric acid, oxalic acid, acid salts, acetic acid, formic acid, and mixtures thereof; preferably, at least one H₃O⁺The ion donor is selected from hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid, at least part of which is selected from Li⁺、Na⁺And/or K + cation-neutralized H₂PO₄ ^-At least partially selected from Li⁺、Na⁺、K⁺、Mg²⁺And/or Ca²⁺Is a cation-neutralized HPO₄ ^2-And mixtures thereof; more preferably, at least one H₃O⁺The ion donor is selected from hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid, or a mixture thereof; and most preferably, at least one H₃O⁺The ion donor is phosphoric acid.

6. Use according to any one of claims 1 to 5, wherein said improvement of the biomechanical properties of the skin is skin firmness, preferably an increase in skin firmness.

7. Use according to any one of claims 1 to 6, wherein the skin is the skin of an arm, in particular a hand, a leg, in particular a foot, the neck, the chest, and/or the face, preferably the face.

8. Use according to any one of claims 1 to 7, wherein the cosmetic and/or dermatological composition has a pH value of 8.5 or less, preferably 8.0 or less, more preferably 7.5 or less, even more preferably 7.0 or less, and most preferably from 4.0 to 7.0.

9. Use according to any one of claims 1 to 8, wherein the surface-reacted calcium carbonate is present in the cosmetic and/or skin care composition in an amount of from 0.1 to 50 wt. -%, preferably from 0.5 to 20 wt. -%, more preferably from 1 to 10 wt. -%, and most preferably from 3 to 10 wt. -%, based on the total weight of the composition.

10. Use according to any one of claims 1 to 9, wherein the cosmetic and/or dermatological composition further comprises water and/or at least one oil, preferably selected from vegetable oils and esters thereof, alkane coconut esters, plant extracts, animal fats, silicones, fatty acids and esters thereof, mineral esters, glycerides and pegylated derivatives thereof, and mixtures thereof.

11. Use according to any one of claims 1 to 10, wherein the cosmetic and/or dermatological composition comprises at least one active agent adsorbed onto and/or absorbed into the surface of the surface-reacted calcium carbonate.

12. The use of claim 11, wherein the at least one active agent is selected from the group consisting of pharmaceutically active agents, biologically active agents, vitamins, disinfectants, preservatives, flavoring agents, surfactants, oils, fragrances, essential oils, and mixtures thereof.

13. Use according to any one of claims 1 to 12, wherein the composition further comprises at least one additive selected from: bleaches, thickeners, stabilizers, chelating agents, preservatives, humectants, emulsifiers, emollients, fragrances, colorants, skin tanning compounds, antioxidants, minerals, pigments, UV-A and/or UV-B filters, and mixtures thereof.

14. Use according to any one of claims 1 to 13, wherein the cosmetic and/or skin care composition is selected from an eye make-up product, a face make-up product, a lip care product, a hand care product, a skin care product, or a combination thereof.

15. The use according to any one of claims 1 to 14, wherein the surface-reacted calcium carbonate does not cause negative side effects, and preferably does not cause skin irritation, after application on the skin.

Examples

1. Measuring method

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

Particle size distribution

The volume-determined median particle size d was evaluated using a Malverm Mastersizer 2000 laser diffraction system (Malvern Instruments Plc., UK)₅₀(volume) and volume-determined top-cut particle size d₉₈(volume). d₅₀(volume) or d₉₈The (volume) values represent diameter values: which is such that 50% or 98% by volume, respectively, of the particles have a diameter smaller than this value. The raw data obtained by this measurement were analyzed using the mie theory, in which the refractive index of the particles was 1.57 and the absorption index was 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.

Median particle size d determined by gravimetric determination by sedimentation₅₀(weight), the sedimentation method is an analysis of sedimentation behavior in a gravity field. By using Sedigraph from Micromeritics Instrument Corporation, USA^TM5120 the measurement is carried out. The methods and apparatus are known to the skilled person and are generally used to determine the particle size distribution of fillers and pigments. The measurement was at 0.1 wt.% Na₄P₂O₇In aqueous solution. The samples were dispersed and sonicated using a high speed stirrer.

Specific Surface Area (SSA)

After conditioning the sample by heating at 250 ℃ for a period of 30 minutes, the specific surface area was measured via the BET method using nitrogen according to ISO 9277. Prior to such measurements, the samples were filtered in a buchner funnel, rinsed with deionized water and dried in an oven at 90 to 100 ℃ overnight. Subsequently, the dry cake was ground thoroughly in a mortar and the resulting powder was placed in a moisture balance at 130 ℃ until a constant weight was reached.

³Specific pore volume of intragranular invasion (in cm/g)

Specific pore volume using a maximum applied mercury pressure of 414MPa (60000psi) (corresponding to a Laplace throat diameter of 0.004 μm (nm))Micromeritics Autopore V9620 mercury porosimeter was measured using mercury intrusion measurements. The equilibration time used for each pressure step was 20 seconds. Sealing the sample material at 5cm³The chamber was used for analysis in a powder penetrometer. Data were corrected for mercury compression, penetrometer expansion and sample material compression using the software Pore-Comp (gas, p.a.c., key, j.p., Matthews, g.p. and Ridgway, c.j., "volume Space Structure of compatible polymers and compatible Calcium 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 indicating that coarse sample packing between any agglomerate structures plays an important role. Less than these diameters is the fine interparticle packing of the particles themselves. If they also have intraparticle pores, the region exhibits a double peak 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 double peak inflection point). The sum of these three regions gives the total pore volume of the powder, but strongly depends on the original sample compaction/settling of the powder at the coarse pore end of the distribution.

By taking the first derivative of the cumulative invasion curve, the pore size distribution (inevitably including pore shielding) based on the equivalent laplace diameter is revealed. The differential curves clearly show the coarse aggregate pore structure region, the interparticle pore region, and the intraparticle pore region, if present. 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 provide the desired pore volume of the inner pores alone, expressed as 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.

2. Pigment material

GCC1

GCC 1 is a high purity natural calcium carbonate obtained from limestone sold by Omya and exhibits the characteristics listed in table 1 below.

SRCC 1

D of SRCC1₅₀＝1.6μm，d₉₈＝10.0μm，SSA＝31.4m²(ii)/g, and an intraparticle intrusion specific pore volume of 0.837cm³(for pore size ranges of 0.004 μm to 0.59 μm).

SRCC1 is obtained as follows: an aqueous suspension of 7 litres of ground calcium carbonate was prepared in a mixing vessel by adjusting the solids content of the ground marble calcium carbonate from Omya Madencilik a.s., Turkey having a mass-based median particle size of 0.4 μm as determined by sedimentation so that a solids content of 15 wt% based on the total weight of the aqueous suspension was obtained.

While mixing the slurry, 290g of phosphoric acid was added to the suspension in the form of an aqueous solution comprising 10 wt% phosphoric acid at a temperature of 70 ℃ over a period of 100 minutes. After the acid was added, the slurry was stirred for an additional 5 minutes before it was removed from the vessel, and the product was filtered to remove excess water and then further dried in an oven.

Table 1: characteristics of the pigment materials used

3. Trade name/supplier/INCI name of other Material-Components

Table 2: ingredients for cosmetic and/or skin care compositions

1 Sasol GmbH, 2 KCC Silicone Corporation, Germany, Korea

3AG, Switzerland 4 Sigma Aldrich, Switzerland

5 Omya Hamburg GmbH, 6 SLI Chemicals GmbH, Germany

7 Georges Walther AG, Switzerland 8 Cognis GmbH, Germany

4. Biomechanical Properties-test results

Table 3: skin care and/or cosmetic composition

The cosmetic composition was prepared as follows:

heating phase A and phase B separately at 80 ℃

Addition of phase B to phase A while stirring (Heidolph, Faust, 300rpm)

Cooling at room temperature

Addition of fractions C and D and homogenization (Ultra Turrax T25-D, IKA, 24000rpm)

Adjusting the pH to 6.0 using lactic acid (10% solution)

4.1 measurement of biomechanical properties of the skin

MPA580 for compactness measurement

(Courage&Khazaka). This measurement is based on an in vivo non-invasive method (in vivo non-invasive method) to assess skin rheological properties: biological extension and elastic changes were measured. This technique involves drawing skin into the bore of a probe by a constant vacuum pressure and for a constant time. The penetration depth of the skin into the probe is measured without friction and mechanical influence by using two optical prisms located at the opening of the probe. The skin elasticity of the skin was performed with a 2mm probe at a constant pressure of 450 mbar and one measurement cycle was performed. The suction time and relaxation time were each 3 seconds. Each measurement is the average of two acquisitions. The skin firmness parameter Uf was studied. FIG. 1 shows aThe obtained skin deformation curve and the measured parameters.

Table 4 shows the test results for comparative skin care and/or cosmetic compositions comprising GCC 1.

Table 4: comparative skin care and/or cosmetic composition comprising GCC 1

As can be derived from the data shown in table 4, the compositions comprising GCC 1, after once daily use for 28 days, cause a certain improvement of the biomechanical properties of the skin, characterized in that: the compactness parameter (R0(Uf)) decreased by an average of 22%.

Table 5: skin care and/or cosmetic compositions of the invention comprising SRCC1

As can be derived from the data shown in table 5, the composition comprising SRCC1 resulted in an improvement of the biomechanical properties of the skin after once daily use for 28 days. The improvement is characterized by a significant reduction in the firmness parameter (R0(Uf)) of 27% on average, and thus an increase in skin firmness. Furthermore, tight skin was observed in 90% of the subjects.

By comparing the data shown in table 4 and table 5, it can be seen that the composition of the present invention comprising surface-reacted calcium carbonate provides better results for the improvement of skin firmness when compared to the composition comprising ground calcium carbonate.

4.2 sensory evaluation of skin Care and/or cosmetic compositions

Compositions 1 comprising GCC 1 and 2 comprising SRCC1, which are related to unpleasant skin sensations such as skin irritation, were tested by the subjects. After a 28 day period, the results of the study were evaluated.

During the test study with composition 1 comprising GCC 1, 5% of the subjects reported a skin/eye irritation sensation.

During the test study, none of the subjects complained of a sensation of irritation after or during administration of composition 2 comprising SRCC 1.

Thus, cosmetic and/or skin care compositions comprising SRCC1 are not irritating and therefore in any case less irritating to the skin than cosmetic and/or skin care compositions comprising GCC 1.