阅读说明：本技术 表面组合物 (Surface composition ) 是由 克里斯蒂娜·门得洛克-埃丁格 亚历山大·斯考里福柯-波斯考克 于 2019-03-19 设计创作，主要内容包括：本发明涉及表面组合物,所述表面组合物包含至少一种极性油和平均粒径为至多300nm的微粉化1,4-二(苯并噁唑-2’-基)苯,以及涉及此类微粉化1,4-二(苯并噁唑-2’-基)苯用于减少此类油至表面的转移的用途。(The present invention relates to a surface composition comprising at least one polar oil and micronized 1, 4-bis (benzoxazol-2 '-yl) benzene having an average particle size of at most 300nm, and to the use of such micronized 1, 4-bis (benzoxazol-2' -yl) benzene for reducing the transfer of such oil to a surface.)

1. A surface composition comprising at least one polar oil having a polarity index of less than 55mN/m, wherein the composition further comprises an average particle size D as determined by laser diffraction_n50 is up to 300nm of micronized 1, 4-bis (benzoxazol-2' -yl) benzene.

2. The surface composition according to claim 1, wherein the polarity index of the at least one polar oil is selected from the range of 1mN/m to 40 mN/m.

3. The surface composition according to claim 2, wherein the polarity index of the at least one polar oil is selected from the range of 1mN/m to 10mN/m and/or the range of 25mN/m to 40 mN/m.

4. The surface composition of claim 3, wherein the polar oil is selected from the group consisting of: isocetyl stearate, dioctyl carbonate, cetearyl isononanoate, C12-13 alkyl tartrate, and coco glyceride and mixtures thereof.

5. The surface composition according to any of the preceding claims, wherein the amount of each polar oil is selected in the range of 1 to 30 wt. -%, more preferably in the range of 2 to 25 wt. -%, most preferably in the range of 3 to 20 wt. -%, based on the total weight of the surface composition.

6. The surface composition according to any of the preceding claims, wherein the amount of the micronized 1, 4-bis (benzoxazol-2' -yl) benzene is selected from the range of 0.1 to 20 wt. -%, preferably from the range of 0.2 to 15 wt. -%, most preferably from the range of 0.3 to 10 wt. -%, based on the total weight of the surface composition.

7. The surface composition according to any of the preceding claims, wherein the micronized 1, 4-bis (benzoxazol-2' -yl) benzene has an average particle size D _n50 is selected from the range of 50nm to 300nm, more preferably 120nm to 280nm, most preferably 150nm to 220 nm.

8. The surface composition according to any of the preceding claims wherein the micronized 1, 4-bis (benzoxazol-2 '-yl) benzene is a solid amorphous micronized 1, 4-bis (benzoxazol-2' -yl) benzene.

9. The surface composition of claim 8 wherein the solid amorphous 1, 4-bis (benzoxazol-2' -yl) benzene is characterized by a specific absorbance E1/1 ≥ 780 at 320 nm.

10. The surface composition according to any of the preceding claims, wherein micronized 1, 4-bis (benzoxazol-2' -yl) benzene is incorporated into the surface composition in the form of an aqueous dispersion thereof.

11. The surface composition according to any preceding claims, wherein the surface composition is an emulsion comprising an oil phase and an aqueous phase.

12. The surface composition according to claim 11 or 12, wherein the amount of the oil phase is selected in the range of 10 to 60 wt. -%, preferably in the range of 15 to 50 wt. -%, most preferably in the range of 15 to 40 wt. -%, based on the total weight of the surface composition.

13. The surface composition according to any of the preceding claims, wherein the surface composition is in the form of an oil-in-water (O/W) emulsion comprising an oil phase dispersed in an aqueous phase in the presence of an O/W emulsifier, preferably in the presence of a phosphate ester emulsifier, most preferably in the presence of cetyl phosphate ester.

14. Use of micronized 1, 4-bis (benzoxazol-2' -yl) benzene having an average particle size of up to 300nm as determined by laser diffraction to reduce transfer of polar oils contained in a surface composition to a surface.

15. A method of reducing transfer of a polar oil to a surface, such as in particular to a glass or plastic surface, the method comprising adding micronized 1, 4-bis (benzoxazol-2' -yl) benzene having an average particle size of up to 300nm as determined by laser diffraction to a surface composition comprising the polar oil.

Examples

1.Preparation of micronized 1, 4-bis (benzoxazol-2' -yl) benzene

1.1. General procedure

All particle sizes were determined by laser diffraction using a Malvern Mastersizer2000, and/or by Coulter Delsa Nano S (dynamic laser light scattering) according to the method as outlined in ISO 13320: 2009.

Differential Scanning Calorimetry (DSC) was performed using a Mettler Toledo DSC1 (temperature range from 25 ℃ to 400 ℃; heating rate: 4 ℃/min; air atmosphere, 2-3mg sample, average from 2 measurements).

X-ray diffraction patterns were recorded in reflectance (Bragg-Brentano) geometry using a Bruker D8 Advance powder X-ray diffractometer. The PXRD diffractometer was equipped with a LynxEye detector. The samples were generally prepared without any special treatment other than applying a slight pressure to obtain a flat surface. A single crystal silicon sample holder with a depth of 1.0mm was used for polymorph screening. The samples were measured uncovered. The tube voltage was 40kV and the current was 40 mA. A slight variable divergence (variable divergence slope) was used in a 3 ° window. The step size was 0.02 ° 2 θ and the step time was 37 seconds. The sample was rotated at 0.5rps during the measurement.

The E1/1 values were determined using a UV/(visible) spectrometer (Perkin Elmer Lambda 650S) at 320nm and corrected for baseline according to the following formula: e1/1 ═ (E1/1 at 320 nm) - (E1/1 at 650 nm).

The UVB: UVA ratio is determined by: the uv spectrum of the respective micronized uv filter dispersed in water at a concentration of 0.001% (w/v) active substance is measured and the ratio is calculated by dividing the area% of 290nm to 319nm (uvb) by the area% of 320nm to 400nm (uva).

1.2 preparation of solid amorphous 1, 4-bis (benzoxazol-2' -yl) benzene coarse particles (DBO-400(A))

A mixture of 702g of polyphosphoric acid and 4.28ml of methanesulfonic acid was heated to 90 ℃. 65g of terephthalic acid and 107g of 2-aminophenol were added. The mixture was stirred at 180 ℃ for 8 hours under an inert atmosphere and then transferred to ice water. The precipitated product was filtered off and washed with water and acetic acid. The precipitate was dispersed in water and the pH was adjusted to 8.0 with sodium hydroxide, filtered and washed with water. The crude product was suspended in a 3.3:1 mixture of toluene and 1-butanol, stirred at 85 ℃ for one hour, filtered, washed with diethyl ether and dried. The resulting crude solid amorphous 1, 4-bis (benzoxazol-2' -yl) benzene particles had a particle size Dn50 of 380nm (Malvern).

1.3 preparation of an aqueous Dispersion of solid amorphous 1, 4-bis (benzoxazol-2' -yl) benzene (DBO-200 Dispersion (A))

A suspension of 175g of DBO-400, 324g of water and 65g of Green APG 0810, obtained as described in (1.2), was prepared. The suspension was then milled with a LabStar laboratory mill using yttrium stabilized zirconia milling beads (0.3mm, available from Tosoh Ceramic, Japan) for 2 hours and the milling chamber was cooled (-12 ℃ saline). After removal of the milling beads, a 30% aqueous dispersion of micronized 1, 4-bis (benzoxazol-2' -yl) benzene was obtained.

Particle size:

1.4 preparation of an aqueous Dispersion of crystalline 1, 4-bis (benzoxazol-2' -yl) benzene (DBO-200 Dispersion (C))

After recrystallization from o-dichlorobenzene and drying of the crude particles obtained as in (1.2), 73.0% crystalline 1, 4-bis (benzoxazol-2' -yl) benzene was obtained, which was subsequently milled in a similar manner to that described in (1.3). After removal of the milling beads, a 30% aqueous dispersion of crystalline 1, 4-bis (benzoxazol-2' -yl) benzene was obtained.

Particle size:

1.5 preparation of an aqueous Dispersion of crude solid amorphous 1, 4-bis (benzoxazol-2' -yl) benzene (DBO-400 Dispersion (A))

A suspension of 1.8g of DBO-400, 3.51g of water and 0.69g of Green APG 0810 obtained as described in (1) was prepared. After this, the suspension was mixed with the magnetic mixture at ambient temperature (22 ℃) until a homogeneous dispersion was obtained. After removal of the magnetic stir bar, a 30% aqueous dispersion of micronized 1, 4-bis (benzoxazol-2' -yl) benzene having an average particle size Dn50 of 380nm (malvern) was obtained.

2.Material transfer

Material transfer was determined by the sponge test as shown below:

sponge cloth (Weitawip Claire from Weita AG: cellulose/cotton fibre mixture, 200g/m²Thickness 5mm) into chips of 76mm by 26mm

Tare sponge sample

400mg of the corresponding sample (═ cosmetic composition) were applied and distributed uniformly over the entire sponge surface of 76mm × 26mm

Weighing the sponge with the applied sample

Tare microscope slides (glass plate 76 mm. times.26 mm. times.1 mm)

Placing a microscope slide (glass plate) on top of the sponge, placing 500g of a counterweight (height: 6.3cm, diameter of the contact area: 3.7cm) on it for 10 seconds to exert a specific pressure on the sample

Carefully take the microscope slide vertically

Weighing the removed microscope slide and determining the amount of sample transferred onto the glass plate accordingly

Repeat the test 10 times for each composition to obtain the mean value (mean) of each sample.

2.1Material transfer according to particle size and formulation type

The formulations summarized in table 1 have been prepared according to standard methods in the art. After this, the material transfer was assessed as described above.

Table 1: transfer resistance (I)

Based on active substances

^#(transfer DBO-400 dispersion-transfer DBO-200 dispersion)/transfer DBO-400 dispersion 100%)

As can be seen from the table, the addition of micronized 1, 4-bis (benzoxazol-2' -yl) benzene according to the present invention significantly reduces the amount of frost transferred to the glass surface compared to the reference, thereby making the glass surface less stained compared to the reference. It is even more advantageous to use more polar oil. Furthermore, the transfer in the O/W formulation is significantly lower than in the W/O formulation.

2.2 transfer of Material according to the polarity index of the oil

Additional O/W emulsions with other polar oils were prepared using DBO-200(A) dispersions similar to the O/W formulations listed in Table 1. Table 2 summarizes the results of the material transfer assessment.

Table 2: transfer resistance (II)

As can be derived from table 2, the best results, i.e. the least material transfer, were obtained for polar oils with a polarity index selected from the range of 1 to 10mN/m and the range of 25 to 40 mN/m.

2.3 Material transfer according to formulation type

Similar to the O/W or W/O formulations listed in Table 1, other O/W or W/O emulsions were prepared using the DBO-200(A) dispersions and polar oils as outlined in Table 3. After this, the material transfer was assessed as described above. The results are summarized in table 3.

Table 3: transfer resistance (III)

As can be seen from table 3, also at the same oil content, the W/O emulsions generally show a significantly higher material transfer compared to the corresponding O/W emulsions.

3.Ultraviolet protection

The formulations summarized in table 4 have been prepared according to standard methods in the art. After this, the in vitro SPF was assessed directly after manufacture (t0) and after 1 month storage at room temperature (t 1). On PMMA plates (fromWW5, 5cm × 5cm, roughness 5 μm) was performed: 32.5mg of the corresponding preparation (i.e. 1.3 mg/cm) ²) Applied uniformly to a PMMA plate and dried for 15 minutes.

In vitro SPF was determined using a Labsphere 2000 uv transmittance analyzer: each PMMA plate was measured 9 times at different points on the plate, resulting in 27 data points. The results were calculated as the average of these 27 data points.

Table 4: in vitro SPF

Based on active substance (i.e. 10% by weight of the corresponding dispersion)

As can be seen from table 4, the use of solid amorphous DBO results in a significantly higher SPF compared to the corresponding crystalline form. Furthermore, such formulations are rendered more storage stable by the in vitro SPF remaining unchanged after 1 month storage at room temperature in the solid amorphous form compared to the SPF significantly reduced after 1 month storage at room temperature for the corresponding crystalline form.